JP2003191266A - Resin composition and sheet / film using the resin composition - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To maintain good transparency of a non-crystalline polyester resin, to have good peeling from a metal roll, and to hardly generate plate-out to the metal roll, and An object of the present invention is to provide a calender-forming polyester-based resin composition that does not cause vertical streaks due to air entrainment in a sheet or film obtained by calendering. SOLUTION: To 100 parts by weight of a polyester resin comprising a repeating unit of a dicarboxylic acid component and a glycol component, 0.2 to 3.0 parts by weight of a fatty acid having 20 or more carbon atoms and 0.01 to 3.0 parts of a fatty acid metal salt. It is compounded by weight.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin composition for calender molding, and a sheet and a film obtained by calender molding the resin composition.

[0002]

2. Description of the Related Art A polyester resin composition, particularly a crystalline polyethylene terephthalate resin (hereinafter referred to as PE) composed of repeating units of terephthalic acid and ethylene glycol.
It is referred to as T resin. ) Has been developed as a molding material for various purposes, and the ones molded into sheets and films are used for food and pharmaceutical packaging materials, container lid materials, and blister packaging containers. Materials and construction,
Widely used as a laminated sheet for home appliances and automobiles.

When a sheet is molded using PET resin, it is generally manufactured by an extrusion molding method.
The extrusion molding method is a molding processing method in which a die is adjusted so that a sheet has a specific thickness, the molten resin is discharged, and the molten resin is rapidly cooled to a temperature lower than its softening temperature and taken out. Therefore, peeling from the take-up roll is easy, but even if the die is adjusted, a part with a different thickness is likely to occur and the thickness accuracy as a sheet is poor, so after printing, laminating, coating, etc. There was a possibility that the sheet would be hampered in processing, and that there would be holes in the sheet during secondary molding such as vacuum / pressure molding. in addition,
Molding of a sheet by an extrusion molding method has a low molding speed, and it is difficult to say that productivity is good.

For these reasons, the calendar molding method is often applied to the production of the sheet or film instead of the extrusion molding method. Calender molding method is a molding processing method of producing a sheet or film having a desired thickness by rolling a molten resin with a heated metal roll (calender roll), and there is no trouble occurring near the die in extrusion molding, It is suitable for producing a large amount of products of the same standard because it is possible to produce a molded sheet / film having good thickness accuracy and excellent quality, and a high molding speed and excellent productivity.

However, the crystalline PE is not
It was almost impossible to produce a sheet or film by applying T resin. This is partly because the melting point of the crystalline PET resin is high and the temperature setting limit in the calender molding machine is limited. However, in the crystalline PET resin, the melt tension becomes extremely small when it becomes a melt at a temperature equal to or higher than the melting point. In addition, it could not be applied to calender molding that requires a large melt tension.

[0006] Therefore, with respect to the PET resin, research and development have been conducted to change the chemical structure to change the processability and the physical properties. Specifically, the crystallinity is controlled by replacing a part of terephthalic acid or ethylene glycol, which is a monomer component of PET resin, with another component to control the crystallinity, and a part thereof is completely amorphous. It is also done. By controlling the crystallinity as described above, it becomes possible to improve the physical properties such as high transparency, and it is possible to obtain the possibility of being applicable to calender molding.

However, with a resin having a large polarity such as PET resin, adhesion to a heated metal roll (calender roll) is remarkable, and calender molding cannot be performed with the resin alone. It has been proposed to incorporate various additives for ease of use. For example, JP-A-11-343353 and JP-A-2000.
-186191, JP 2000-302951, JP 2000-327891, JP 200
See Japanese Patent Publication No. 1-64496. As the additive for achieving the easy peeling property from the metal roll, those having a low affinity with the resin are generally considered to be effective.
However, when such an additive is added, the transparency of the formed sheet / film may be reduced or it may lead to plate-out on the metal roll.Therefore, control the crystallinity of the resin and apply it to calender molding. Even if it is modified so that it can be modified, in the PET-based polyester resin,
It was extremely difficult to facilitate peeling from the metal roll while not impairing transparency and at the same time preventing plate-out to the metal roll.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation as described above, and a PET-based polyester resin, in particular, a polyester-based resin (non-crystalline polyester-based resin) whose crystallinity is controlled While maintaining the characteristic transparency, peeling from the metal roll (calendar roll) is good, there is almost no plate out on the metal roll, and the sheet or film obtained by calender molding has air. It is an object of the present invention to provide a polyester resin composition for calendar molding in which no vertical streak is generated due to the inclusion of the above, and sheets and films obtained by calender molding the polyester resin composition.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention calendered a resin composition obtained by mixing a specific amount of a specific additive with a specific polyester resin. It has been found that the above-mentioned problems can be solved by using a molding polyester resin composition, and the present invention has been completed.

That is, the polyester resin composition according to the present invention comprises terephthalic acid, naphthalene dicarboxylic acid,
At least 8 kinds of one or a mixture of two or more kinds selected from 1,4-cyclohexanedicarboxylic acid and isophthalic acid.
Repetition of 0 mol% or more of dicarboxylic acid component and glycol component in which at least 80 mol% or more of one or a mixture of two or more selected from ethylene glycol, neopentyl glycol, diethylene glycol and 1,4-cyclohexanedimethanol is used. 0.2 to 3.0 parts by weight of a fatty acid having 20 or more carbon atoms and 0.01 to 100 parts by weight of a fatty acid metal salt per 100 parts by weight of a polyester resin composed of units
It is characterized by being mixed with 3.0 parts by weight. At this time, the blending amount of the fatty acid metal salt is more preferably equal to or less than the blending amount of the fatty acid. Also,
The sheet / film according to the present invention is formed by the calender molding method using the above polyester resin composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. The polyester resin used in the present invention is terephthalic acid, naphthalene dicarboxylic acid,
At least 8 kinds of one or a mixture of two or more kinds selected from 1,4-cyclohexanedicarboxylic acid and isophthalic acid.
1 selected from ethylene glycol, neopentyl glycol, diethylene glycol, and 1,4-cyclohexanedimethanoe with a dicarboxylic acid component of 0 mol% or more.
One kind or a mixture of two or more kinds is composed of a repeating unit of a glycol component which is at least 80 mol% or more.

