JP2001294732A - Copolyester-based resin composition and sheet prepared from the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition, the melt of which has an extremely increased melt tension in the state of maintaining transparency, and exhibits a good sheet processability, so that a sheet excellent in transparency is obtained. SOLUTION: There are provided a copolyester-based resin composition comprising 99-50 wt.% of a non-crystalline copolyester containing, as repeating units, a dicarboxylic acid component comprising at least 90 mol% of terephthalic acid and a glycol component comprising 10-95 mol% of 1,4- cyclohexanedimethanol and 90-5 mol% of ethylene glycol and 1-50 wt.% of a polyvinyl chloride resin, wherein the polyvinyl chloride resin is a polyvinyl chloride resin composition in which upto 100 pts.wt. of a plasticizer is blended with 100 pts.wt. of the polyvinyl chloride resin, and a sheet prepared from the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a copolyester resin composition having good moldability in various molding processes, and further having good transparency of the obtained molded article, and a sheet obtained from the composition. It is about.

[0002]

2. Description of the Related Art A dicarboxylic acid component containing at least 90 mol% of terephthalic acid and a glycol component containing 10-95 mol% of 1,4-cyclohexanedimethanol and 90-5 mol% of ethylene glycol have been known as repeating units. A noncrystalline copolyester (hereinafter referred to as P
(Abbreviated as ETG) is generally known.

[0003] This PETG is formed into various molded articles by secondary molding such as injection, extrusion, blow, and vacuum molding, and the molded article has transparency, surface gloss, chemical resistance, oil resistance, and gamma ray resistance. Utilizing the characteristics of sterilization, aromatic barrier properties, impact resistance, and heat resistance, food packaging, packaging materials,
It is used for medical equipment, home appliance parts, daily necessities, and industrial materials.

[0004] Crystalline PET composed of repeating units of terephthalic acid and ethylene glycol is used as a material for molding, but when it is melted at a temperature higher than the melting point (about 280 ° C), the melt tension becomes extremely high. Smaller, extrusion,
It could not be applied to molding requiring a large melt tension, such as blow, calender, and vacuum molding. In addition, since the crystallization speed is low, the degree of crystallization is greatly affected by cooling conditions, and there is also a problem that quality control of products is not easy.

However, since PETG is non-crystalline, these problems existing in crystalline PET are solved, so that it can be applied to various moldings and a product having stable quality can be obtained. Although it can be said that the applicable forming method has greatly increased compared to crystalline PET, this PETG has a problem that the temperature dependence of the melt tension is large and the processable condition width is narrow. is there. In addition, there is also a problem that the melt tension is too small to produce a thin sheet by applying to calendering. Therefore, in order to be able to sufficiently apply PETG to various moldings, including an increase in the processing condition width and an increase in applicable processing methods, further higher melt tension is required.

In general, there are several ways to increase the melt tension. One of them is a method of increasing the molecular weight. However, in general, it is difficult to increase the molecular weight of the polyester resin, and furthermore, this method also increases the shear viscosity, which causes problems such as a decrease in productivity and an increase in load on a processing machine. There is also a method of increasing the melt tension by expanding the molecular weight distribution. However, there is a limit to the expansion of the molecular weight distribution, and the effect of increasing the melt tension is not so large as long as it can be expanded. With a similar idea, a method of blending a small amount of a component having a very large molecular weight has been reported, but it is difficult to produce a high molecular weight component and it is difficult to finely disperse these components uniformly, so that sufficient effects are obtained. May not be exhibited, or may become a foreign substance and adversely affect the appearance of the product.

Further, a method of blending a resin having a large melt tension is often used. For example, in the field of polyolefin resins, linear high-density polyethylene (HDPE) and linear low-density polyethylene (LLDP) having a low melt tension are used.
E) low-density polyethylene (LDPE) or ethylene-vinyl acetate copolymer (EV
A method of blending a resin having a large melt tension such as A) is known. However, in this method, a large amount of resin having a large melt tension must be blended to some extent, and furthermore, if the resins to be mixed are mixed or not mixed molecularly, the refractive index should not be close. The molded product becomes cloudy.