Among these, including easy availability as a material, a dicarboxylic acid component containing at least 90 mol% of terephthalic acid, 10-95 mol% of 1,4-cyclohexanedimethanol and 9 mol of ethylene glycol.
It is preferable to use a polyester resin having a repeating unit of a glycol component of 0 to 5 mol%, and among them, an amorphous polyester resin is preferably used. The reason for this is that non-crystalline polyester resin is advantageous for calender molding that requires large melt tension because it can be melted at low temperature, and at the same time the surface smoothness of the sheet or film obtained by calender molding. And the transparency is good. Although the non-crystallinity of the polyester resin varies depending on the composition ratio of the monomer components, terephthalic acid is 100 mol% and ethylene glycol is 30 mol% in order to achieve non-crystallinity and at the same time improve the moldability by calender molding. ~ 90 mol%, 10-70 1,4-cyclohexanedimethanol
Mol% is preferable, and terephthalic acid is 1
00 mol%, ethylene glycol 65-80 mol%, 1,4-cyclohexanedimethanol 2
It is preferably 0 to 35 mol%.

The polyester resin preferably used in the present invention comprises a dicarboxylic acid component containing terephthalic acid,
It is obtained by reacting 1,4-cyclohexanedimethanol and a glycol component containing ethylene glycol, and then polycondensing in the presence of a specific catalyst. That is, a dicarboxylic acid component containing at least 90 mol% terephthalic acid and a glycol component containing 10 to 95 mol% 1,4-cyclohexanedimethanol and 90 to 5 mol% ethylene glycol component are esterified or transesterified. At a temperature sufficient to cause the reaction to take place, and the resulting reaction product is then subjected to an absolute pressure of less than 1.333 KPa for less than 2 hours for a period of less than 2 hours and a Mn of 0-75 ppm Mn, based on the weight of the copolyester. 50-1
50 ppm Zn, 5-20 ppm Ti, 5-200
Polycondensation in the presence of a catalyst and inhibitor system consisting of ppm Ge and 10-80 ppm P results in a colorless transparent copolyester.

The dicarboxylic acid component of the polyester resin used in the present invention includes terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
One or a mixture of two or more selected from isophthalic acid accounts for at least 80 mol% or more. Regarding the remaining dicarboxylic acid component of less than 20 mol%, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, azelaic acid, dodecanedioic acid, fumaric acid, maleic acid, itaconic acid, orthophthalic acid, 2,6- Examples thereof include naphthalenedicarboxylic acid, 2,6-naphthalenedidimethylenecarboxylic acid, and paraphenylenedicarboxylic acid. Furthermore, in the dicarboxylic acid component of less than 20 mol%,
A small amount of trivalent or tetravalent carboxylic acid may be blended to introduce long chain branching into the molecular structure of the polyester resin. The melt tension can be increased by introducing a long chain branch into the molecular structure of the polyester resin, which is convenient for calendar molding. The trivalent carboxylic acid may be trimellitic acid, and the tetravalent carboxylic acid may be pyromellitic acid.

On the other hand, as the glycol component of the polyester resin used in the present invention, ethylene glycol,
Neopentyl glycol, diethylene glycol, 1,
One or a mixture of two or more selected from 4-cyclohexanedimethanol accounts for at least 80 mol% or more. Regarding the remaining glycol component of less than 20 mol%, for example, propylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3- Propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3
-Propanediol, 1,3-butanediol, 1,4
-Butanediol, neopentyl glycol, 1,5-
Pentadiol, 1,6-hexanediol, 1,8-
Octanediol, 2,2,4-trimethyl-1,6-
Hexanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the like can be mentioned. In the case of the glycol component contained in the polyester resin, 20
You may make it introduce | transduce a long-chain branch into the molecular structure of polyester resin by mix | blending a small amount of trivalent or tetravalent alcohol in less than mol% of glycol components. here,
Examples of trivalent alcohols include trimethylolpropane, and examples of tetravalent alcohols include pentaerythritol.

Further, the molecular weight of the polyester resin preferably used in the present invention is not particularly limited, but if the number average molecular weight is less than 10,000, the melt tension of the molten resin is small, and the molding process in calendar molding is performed. The possible temperature range is narrowed and the number average molecular weight is 2
If it exceeds 00000, the viscosity of the molten resin becomes large and the load on the calender molding equipment becomes large, or the surface smoothness of the obtained sheet or film becomes poor. Therefore, considering that the surface smoothness of the obtained sheet or film is good while maintaining the load on the calender molding equipment and a wide range of molding processing conditions, the number average molecular weight is in the range of 10,000 to 200,000. preferable.

The molecular weight distribution of the polyester resin used in the present invention is not particularly limited. However, in order to achieve both a large melt tension required for calender molding and a low viscosity for the purpose of reducing the load on calender molding equipment, the molecular weight distribution is generally over the entire molecular weight distribution, as is generally done. Widen
It is effective to add a small amount of ultra high molecular weight resin. In some cases, these can be dealt with by polymerization, but they can also be dealt with by a method of mixing polyester resins of the same kind having different molecular weights.

Some polyester resins usable in the present invention are already on the market. For example, an amorphous polyester resin composed of 100 mol% of terephthalic acid, 60 to 75 mol% of ethylene glycol, and 40 to 25% of 1,4-cyclohexanedimethanol is an Eastman Chemical
l Products, Inc. From Kodar PE
TG Copolyester Grade Easta
r PETG 6763 and TsunamiCopol
yester grade GS1, GS2, GS3, GS
4, etc., and these products are preferably used for the present invention.

On the other hand, in the present invention, the fatty acid blended in the polyester resin is limited to fatty acids having 20 or more carbon atoms. That is, since fatty acids become more volatile at lower temperatures as the number of carbon atoms decreases, blending a fatty acid having less than 20 carbon atoms into a polyester resin results in a temperature suitable for calendering the polyester resin from 170 ° C. Since the amount of volatilization becomes large in the range of 220 ° C., it becomes difficult to maintain the peeling from the metal roll for a long time, and the peelability from the metal roll varies depending on the conditions. Therefore, in order to stably achieve easy peeling from the metal roll for a long time under a suitable temperature condition for calendering the polyester resin, it is necessary that the fatty acid has 20 or more carbon atoms.

The fatty acids having 20 or more carbon atoms include
For example, behenic acid, tetracosanoic acid, hexacosanoic acid,
Examples include heptacosanoic acid, montanic acid, triacontanoic acid, dotriacontanoic acid, and the like. These fatty acids are
Although highly pure products are available as reagents, they are often expensive and are not generally used as additives for resin compositions. However, some fatty acids having 20 or more carbon atoms are provided at low cost as additives for resins such as montanic acid. In the present invention, fatty acids for resin additives containing montanic acid are also included. Is preferably used.

On the other hand, when a fatty acid having 20 or more carbon atoms is blended with a polyester resin, the glass transition temperature of the polyester resin is lowered. this is,
It shows that the fatty acid having 20 or more carbon atoms can be easily mixed with the polyester resin. Generally, as an additive to be added to a resin for improving the releasability from a metal, those having a low affinity with the resin and being difficult to mix are preferable, but a fatty acid having 20 or more carbon atoms is a polyester type. It has a feature that it can be easily mixed with a resin and that its releasability from a metal can be improved. For this reason, it is possible to achieve the characteristics that the formed sheet / film has excellent transparency and plate-out to the metal roll does not occur even though the peelability from the metal roll is good. With respect to fatty acids having 20 or more carbon atoms, this point is different from other release agents and lubricants for polyester resins.

When a fatty acid having 20 or more carbon atoms is blended with the polyester resin, the blending amount is in the range of 0.2 to 3.0 parts by weight with respect to 100 parts by weight of the polyester resin. If the amount of the fatty acid having 20 or more carbon atoms is less than 0.2 parts by weight, the releasability from the metal roll becomes insufficient. If the amount exceeds 3.0 parts by weight, the sheet or film becomes transparent. This is because the sex is reduced. Therefore, in the present invention, in order to stably achieve easy peelability from a metal roll in calender molding, and at the same time to achieve high transparency of a sheet or film, the blending amount of a fatty acid having 20 or more carbon atoms is a polyester type. It is limited to the range of 0.2 to 3.0 parts by weight with respect to 100 parts by weight of the resin.

Furthermore, in the polyester resin composition of the present invention, it is essential to add a fatty acid metal salt in addition to the fatty acid having 20 or more carbon atoms. If you use a fatty acid with 20 or more carbon atoms and specify its blending amount,
Although it is possible to produce a sheet or film that is easily separated from a metal roll and has good transparency, a molten resin pool (usually called a bank) formed between metal rolls in calendar molding. Since air may be entrained in the film and appear as vertical stripes on the surface of the sheet or film, it is effective to use a fatty acid metal salt in combination in order to solve such a problem.

In this case, the carbon number of the fatty acid portion of the fatty acid metal salt is not particularly limited. Examples of the fatty acid metal salt include lithium stearate, magnesium stearate, calcium stearate, potassium stearate, aluminum stearate, strontium stearate, barium stearate, cadmium stearate, zinc stearate, lead stearate, calcium laurate. , Barium laurate, cadmium laurate, zinc laurate, lithium myristate, zinc oleate, calcium behenate, zinc behenate, magnesium behenate, lithium behenate, calcium montanate, magnesium montanate, sodium montanate, 2 -Cadmium ethylhexoate, zinc 2-ethylhexoate, and the like. Some of these fatty acid metal salts are commercially available as additives for resins, and these are preferably used in terms of economy.

The blending amount of the fatty acid metal salt in the polyester resin is preferably 0.01 to 3.0 parts by weight based on 100 parts by weight of the polyester resin. The fatty acid metal salt can eliminate the harmful effects when only a small amount of the above fatty acid is blended, but if the blending amount is less than 0.01 parts by weight, the desired effect cannot be obtained, and the blending amount is 3.0 parts by weight. If it exceeds, the transparency of the molded sheet or film will decrease. Therefore, in order to maintain the high transparency of the polyester resin while exhibiting the effect of using the fatty acid metal salt in combination, the amount of the fatty acid metal salt is 0.01%.
It is preferably in the range of 3.0 to 3.0 parts by weight.

On the other hand, when the content of the fatty acid metal salt is larger than the content of the fatty acid, the releasability from the metal roll is somewhat inferior, and depending on the conditions, the calender molding process may have a problem. In order to carry out stable calender molding within a range of molding conditions and produce a sheet or film having a good appearance, it is preferable that the amount of the fatty acid metal salt is equal to or less than that of the fatty acid.

Regarding the polyester-based composition in which the fatty acid and the fatty acid metal salt are used in combination, a fatty acid ester or an oxidized polyethylene wax is used in combination for the purpose of supplementing the improvement of the peelability from the metal roll. May be valid. However, since the fatty acid ester or the oxidized polyethylene wax has a great effect of improving the releasability, the transparency of the resin is lowered and the plate-out is likely to occur. Therefore, it is necessary to control the amount to be small when compounding. Specifically, it is preferably equal to or less than the amount of the fatty acid or the fatty acid metal salt compounded, and 0.5 parts by weight or less.