[0008] In the case of PETG as well, the melt tension can be increased by this method, but PETG has the greatest feature of transparency, and has little significance in improving the moldability after losing transparency. From the above, regarding PETG,
At present, it is quite difficult to increase the melt tension and further improve the moldability while maintaining the transparency, which is a characteristic of the method.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned general circumstances surrounding PETG, and has been developed in a state where the melt tension of the melt is significantly increased while maintaining the transparency characteristic of PETG. An object of the present invention is to provide a polyester resin composition and a sheet obtained therefrom.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, PETG has been added to polyvinyl chloride resin (hereinafter abbreviated as PVC resin).
Alternatively, it has been found that by blending a PVC resin composition in which a plasticizer is blended with the PVC resin, the melt tension of the melt is significantly increased. Furthermore, it was also found that by forming the composition into a sheet using a known apparatus, a sheet having good sheet processability and good transparency can be obtained, thereby completing the present invention.

The solution is to provide a copolyester resin composition comprising 99 to 50% by weight of PETG and 1 to 50% by weight of a PVC resin, or a PVC resin in the composition is added to 100 parts by weight of the PVC resin. Plasticizer 10
It is a copolyester-based resin composition comprising a PVC-based resin composition containing up to 0 parts by weight, and a sheet obtained from such a composition.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The dicarboxylic acid component containing at least 90 mol% or more of terephthalic acid and 1,4-cyclohexanedimethanol used in the present invention are 10 to 9%.
The non-crystalline copolyester having a repeating unit of 5 mol% and a glycol component in which ethylene glycol is 90 to 5 mol% is generally known as PETG as described above. Japanese Patent Application No. 6-524
As exemplified in Japanese Patent Publication No. 328 (Japanese Patent Application Laid-Open No. Hei 8-509768), after reacting terephthalic acid and a glycol component containing 1,4-cyclohexanedimethanol and ethylene glycol, in the presence of a specific catalyst, By polycondensation, a colorless and transparent copolyester is obtained.

Specific examples of the production include a dicarboxylic acid component containing at least 90 mol% of terephthalic acid, 10-95 mol% of 1,4-cyclohexanedimethanol and 90-5 mol% of an ethylene glycol component. Is reacted at a temperature sufficient to effect esterification or transesterification. Then
The resulting reaction product is subjected to 0-75 ppm Mn, 50-150 pp, based on the weight of the copolyester, under an absolute pressure of less than 1.333 KPa for less than 2 hours.
polycondensation in the presence of a catalyst and inhibitor system consisting of m Zn, 5-20 ppm Ti, 5-200 ppm Ge and 10-80 ppm P.

The dicarboxylic acid portion of PETG is composed of at least 90 mol% of a repeating unit derived from terephthalic acid. The repeating units composed of less than 10 mol% of a dicarboxylic acid include succinic acid, glutaric acid, adipic acid and sebacic acid. Acid, fumaric acid, maleic acid, itaconic acid,
Other common acids such as those selected from 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid and naphthalenedicarboxylic acid.

On the other hand, the glycol component of PETG includes 1
It contains repeating units from 0 to 95 mol% of 1,4-cyclohexanedimethanol and 90 to 5 mol% of ethylene glycol. In addition, this glycol component includes
Less than 10 mol% of 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- General glycol components such as cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol may be contained.

Incidentally, these PETGs are, for example, Ea
stman Chemical Products, I
nc. (Hereinafter abbreviated as Eastman Chemical Co., Ltd.) and the product name "Koda PETG Copolyest."
er "grade Eastar PETG 6763 or" Ektar PETG Copolyester "
r "grade GN 001.

Further, with respect to PETG used in the present invention, a dicarboxylic acid component containing at least 90 mol% of terephthalic acid, 10-95 mol% of 1,4-cyclohexanedimethanol and 90-5 mol% of ethylene glycol The molecular weight (solution viscosity, melt viscosity) and the like are not particularly limited as long as the copolyester has a glycol component as a repeating unit and is non-crystalline.