Regarding the fatty acid ester used here,
The carbon number of the fatty acid portion is not particularly limited. However,
Considering the volatility of the obtained ester, the aliphatic saturated carboxylic acid having 12 to 28 carbon atoms and 2 to 30 carbon atoms are considered.
Synthetic waxes or natural waxes consisting of esters with saturated aliphatic alcohols are preferred. Examples of the aliphatic saturated carboxylic acid having 12 to 28 carbon atoms which composes the synthetic wax include lauric acid, mistyric acid, stearic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid and the like. 2-30 aliphatic saturated alcohols include, for example, ethyl alcohol, octyl alcohol, lauryl alcohol, stearyl alcohol,
Monohydric alcohols such as behenyl alcohol, pentacosyl alcohol, ceryl alcohol, octacosyl alcohol, and melysyl alcohol, and ethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2 Examples thereof include dihydric alcohols such as 3-butanediol, and polyhydric alcohols such as trihydric alcohols such as glycerin.

Further, as the above-mentioned synthetic wax, for example, stearyl laurate, stearyl mistyrate,
Stearyl stearate, octyl behenate, lauryl behenate, myristyl behenate, stearyl behenate,
Behenyl behenate, pentacotyl behenate, ceryl lignocerate, octacocyl lignocerate, melicyl lignocerate, stearyl cerotate, behenyl serotiate, ceryl cerate, merycyl cerotate, ethyl montanate, ceryl montanate, glycol glycol montanate, etc. Can be mentioned. Examples of natural waxes include montan wax, carnauba wax, bees wax, candelilla wax, nuka wax, and ivorot wax. Among them, montanic acid glycol ester, montanic acid glyceride, montan wax, and the like are preferable in view of volatility and releasability with respect to metal rolls, and these substances are commercially available as an additive for resin, which is economical. And these are preferably used.

The type of the oxidized polyethylene wax is not particularly limited, and may be either low density or high density. However, considering the releasability from the metal roll, the acid value is 1-40 mgKOH / g
Then, a partially oxidized polyethylene wax having a weight average molecular weight of 10,000 or less is preferable. Some of these substances are also commercially available as additives for resins, and these are preferably used in terms of economy.

The polyester resin composition for calendering according to the present invention comprises a polyester resin in the form of pellets or powder, a fatty acid having 20 or more carbon atoms and a fatty acid metal salt, and if necessary, a fatty acid ester or an oxidant. It can be produced by simply mixing the type polyethylene wax or by melt-kneading in advance with a kneader. As the kneader used here, a known device can be used, but a roll, a single-screw or twin-screw extruder, a kneader, a co-kneader, a planetary mixer, a Banbury mixer, etc., which can be handled easily and can be uniformly dispersed. Is preferably used.

The polyester resin composition of the present invention is a material obtained by blending a polyester resin with a fatty acid, a fatty acid metal salt, a fatty acid ester and an oxidized polyethylene wax at a high concentration (usually called a masterbatch). ) Are prepared in advance and they are simply mixed, or the polyester resin and the masterbatch are melt-kneaded. The kneading machine exemplified above is also suitably used for the production of the masterbatch.

On the other hand, in the polyester resin composition of the present invention, conventionally known antioxidants such as hindered phenol type, thioether type, amine type and phosphoric acid type antioxidants are used as long as the processability in calendar molding is not impaired. Or a conventionally known ultraviolet absorber such as benzophenone-based, benzoate-based, benzotriazole-based, cyanoacrylate-based, hindered amine-based, or anion-based,
Cationic or nonionic low or high molecular type antistatic agents, thickeners such as epoxy compounds and isocyanate compounds, colorants such as dyes and pigments, UV blocking agents such as titanium oxide and carbon black, glass fibers And fillers such as carbon fiber, silica, clay, calcium carbonate, barium sulfate, glass beads, talc, flame retardant, plasticizer, foaming agent, antibacterial agent, antifungal agent, fluorescent agent, surfactant, A cross-linking agent, etc. can be appropriately added.

Further, the polyester resin composition of the present invention contains a polyolefin-based resin, a polyvinyl chloride-based resin, a polystyrene-based resin, a polyether-based resin, a polyester-based resin, a polyamide-based resin, within a range that does not impair the molding processability in calendar molding. Other thermoplastic resin such as polyimide may be blended.

The polyester resin composition of the present invention is a resin composition suitable for being formed into a sheet or film by a calender molding machine after melt-kneading using a mixer or a uniaxial or biaxial extruder. At the time of producing a sheet or film, the releasability of the molten resin from the metal roll is good, and the transparency is also good. Further, plate out to the metal roll does not occur, and vertical streaks due to air entrainment do not occur in the obtained sheet or film. Therefore, by calendering the polyester resin composition, a sheet and a film having an excellent appearance can be molded with high productivity.

Sheets and films obtained by calendar molding using the polyester resin composition according to the present invention are transparent or colored sheets for decorative sheets or films, films, sheets or films for cards, and various types. It is preferably used as a sheet or film for packaging containers.

[0037]

EXAMPLES Next, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples.