In addition, PETG includes known antioxidants such as hindered phenols and thioethers, weathering agents such as benzophenols and hindered amines, epoxy compounds and isocyanate compounds as long as the object of the present invention is not impaired. Thickeners such as silicone oil, metal stearates, metal montanates, molding release agents such as montanic acid ester waxes, coloring agents such as dyes and pigments, and flame retardants blended into polyester resins,
A plasticizer, a foaming agent, a bactericide, a surfactant and the like can be optionally contained.

On the other hand, the PVC resin used in the present invention is a polymer containing vinyl chloride, and is copolymerized with a homopolymer of vinyl chloride, a chlorinated polyvinyl chloride polymer, and a vinyl chloride monomer. And vinyl chloride copolymers obtained by random copolymerization, graft copolymerization or block copolymerization with one or more of the possible monomers, or a mixture of two or more of these polymers. However, when sheet molding or the like is performed using a composition with PETG, a homopolymer of vinyl chloride is preferred in that the molded article has the highest transparency.

Examples of monomers copolymerizable with the vinyl chloride monomer include ethylene, propylene, butene, pentene-1, butadiene, styrene, α-methylstyrene, acrylonitrile, vinylidene chloride, vinylidene cyanide, Alkyl vinyl ethers such as methyl vinyl ether, carboxylic acid vinyl esters such as vinyl acetate, aryl ethers such as methoxystyrene, dialkyl maleic acids such as dimethyl maleic acid, fumaric esters such as dimethyl fumarate, N-vinyl pyrrolidone And alkyl acrylates such as vinyl pyridine, vinyl silanes and butyl acrylate, and alkyl methacrylates such as methyl methacrylate.

With respect to the degree of polymerization of the PVC resin,
There is no particular limitation, and any one can be used. However, the number average degree of polymerization is preferably 500 or more from the viewpoint of increasing the effect of increasing the melt tension, and the number average degree of polymerization is preferably 3000 or less from the viewpoint of improving dispersibility in PETG.

Further, according to the present invention, the PVC resin contains 100 parts by weight of a plasticizer and 100 parts by weight of a plasticizer.
A composition containing up to parts by weight may be used. By adding a plasticizer to the PVC resin, the disintegration (gelation) of the particle structure of the PVC resin is promoted, and the dispersibility of the PVC resin in PETG is improved.

Examples of the plasticizer to be blended include di-n-butyl phthalate, di-2-ethylhexyl phthalate,
Phthalic acid-based plasticizers such as di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisooctyl phthalate, octyldecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl isophthalate, and dicyclohexyl phthalate; Di-2-ethylhexyl adipate, di-n-decyl adipate, diisodecyl adipate, dibutyl sebacate, di-2-sebacate
Aliphatic ester-based plasticizers such as ethylhexyl, trimellitic acid-based plasticizers such as trioctyl trimellitate and tridecyl trimellitate, tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate, Phosphoric acid ester plasticizers such as tricresyl phosphate and trixylenyl phosphate; epoxy plasticizers such as epoxy soybean oil; polyester polymer plasticizers; and one or more of these. Can be used.

When a plasticizer is added to the PVC resin, the amount of the plasticizer is 100 parts by weight per 100 parts by weight of PVC.
Up to 100 parts by weight, but if the amount of the plasticizer exceeds 100 parts by weight, the surface of a molded article such as a sheet becomes sticky,
Not preferred.

The PVC resin or a PVC resin composition containing a plasticizer added thereto may contain a stabilizer (for example, a metal soap such as barium stearate or an organic tin such as tin laurate). Phosphite-based stabilizers such as tetraphenyl polypropylene glycol diphosphite, and hydrotalcite-based stabilizers such as perchloric acid-treated hydrotalcite.)
And lubricants (for example, fatty acid ester waxes such as n-butyl stearate, hydrocarbon waxes, metal soaps such as magnesium stearate and zinc stearate), acrylic processing aids (for example, methyl methacrylate) Methyl methacrylate alkyl acrylate copolymer such as butyl acrylate copolymer),
Colorants, flame retardants (eg, antimony trioxide, zinc borate, etc.), process oils (eg, aromatic, naphthenic, paraffinic, and other mineral oils, castor oil, cottonseed oil, linseed oil, rapeseed oil) , Soybean oil,
Palm oil, palm oil, peanut oil, wood wax, pine oil,
Vegetable oils such as olive oil, and softening agents for resins such as synthetic oils), and the like.