<Example 1> As a polyester resin,
Eastman Chemical Product
s, Inc. Kodar PETG Co., Ltd.
ester grade Eastar PETG 6763
(Hereinafter, this is described as [A1].) Was used. In this polyester resin [A1], the dicarboxylic acid component is 100 mol% of terephthalic acid, other dicarboxylic acid components are not included, and the glycol component is ethylene glycol 60 to 60%.
75 mol% and 1,4-cyclohexanedimethanol 40
It is a polyester resin in the form of pellets having a number average molecular weight of 26000, which is composed of repeating units of the dicarboxylic acid component and the glycol component, and has a content of -25 mol% and no other glycol component. Further, this polyester resin [A1] is non-crystalline since no response corresponding to the melting of crystals and the crystallization from the melt was observed in the measurement with a differential scanning calorimeter. And the carbon number is 20
As the above fatty acid, montanic acid wax which is a flake-like solid at room temperature (manufactured by Clariant Japan Co., Ltd .; Grade Licowax S; hereinafter referred to as [B1]) was used. In addition, as the fatty acid metal salt, calcium montanate (manufactured by Clariant Japan Co., Ltd .; grade Licomont Ca, which is a powdery solid at room temperature) is used.
V102; hereinafter, this is referred to as [C1]. ) Was used.
The mixing ratio of the polyester resin [A1], the fatty acid [B1] having 20 or more carbon atoms, and the fatty acid metal salt [C1] is [A1]: [B1]: [C1] = 100:
0.75: 0.75, and a phenolic antioxidant (made by Asahi Denka Co., Ltd .; ADEKA STAB, grade AO-60; hereinafter referred to as AO-60).
Was blended in an amount of 0.5 part by weight, and a sheet was produced using a general calender molding method. Specifically, the polyester resin [A1], the fatty acid [B1] having 20 or more carbon atoms, and the fatty acid metal salt [C1] are uniformly mixed with a Henschel mixer, and the resin temperature is 160 to 175 with a Banbury mixer.
The polyester resin composition was prepared by kneading until the temperature became in the range of ° C. This was rolled using a reverse L-shaped four-roll calendering machine adjusted to a constant temperature, taken up, cooled, and then subjected to a thickness of 150 μm and a width of 1000 mm.
The sheet of was produced. Then, in the molding process of the sheet, the peelability of the material (molten resin) from the calender roll, the presence or absence of plate out to the calender roll, and the presence or absence of vertical stripes due to air entrainment are evaluated,
The haze was measured by the following sample and method as an index of the transparency of the sheet. The quality of each evaluation item was evaluated according to the following evaluation criteria. The evaluation results of each example are shown in Table 1, and the evaluation results of each comparative example are shown in Table 2.

[Measurement of haze] Measurement of haze is performed according to JIS
According to K 7105, a direct-reading haze computer (model HGM-2D) manufactured by Suga Test Instruments Co., Ltd. was used. Five 5 cm × 5 cm flat plates were cut out from the central portion of a 150 μm-thick sheet obtained by calendering, and the haze was measured, and the average value was used as a representative value.

[Evaluation Criteria] (1) Evaluation of releasability from metal roll Evaluation of releasability 1; Before molding with a calender molding machine, the releasability from metal was simply evaluated using a small mixer. As a small mixer, a lab mixer (R-60) manufactured by Toyo Seiki Seisakusho Co., Ltd. and having a capacity of 60 cc was used. At that time, the temperature of the mixer was set to 180 ° C., the mixture was kneaded at 60 rpm for 10 minutes, and the releasability of the melt from the mixer was evaluated. This evaluation was carried out before the calender molding was carried out. If the peelability was not obtained by this evaluation, the subsequent calender molding was not carried out because the peelability was insufficient. Then, for those having good peelability as evaluated by a small mixer, calender molding was carried out and the peelability was evaluated according to the following criteria. Evaluation of releasability 2: When the sheet-shaped melt entwined with the calender roll was peeled from the roll set at 190 ° C., it was evaluated as good (◯), and when it was adhered, it was evaluated as unacceptable (×). (2) Evaluation of occurrence of plate-out on metal rolls When the plate-out did not occur on the calender roll within 2 hours of continuous forming, it was rated as good (○), and when plate-out occurred, it was rated as bad (x). . (3) Evaluation of vertical streak generation due to air entrainment In the rolling process with the calendar roll, when no vertical streak was generated in the obtained sheet without air entrainment into the material, it was regarded as good (○) and obtained. The case where vertical streaks occurred in the sheet was marked as (X). (4) Evaluation of Transparency When the measured haze value is less than 5%, it is excellent (⊚), and when the haze value is 5% or more and less than 10%, it is good (∘), and the haze value is When it was 10% or more, it was judged as unacceptable (x). In addition, in the case of excellent (◎) and good (○),
The transparency of the produced sheet was considered to be good.

Example 2 As in Example 1, the polyester resin [A1] and the fatty acid [B] having a carbon number of 20 or more are used.
1] and a fatty acid metal salt [C1] were used as the polyester resin composition. However, polyester resin [A1]
And the mixing ratio of the fatty acid [B1] having 20 or more carbon atoms and the fatty acid metal salt [C1] in terms of weight ratio [A1]: [B1]:
[C1] = 100: 1.05: 0.06, and otherwise the same as in Example 1.

<Example 3> As in Example 1, the polyester resin [A1] and the fatty acid [B] having 20 or more carbon atoms are used.
1] and a fatty acid metal salt [C1] were used as the polyester resin composition. However, polyester resin [A1]
And the mixing ratio of the fatty acid [B1] having 20 or more carbon atoms and the fatty acid metal salt [C1] in terms of weight ratio [A1]: [B1]:
[C1] = 100: 0.75: 1.5, and otherwise the same as in Example 1.

Example 4 [A1] was used as the polyester resin, and [B1] was used as the fatty acid having 20 or more carbon atoms.
1] and as a fatty acid metal salt, powdery solid zinc behenate at room temperature (manufactured by Nitto Kasei Co., Ltd .; grade ZS)
-7: Hereinafter, this is described as [C2]. ) Was used. Then, the mixing ratio of the polyester resin [A1], the fatty acid [B1] having a carbon number of 20 or more, and the fatty acid metal salt [C2] is [A1]: [B1]: [C2] = 100: 1.0.
The ratio was set to 5: 0.06, and otherwise the same as in Example 1.

<Example 5> [A1] was used as the polyester resin, and behenic acid (manufactured by Kosei Co., Ltd .; for additives; below) was a powdery solid at room temperature as a fatty acid having 20 or more carbon atoms. , Which is referred to as [B2]. [C2] was used as the fatty acid metal salt. And
The mixing ratio of the polyester resin [A1], the fatty acid [B2] having 20 or more carbon atoms, and the fatty acid metal salt [C2] is [A1]: [B2]: [C2] = 100: 1.05:
The value was set to 0.06, and the other conditions were the same as in Example 1.