The copolyester-based resin composition of the present invention is obtained by adding a PET-based resin or a PVC-based resin composition to PETG in a weight fraction of PETG: PVC-based resin or PVC-based resin composition = 99: 1 to 50:50. It can be obtained by blending as follows. Even if a small amount of the PVC resin is blended with PETG, the effect of increasing the melt tension can be obtained. Therefore, the lower limit of the blending amount of the PVC resin here defines a range in which a practically significant effect is exhibited. On the other hand, even if the amount of the PVC resin exceeds 50% by weight, the desired effect of increasing the melt tension can be obtained. However, in this case, the blending amount of the PVC resin is 50% by weight.
And PETG is a minor component in the copolyester-based resin composition. Therefore, many characteristics of PETG such as heat resistance disappear, which is not preferable.

As a method for producing the copolyester resin composition of the present invention, a conventionally known method is used. However, the PVC resin is often supplied in the form of powder, and the powder has a hierarchical structure with different particle sizes. Therefore, depending on the kneading method and kneading conditions, PVC resin particles will remain even if kneaded with PETG, and PETG will remain.
And good dispersibility of the PVC resin cannot be obtained. For this purpose, the order of kneading and the disintegration (gelation) of PVC resin particles are considered.
It is necessary to knead the PVC resin first to break down the particle structure of the PVC resin (promoted gelation)
It is preferable to mix it with ETG. The reason for blending the plasticizer with the PVC resin is to promote the collapse (gelation) of the particle structure of the PVC resin.

As the kneading apparatus for producing the composition of the present invention, various conventional apparatuses can be used. However, in order to improve the ease of handling and the dispersibility of PETG and the PVC resin, a roll is used. , A plastmill, a kneader, a Banbury mixer and a single- or twin-screw extruder are preferred, and the preparation of the composition can be carried out using
It is preferable to melt-knead at a temperature equal to or higher than the temperature at which the ETG becomes a melt.

In addition, in order to form a sheet using the composition of the present invention, a conventionally known apparatus can be used, and examples thereof include a roll processing apparatus such as a calender apparatus, an extruder, and an inflation apparatus.

[0030]

EXAMPLES The present invention will be described in more detail with reference to specific examples and comparative examples, but the present invention is not limited to these examples. Examples 1 to 7 and Comparative Examples 1 and 2 show examples relating to a copolyester-based resin composition in which PETG and a PVC-based resin or a plasticizer is blended with a PVC-based resin.

Example 1 In Example 1, grade Eastar PETG 6763 manufactured by Eastman Chemical Company is used as PETG. Hereinafter, this is referred to as [A1]. Note that P in [A1]
For ETG, the dicarboxylic acid moiety is terephthalic acid 1
00 mol%, and does not include other dicarboxylic acid repeating units. The glycol component comprises a repeating unit of ethylene glycol and 1,4-cyclohexanedimethanol, and does not include other glycol components.
Further, the PETG of [A1] is non-crystalline, with no peak corresponding to melting observed in the DSC heating curve. On the other hand, as the PVC resin, a grade S9007 PVC resin manufactured by Kureha Chemical Industry Co., Ltd. is used. this is,
The number average degree of polymerization is about 700. Hereinafter, this is referred to as [B1]
It is written.

First, [B1] is set to [B1] 100
KV, a barium-zinc-based stabilizer, is
3.405 parts by weight of -405W (manufactured by Kyodo Yakuhin), barium-
2.4 parts by weight of a zinc-based stabilizer KP-905HG (manufactured by Kyodo Yakuhin) was added, and this mixture was charged into a 60 cc Brabender mixer (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: Labo Plastmill). Kneading for a minute and then separately [A
1) A composition obtained by mixing 0.7 parts by weight of RX-PO-8, a stabilizer manufactured by Daikyo Kasei Kogyo Co., with respect to 100 parts by weight, was charged into the Brabender mixer, and kneaded for 4 minutes to obtain a composition. I got

At this time, the components were mixed so that the mixing ratio of [A1] and [B1] was [A1]: [B1] = 75: 25 by weight, and the mixture was mixed at a mixer temperature of 180 ° C. and a rotation speed of 50 rpm. To prepare a composition. The lump composition obtained here was melt-compressed to form a sheet having a thickness of about 1 mm.
Measure the melt tension with a small piece of mm square and about 5 cm x 5
Haze was measured for transparency in cm sheets. For compression molding, a compression molding machine manufactured by Shinto Metal Industry Co., Ltd., model ASFA-70, was used.
Performed at 8 ° C.