<Example 6> [A1] was used as the polyester resin, and [B1] was used as the fatty acid having 20 or more carbon atoms.
1] was used. As the fatty acid metal salt, magnesium montanate (manufactured by Nitto Kasei Co., Ltd .; grade MS-8; hereinafter referred to as [C3]), which is a powdery solid at room temperature, was used. Then, the polyester resin [A
1] and a fatty acid having 20 or more carbon atoms [B1] and a fatty acid metal salt [C3] in a weight ratio of [A1]: [B1]:
[C3] = 100: 1.05: 0.06, and otherwise the same as in Example 1.

<Example 7> As a polyester resin,
Eastman Chemical Product
s, Inc. Made by Tsunami Copolyest
er grade GS2 (hereinafter referred to as [A2]) was used. This polyester resin [A2] is
The dicarboxylic acid component is 100 mol% terephthalic acid and does not contain other dicarboxylic acids, and the glycol component is 60 to 75 mol% ethylene glycol and 40 to 25 mol% 1,4-cyclohexanedimethanol. And a number average molecular weight consisting of repeating units of these dicarboxylic acid component and glycol component is 250
00 is a pellet-type polyester resin. Also,
This polyester resin [A2] is non-crystalline, in which no response corresponding to the melting of crystals and the crystallization from the melt was observed in the measurement with a differential scanning calorimeter. The mixing ratio of the polyester resin [A2], the fatty acid [B1] having 20 or more carbon atoms and the fatty acid metal salt [C1] is [A2]: [B1]: [C1] = 100: 1.0.
The ratio was set to 5: 0.06, and otherwise the same as in Example 1.

<Example 8> As in Example 2, the polyester resin [A1] and the fatty acid [B] having a carbon number of 20 or more were used.
1] and a fatty acid metal salt [C1] were used as the polyester resin composition. However, a masterbatch in which a fatty acid [B1] having 20 or more carbon atoms and a fatty acid metal salt [C1] are highly filled is prepared in advance, and a predetermined amount of the masterbatch is blended with a polyester resin [A1]. Thus, a composition having an intended mixing ratio was prepared. In the masterbatch, the mixing ratio of the polyester resin [A1], the fatty acid [B1] having 20 or more carbon atoms and the fatty acid metal salt [C1] is [A1]: [B1]: [C1] = 10 by weight.
It was produced at a ratio of 0: 7.5: 0.4, and a twin-screw extruder having a cylinder diameter of 35 mmφ was used for the production. A predetermined amount of the masterbatch prepared here is blended with the polyester resin [A1], and [A1]: [B1]: [C1]
= 100: 1.05: 0.06, and 0.5 parts by weight of an antioxidant (AO-60) is added to the mixture.
Similar to Example 1, thickness 150 μm, width 1000 m
m sheets were produced.

<Example 9> As in Example 7, the polyester resin [A2] and the fatty acid [B] having 20 or more carbon atoms were used.
1] and a fatty acid metal salt [C1] were used as the polyester resin composition. However, a masterbatch in which a fatty acid [B1] having 20 or more carbon atoms and a fatty acid metal salt [C1] are highly loaded is prepared in advance, and a predetermined amount of the masterbatch is blended with a polyester resin [A2]. Thus, a composition having an intended mixing ratio was prepared. The masterbatch has a polyester resin [A2] and 2 carbon atoms
The mixing ratio of the fatty acid [B1] of 0 or more and the fatty acid metal salt [C1] is [A2]: [B1]: [C1] = 10 by weight.
It was produced at a ratio of 0: 7.5: 0.4, and a twin-screw extruder having a cylinder diameter of 35 mmφ was used for the production. The masterbatch produced here is used as a polyester resin [A2].
A predetermined amount is blended with [A2]: [B1]: [C
1] = 100: 1.05: 0.06, and 0.5 parts by weight of an antioxidant (AO-60) was added to this, and in the same manner as in Example 1, a thickness of 150 μm, Width 10
A 00 mm sheet was prepared.

<Example 10> As in Example 1, the polyester resin [A1] and the fatty acid [B] having 20 or more carbon atoms were used.
1] and a fatty acid metal salt [C1] in combination with a fatty acid ester. As fatty acid ester,
An ester of montanic acid and 1,4-butanediol (Montanic acid wax manufactured by Clariant Japan KK; Grade Licowax E; hereinafter referred to as [D1]) was used. And polyester resin [A1]
And the mixing ratio of the fatty acid [B1] having 20 or more carbon atoms, the fatty acid metal salt [C1] and the fatty acid ester [D1] in weight fraction [A1]: [B1]: [C1]: [D1] = 10
0: 0.75: 0.04: 0.04, and 0.5 parts by weight of an antioxidant (AO-60) was added to the mixture, and the same procedure as in Example 1 was performed to obtain a thickness of 150 μm. , Width 10
A 00 mm sheet was prepared.

<Example 11> As in Example 7, the polyester resin [A2] and the fatty acid [B] having 20 or more carbon atoms were used.
1] and a fatty acid metal salt [C1] in combination with an oxidized polyethylene wax. As an oxidized polyethylene wax, acid value is 15 ~ 19mgKOH
/ g (Clariant Japan KK; grade Licowax PED191; hereinafter referred to as [D2]
Is written. ) Was used. Then, the polyester resin [A
2], a fatty acid [B1] having 20 or more carbon atoms, a fatty acid metal salt [C1], and an oxidized polyethylene wax [D2] in a weight ratio of [A2]: [B1]: [C1]:
[D2] = 100: 0.75: 0.04: 0.04, and the phenolic antioxidant (AO
-60) was mixed in an amount of 0.5 part by weight to prepare a sheet having a thickness of 150 μm and a width of 1000 mm in the same manner as in Example 1.