Example 2 Example 2 is the same composition as [A1] and [B1] in Example 1. However, the mixing ratio of [A1] and [B1] is such that [A1]: [B1] = 50: 50 by weight fraction, and the other conditions are the same as in Example 1.

Example 3 In Example 3, the same [A1] as in Example 1 was used for PETG, and a PVC resin manufactured by Chisso Corporation was used as a PVC resin.
Nipolit, grade SL is used. It has a number average degree of polymerization of about 1050. Hereinafter, this is referred to as [B2]. Here, it is the same as Example 1 except that [B1] of Example 1 is changed to [B2].

Embodiment 4 In Embodiment 4, the same [A1] as in Embodiment 1 is used for PETG. Here, a PVC resin, Nipolit, and grade SM manufactured by Chisso Corporation are used as the PVC resin. It has a number average degree of polymerization of 1300. Hereinafter, this is referred to as [B
3]. Here, [B1] of the first embodiment is changed to [B3]
This example is the same as Example 1 except for the above.

Example 5 Example 5 is the same composition as [A1] and [B3] as in Example 4. However, the mixing ratio of [A1] and [B1] is such that [A1]: [B1] = 98: 2 by weight fraction, and the other conditions are the same as in Example 4.

Example 6 Example 6 is the same composition as [Example 1] consisting of [A1] and [B2], and the mixed composition is also the same as Example 2. However,
[B2] is obtained by blending 10 parts by weight of di-2-ethylhexyl phthalate (hereinafter referred to as DOP) with respect to 100 parts by weight of [B2]. It is the same as Example 2 except that DOP was blended with the PVC resin.

Example 7 Example 7 is the same composition of [A1] and [B3] as in Example 4, and the mixed composition is also the same as in Example 4. However,
In [B3], DOP30 was added to 100 parts by weight of [B3].
It is a mixture of parts by weight.

Comparative Example 1 Comparative Example 1 is a simple substance of [A1] used in Examples 1 to 7, and was not mixed with a PVC resin, and was all [A1].
A mixture of 0.7 parts by weight of RX-PO-8, a stabilizer manufactured by Daikyo Kasei Kogyo, with 100 parts by weight of [A1] was melt-kneaded in the same manner as in Example 1. Thereafter, a compression molded sheet was produced.

Comparative Example 2 In Comparative Example 2, low-density polyethylene (LDPE) obtained by a high-pressure radical polymerization method was blended with [A1] used in Examples 1 to 7. Petrocene, grade 360 manufactured by Tosoh Corporation is used for LDPE. This is 190
The melt flow rate (MFR) measured under a load of 2160 g at 1.6 ° C. is 1.6 g / 10 min. Hereinafter, this is referred to as [C1]. Here, except that [B1] containing the stabilizer described in Example 1 was changed to [C1], melt kneading was performed in the same manner as in Example 1, and then a compression molded sheet was produced.

[0042]

[Table 1]

Table 1 shows the haze relating to the melt tension and the transparency of the compression-molded sheets of Examples 1 to 7 and Comparative Examples 1 and 2. From Table 1, it is possible to mix PVC-based resin with PETG or DOP with PVC-based resin. By blending the obtained PVC-based resin composition, it was found that the haze was hardly changed and the melt tension was increased. By blending LDPE with PETG, the melt tension was increased, but the haze was increased. This indicates that blending LDPE cannot achieve both transparency and an increase in melt tension. The melt tension and the haze were measured by the following methods.