<Comparative Example 1> [A1] alone was used as the polyester resin, and this polyester resin [A1] was used.
0.5 parts by weight of a phenolic antioxidant (AO-60) was mixed with 100 parts by weight. When this polyester resin composition was subjected to a peeling test using a mixer, the molten resin adhered strongly to the mixer, and peeling was impossible. From this, it was judged that it was impossible to produce a sheet using a calender molding machine with a polyester resin composition obtained by blending a polyester resin [A1] with an antioxidant, and calender molding was carried out. There wasn't.

Comparative Example 2 A peeling test using a mixer was conducted in the same manner as in Comparative Example 1 except that [A2] was used alone as the polyester resin. Calender molding was not performed because the molten resin could not be peeled off from the mixer.

<Comparative Example 3> Polyester resin [A1]
And a polyester-based resin composition consisting only of fatty acid [B1] having 20 or more carbon atoms, and no fatty acid metal salt is blended. Polyester resin [A1] and carbon number 20
The mixing ratio of the above fatty acids [B1] is [A
1]: [B1] = 100: 1.05, 0.5% by weight of an antioxidant (AO-60) was added, and then Example 1 was used.
Similarly to the above, a sheet having a thickness of 150 μm and a width of 1000 mm was produced. Vertical streaks were generated on this sheet due to the inclusion of air. According to this comparative example, the polyester resin composition composed only of the polyester resin [A1] and the fatty acid [B1] having 20 or more carbon atoms cannot suppress the generation of vertical stripes due to the entrainment of air. Is understood.

<Comparative Example 4> [A1] was used as the polyester resin, [C1] was used as the fatty acid metal salt, and stearic acid having less than 20 carbon atoms as fatty acid (Kanto Kagaku KK; purity; 95% powdered reagent; hereinafter referred to as [B3].) Is a polyester resin composition. Then, the mixing ratio of the polyester resin [A1], the fatty acid [B3] having less than 20 carbon atoms and the fatty acid metal salt [C1] is [A1]:
[B3]: [C1] = 100: 3.0: 0.06,
0.5% by weight of AO-60 was added as an antioxidant, and a peeling test with a mixer was conducted in the same manner as in Comparative Example 1. As a result, peeling of the molten resin from the mixer was impossible, so calender molding was not performed.

<Comparative Example 5> This is a polyester resin composition comprising only the polyester resin [A1] and the fatty acid metal salt [C1], and contains no fatty acid. Specifically, polyester resin [A1] and fatty acid metal salt [C
The mixing ratio of [1] is [A1]: [C1] = 10 by weight.
The ratio was set to 0: 1.5, 0.5% by weight of an antioxidant (AO-60) was blended, and a peeling test with a mixer was conducted in the same manner as in Comparative Example 1. As a result, peeling of the molten resin from the mixer was impossible, so calender molding was not performed.

Comparative Example 6 As in Example 1, the polyester resin [A1] and the fatty acid [B] having 20 or more carbon atoms are used.
1] and a fatty acid metal salt [C1], the polyester resin composition is a polyester resin [A1], a fatty acid [B1] having 20 or more carbon atoms, and a fatty acid metal salt [C1].
The mixing ratio of [A1]: [B1]: [C1] in weight fraction
= 100: 0.15: 0.04.
0.5 parts by weight of an antioxidant (AO-60) was added to this, and a peeling test with a mixer was conducted in the same manner as in Comparative Example 1. As a result, a part of the molten resin adhered to the mixer, and complete peeling was impossible. Therefore, calender molding was not performed.

<Comparative Example 7> As in Example 1, a polyester resin [A1] and a fatty acid [B] having 20 or more carbon atoms are used.
1] and a fatty acid metal salt [C1], the polyester resin composition is a polyester resin [A1], a fatty acid [B1] having 20 or more carbon atoms, and a fatty acid metal salt [C1] are mixed in a weight ratio. And [A1]: [B1]: [C1] =
It was blended so as to be 100: 3.5: 0.06. To this, 0.5 part by weight of an antioxidant (AO-60) was added, and then, in the same manner as in Example 1, the thickness was 150 μm and the width was 10 μm.
A 00 mm sheet was prepared. According to this comparative example, it is understood that the transparency decreases as the blending amount of the fatty acid [B1] having 20 or more carbon atoms increases.

<Comparative Example 8> Polyester resin [A1]
And the mixing ratio of the fatty acid [B1] having 20 or more carbon atoms and the fatty acid metal salt [C1] in weight fraction [A1]: [B1]:
[C1] = 100: 1.05: 0.005, and 0.5 parts by weight of an antioxidant (AO-60) was added to the mixture. 150μ
A sheet having a width of m and a width of 1000 mm was produced. According to this comparative example, it is understood that when the amount of the fatty acid metal salt [C1] is small, the effect of suppressing the generation of vertical stripes on the surface of the sheet is not observed.

<Comparative Example 9> Polyester resin [A1]
And the mixing ratio of the fatty acid [B1] having 20 or more carbon atoms and the fatty acid metal salt [C1] in weight fraction [A1]: [B1]:
[C1] = 100: 1.05: 3.5, and 0.5 parts by weight of an antioxidant (AO-60) was added to the mixture. 150 μm,
A sheet having a width of 1000 mm was produced. According to this comparative example, when the blending amount of the fatty acid metal salt [C1] is large, the peelability from the calender roll becomes insufficient, and particularly when the roll temperature is high to smooth the surface of the sheet, the peelability is high. It is understood that the transparency becomes insufficient and, in addition, the transparency decreases.

<Comparative Example 10> Polyester resin [A
1] is used, the fatty acid ester [D1] used in Example 10 is used in place of the fatty acid, and [C1] is used as the fatty acid metal salt.
Was used. Then, the mixing ratio of the polyester resin [A1], the fatty acid ester [D1], and the fatty acid metal salt [C1] is [A1]: [D1]: [C1] = 100: by weight.
1.05: 0.06, and otherwise the same as Example 1. According to this comparative example, it is understood that even if the fatty acid ester [D1] is used instead of the fatty acid [B1], the peelability from the calender roll is achieved, but plate-out occurs.

Comparative Example 11 [A2] was used as the polyester resin, the oxidized polyethylene wax [D2] used in Example 11 was used in place of the fatty acid, and [C1] was used as the fatty acid metal salt. Then, the mixing ratio of the polyester resin [A2], the oxidized polyethylene wax [D2] and the fatty acid metal salt [C1] is [A2] by weight.
[D2]: [C1] = 100: 1.05: 0.06, and otherwise the same as in Example 1. According to this comparative example, when the oxidized polyethylene wax [D2] is used instead of the fatty acid [B1] having 20 or more carbon atoms, the peelability from the calender roll is achieved, but plate-out may occur. To be understood.

<Comparative Example 12> Polyester resin [A
1] was used instead of the fatty acid, and polyethylene wax (manufactured by Clariant Japan KK; grade Licow)
ax PE520; hereinafter, this is referred to as [D3]. ) Was blended and [C1] was used as the fatty acid metal salt. Then, the mixing ratio of the polyester resin [A1], the polyethylene wax [D3] and the fatty acid metal salt [C1] is [A1]: [D3]: [C1] = 100: 3.0:
0.06, and an antioxidant (AO-60) was added to this.
After blending 5% by weight, a peeling test with a mixer was performed as in Comparative Example 1. As a result, peeling of the molten resin from the mixer was impossible, so calender molding was not performed.

<Comparative Example 13> Polyester resin [A
2], ethylene bisstearic acid amide (manufactured by Clariant Japan KK; amide wax, grade Licolub FA1; hereinafter referred to as [D4]) is blended in place of the fatty acid to prepare a fatty acid metal salt [ C1] was used. Then, the polyester resin [A
2], ethylenebisstearic acid amide [D4] and fatty acid metal salt [C1] in a mixing ratio by weight [A2]: [D
4]: [C1] = 100: 3.0: 0.06, 0.5% by weight of an antioxidant (AO-60) was added to the mixture, and peeling was performed with a mixer in the same manner as in Comparative Example 1. A test was conducted, but since the molten resin could not be separated from the mixer, calender molding was not carried out.

<Comparative Example 14> Polyester resin [A
2] is used, and a polymer lubricant of acrylic acid (made by Mitsubishi Rayon Co., Ltd .; Metablen, grade L-1000; hereinafter referred to as [D5]) is blended in place of the fatty acid.
[C1] was used as the fatty acid metal salt. The mixing ratio of the polyester resin [A2], the polymeric lubricant of acrylic acid [D5], and the fatty acid metal salt [C1] is [A2]: [D
5]: [C1] = 100: 3.0: 0.06, 0.5% by weight of an antioxidant (AO-60) was added to the mixture, and peeling was performed with a mixer in the same manner as in Comparative Example 1. A test was conducted, but since the molten resin could not be separated from the mixer, calender molding was not carried out.

<Comparative Example 15> [A1] is used as the polyester resin, and [B1] is used as the fatty acid having 20 or more carbon atoms.
1] was used instead of the fatty acid metal salt in Example 10
The fatty acid ester [D1] used in 1 above was used in combination. Example 2 was performed in the same manner as in Example 2 except that the fatty acid ester [D1] was used instead of the fatty acid metal salt [C1]. According to this comparative example, it is understood that when the fatty acid ester [D1] is used instead of the fatty acid metal salt [C1], the effect of suppressing the generation of vertical streaks due to the entrainment of air is not seen.

<Comparative Example 16> [A1] was used as the polyester resin, and [B1] was used as the fatty acid having 20 or more carbon atoms.
1] was used instead of the fatty acid metal salt in Example 11
Oxidized polyethylene wax [D2] used in Step 1 was used in combination. Example 2 was performed in the same manner as in Example 2 except that the oxidized polyethylene wax [D2] was used instead of the fatty acid metal salt [C1]. According to this comparative example, the oxidized polyethylene wax [D] was used instead of the fatty acid metal salt [C1].
It is understood that when [1] is used, the effect of suppressing the generation of vertical streaks due to the entrainment of air is not observed.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

As is clear from the evaluations disclosed in Tables 1 and 2, according to the polyester resin composition of the present invention, it is possible to control the crystallinity of the polyester resin (non-crystalline polyester resin). , Almost no sticking to the metal roll (calender roll) or plate out to the metal roll during calender molding, and the obtained sheet / film has good transparency, and air is entrained in the sheet or film. It is understood that the composition is suitable for high-speed production of a sheet or film by calendering without causing vertical streaks.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B29L 7:00 B29L 7:00 F term (reference) 4F071 AA45 AA46 AA47 AC09 AE11 AH04 AH05 BB04 BC01 4F204 AA24 AB07 AB19 FA07 FB02 FF01 FF06 4J002 CF031 CF041 CF051 CF061 CF071 CF081 CF091 EF056 EG027 EG037 EG047 FD176 FD177 GB00 GG00

Claims (3)

[Claims] 1. A dicarboxylic acid component containing at least 80 mol% of at least 80 mol% of a mixture of one or more selected from terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and isophthalic acid, and ethylene glycol, neo. At least 80 mol% of one or a mixture of two or more selected from pentyl glycol, diethylene glycol and 1,4-cyclohexanedimethanol
0.2 to 3.0 parts by weight of a fatty acid having 20 or more carbon atoms and 0.01 parts of a fatty acid metal salt are added to 100 parts by weight of a polyester resin composed of repeating units of the glycol component.
A polyester resin composition for calendar molding, characterized in that the polyester resin composition is blended in an amount of up to 3.0 parts by weight. 2. The polyester resin composition for calendar molding according to claim 1, wherein the blending amount of the fatty acid metal salt is equal to or less than the blending amount of the fatty acid. 3. A sheet or film formed by a calendering method using the polyester resin composition according to claim 1.