Measurement of Melt Tension The melt tension was measured using a capillary rheometer (manufactured by Toyo Seiki Seisaku-sho, Ltd., trade name: Capillograph) with a die having a capillary diameter of 2.095 mm and a capillary length of 8 mm attached. The measurement was performed at a piston descending speed of 10 mm / min, an extruded melt take-up speed of 5 m / min, and a cylinder temperature of 180 ° C.

Measurement of Haze The haze was measured using a direct reading haze computer, model HGM-2D, manufactured by Suga Test Instruments Co., Ltd. About 1mm thick
From the compression molded sheet, four sheets of 5 cm × 5 cm were cut out, the haze of each was measured, and the average value was defined as the haze value. Here, the haze value is used as an index of transparency. The smaller the haze value is, the more transparent the haze value is. However, the value also depends on the thickness of the test piece used for the measurement, and it is not possible to simply distinguish between transparent and opaque by numbers. Therefore, also here, transparent and opaque were distinguished by relative comparison rather than separating transparent and opaque as the absolute value of the haze value.

Next, as Examples 8 to 11 and Comparative Examples 3 and 4, examples relating to sheets obtained from a copolyester resin composition obtained by mixing PETG and a PVC resin or a plasticizer with a PVC resin will be described.

Example 8 In Example 8, a sheet was prepared from the same composition of [A1] and [B1] as in Example 1 using a test roll molding machine. The test roll forming machine is manufactured by Nippon Roll Manufacturing Co., Ltd. The surface speed of the roll is 10 m / min for the front roll and 8 m / mi for the rear roll.
n, the roll temperature was set at 185 ° C., and the roll gap was adjusted so that the sheet thickness was about 0.4 mm.

First, 3.4 wt. Of KV-405W (manufactured by Kyodo Yakuhin), a barium-zinc-based stabilizer, was added to 100 wt. Parts of [B1] in [B1] in the same manner as in Example 1. Part, KP-9 which is a barium-zinc based stabilizer
A mixture of 2.4 parts by weight of 05HG (manufactured by Kyodo Yakuhin) was added, and then RX-PO-8, a stabilizer manufactured by Daikyo Kasei Kogyo Co., Ltd., was added separately to [A1] per 100 parts by weight of [A1].
Was added in an amount of 0.7 parts by weight. In addition, the sample amount was set such that the total resin content of [A1] and [B1] was 100 g.

Example 9 In Example 9, a sheet was formed by using the same composition of [A1] and [B3] as in Example 4 and molding the sheet under the same method and conditions as in Example 8. . In addition, the sample amount was set such that the total resin content of [A1] and [B3] was 100 g.

Example 10 In Example 10, a sheet was formed by using the same composition of [A1] and [B3] as in Example 5, and forming a sheet under the same method and conditions as in Example 8. . In addition, the sample amount was set such that the total resin content of [A1] and [B3] was 100 g.

Example 11 Example 11 is a composition of Example 7, ie, [B3]
A composition prepared by blending 30 parts of DOP with 100 parts of [A]
Using the composition blended in 1), the same method as in Example 8,
The sheet was formed under the conditions to produce a sheet. In addition, the sample amount is 100 when the total of the resin components of [A1] and [B3] is 100.
g.

Comparative Example 3 Comparative Example 3 is an example of Examples 8 to 11, in which [A1] alone used in those examples was formed into a sheet under the same apparatus and conditions as in Example 8. The sample amount was [A1] 1
00g, and a stabilizer, RX-P manufactured by Daikyo Kasei Kogyo Co., Ltd.
0.7 g of O-8 was blended.

Comparative Example 4 Comparative Example 4 is also an example of Examples 8 to 11, and [A] of Comparative Example 2
A sheet was formed from the composition consisting of [1] and [C1] using the same method and conditions as in Example 8 to produce a sheet. In addition, the sample amount was set such that the total resin content of [A1] and [C1] was 100 g.

[0054]

[Table 2]

Table 2 shows the results of visual evaluation and the haze of the melt tension of the compositions used in Examples 8 to 11 and Comparative Examples 3 and 4, and the moldability of the sheet. From Table 2, Examples 8 to
Compared to No. 11, the sheet formability of the [A1] alone of Comparative Example 3 was extremely poor, and [C1] of Comparative Example 4 was
That is, by blending LDPE, Examples 8 to
As in the case of No. 11, the sheet formability was improved, but the haze was extremely large.

Further, in Table 2, the sheet formability was determined as in Example 9.
And Example 8 have the same evaluation, but the composition used in Example 9 has a higher melt tension than the composition used in Example 8, and when strictly evaluated, the sheet formability of Example 9 is higher. It is better than Example 8. However, the sheet of Example 9 has a larger haze than the sheet of Example 8. The composition used in Example 10 was the same as the composition used in Example 9, but the blending amount of the PVC resin was small and the melt tension was small. Examples 10 and 9 for sheet formability
Is the same, but when strictly evaluated in the same manner as described above, Example 10 is slightly inferior in sheet formability to Example 9. However, in each case, the evaluation was within the range of ○. The sheet of Example 10 has a smaller haze than the sheet of Example 9.

Further, the sheet formability was also determined by DO
Example 11 using the PVC resin composition containing 30 parts of P and Example 9 not containing DOP have the same evaluation. However, when strictly evaluated in the same manner as described above, the melt tension of the composition is In Example 11, the sheet formability was slightly inferior to Example 9 because of the small. However, the difference was slight, and in all cases, the evaluation was within the range of ○. Example 11
Is smaller than that of the sheet of Example 9.

The haze relating to the melt tension and the transparency was measured by the same method as described above, and the effect of improving the formability in sheet molding and the transparency of the sheet were evaluated by the following methods. .

The effect of improving the moldability was evaluated by visually observing the improvement in sheet releasability and drawdown resistance, and the evaluation results were indicated by ○ and ×. Regarding sheet releasability, ○: when the sheet peels below the center of the roll ×: when the sheet peels above the center of the roll For drawdown resistance, when the sheet is pulled, ○: when pulling the sheet The previous shape as it is, or the part where the start of taking over is slightly constricted when taking over is completed. ×: The sheet extends over a wide area and becomes narrow over the entire sheet.

[0060]

According to the present invention, terephthalic acid contains at least 90
Mol% or more of a dicarboxylic acid component and a non-crystalline copolyester 99-5 containing a glycol component of 10-95 mol% of 1,4-cyclohexanedimethanol and 90-5 mol% of ethylene glycol as repeating units.
Since it is a copolyester resin composition composed of 0% by weight and 1 to 50% by weight of a polyvinyl chloride resin, it can be applied to various molding processes while maintaining the transparency characteristic of the used copolyester, ie, PETG. In this case, the melt tension, which is important for developing good processing characteristics, is remarkably increased.

The above-mentioned polyvinyl chloride-based resin is used in an amount of 100 parts by weight of the polyvinyl chloride-based resin.
By being a polyvinyl chloride resin composition containing up to parts by weight, the collapse (gelation) of the particle structure of the PVC resin is promoted, and the dispersibility of the PVC resin in PETG is improved. The melt tension is significantly increased, and the workability is improved.

Further, by applying the copolyester-based resin composition to sheet molding, the sheet processability can be greatly improved, the range of processing conditions can be significantly widened, and in addition, a thin sheet can be produced. Many advantages can be obtained in terms of molding processing, such as application to calender molding by means of

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA24 AA45 AC10 AE04 BB03 BB04 BB06 BC01 4J002 BD042 BD052 BD062 BD072 BD082 BD092 BD182 CD163 CF033 CF051 CF061 EH096 EH146 EW046 FD020 FD023 FD0200 FD030

Claims (3)

[Claims] 1. A repeating unit comprising a dicarboxylic acid component in which terephthalic acid is at least 90 mol% or more and a glycol component in which 1,4-cyclohexanedimethanol is 10 to 95 mol% and ethylene glycol is 90 to 5 mol%. Amorphous copolyester 99-50% by weight
And a copolyester resin composition comprising 1 to 50% by weight of a polyvinyl chloride resin. 2. A polyvinyl chloride resin composition in which the polyvinyl chloride resin is blended with 100 parts by weight of a plasticizer per 100 parts by weight of the polyvinyl chloride resin.
The copolyester resin composition as described in the above. 3. A sheet comprising the copolyester resin composition according to claim 1 or 2.