JP3453305B2 - Sheet-shaped molded product - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a sheet-like molded article made of a polyester block copolymer composition having excellent flexibility, transparency, heat resistance and chemical resistance, and a method for producing the same. More specifically about the production method, by molding a specific polyester block copolymer resin composition into a sheet form from a molten state under specific temperature conditions, a sheet excellent in flexibility, transparency, heat resistance, and chemical resistance. The present invention relates to a method for producing a molded article.

[0002]

2. Description of the Related Art Conventionally, a vinyl chloride sheet has been used as a sheet made of a thermoplastic resin and having flexibility and excellent transparency. However, vinyl chloride is not only environmentally problematic due to the generation of dioxins when incinerated, but also the range of use was limited due to stains on the surface of molded products due to seepage of plasticizer and low heat resistance of molded products. .

Therefore, products made of transparent olefin resin, which has a low environmental load, and made into a sheet, have begun to be used.
However, there are cases in which the properties are insufficient due to surface scratching properties, hot stamping properties, and the like. In particular, when a transparent sheet is used as a table cloth or the like, there is a problem that when the kettle heated to about 100 ° C. is directly placed, the remaining portion of the kettle remains on the sheet.

A transparent sheet of urethane resin is also used, but it is not good because of poor weather resistance and stain resistance.

[0005]

An object of the present invention is to obtain a sheet-like molded article which is excellent in flexibility, transparency, heat resistance and non-adhesiveness and has a low environmental load.

[0006]

[Means for Solving the Problems] The inventors of the present invention have excellent flexibility, transparency and non-adhesiveness by molding a specific polyester block copolymer resin composition into a sheet under specific conditions. The inventors have found that a sheet-shaped molded product can be obtained, and completed the present invention.

That is, the present invention relates to A. 20 to 80% by weight of a hard segment, which is polybutylene terephthalate, which contains terephthalic acid as an acid component of 60 mol% or more and tetramethylene glycol as a diol component of 60 mol% or more, and an aromatic dicarboxylic acid
100% by weight of a polyester block copolymer (A) comprising 80 to 20% by weight of a soft segment, which is a polyester having a long-chain diol having 5 to 12 carbon atoms as a diol component, in an amount of 0 mol% or more as an acid component, and B. 100 parts by weight of a resin component consisting of 0 to 100% by weight of polybutylene terephthalate (B) and C.I. A saturated fatty acid Na salt (C) having 16 or more carbon atoms is contained in an amount of 0.5 to 5 parts by weight with respect to 100 parts by weight of a resin component, and a haze of a sheet-shaped molded product having a thickness of 100 μm is 1
It is a sheet-like molded product molded from a polyester block copolymer resin composition having a content of 0% or less. Hereinafter, the present invention will be described in detail.

[Polyester block copolymer (A)]
The polyester block copolymer (A) comprises a hard segment (a) and a soft segment (b).

[Hard segment (a)] The hard segment (a) is a polybutylene terephthalate containing terephthalic acid as an acid component of 60 mol% or more and tetramethylene glycol as a diol component of 60 mol% or more. This polybutylene terephthalate has crystallinity.

The terephthalic acid component can be derived from its ester-forming derivative and the tetramethylene glycol component can be derived from its ester-forming derivative.

These terephthalic acid and tetramethylene glycol may each independently form polybutylene terephthalate, or may form polybutylene terephthalate together with other copolymerization components.

As the copolymerization component, examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid and sebacic acid; alicyclic rings such as cyclohexanedicarboxylic acid. Group dicarboxylic acids can be exemplified.

Examples of the diol component as the copolymerization component include aliphatic glycols such as ethylene glycol and hexamethylene glycol; alicyclic diols such as cyclohexanedimethanol; and aromatic diols such as bisphenol A and hydroquinone. it can.

The proportion of the copolymerization component in the hard segment (a) is 40 mol% or less of the total dicarboxylic acid component and the total diol component for the dicarboxylic acid component and the diol component, respectively. If it exceeds 40 mol%, the crystallinity decreases and molding becomes difficult.

When an aliphatic dicarboxylic acid is copolymerized as the dicarboxylic acid component, the copolymerization ratio is 1 of all dicarboxylic acid components in order to maintain good transparency and heat resistance.
It is preferably less than 0 mol%.

[Soft segment (b)] The soft segment (b) is an aromatic polyester having an aromatic dicarboxylic acid as an acid component of 60 mol% or more and a long-chain diol having 5 to 12 carbon atoms as a diol component. . As the aromatic polyester, an aromatic polyester having a polymer melting point of 100 ° C. or lower, preferably 50 ° C. or lower, or amorphous is preferable.

To make it amorphous, it is preferable to use isophthalic acid as the aromatic dicarboxylic acid.

Further, in order to improve impact resistance in a low temperature atmosphere, it is effective to use an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid together as an acid component. In this case, in order to maintain transparency, the amount of the aliphatic dicarboxylic acid copolymerized is preferably 0 to 25 mol% of the total dicarboxylic acid components, and more preferably 0 to 10 mol%.

In order to maintain transparency, the aliphatic dicarboxylic acid is preferably a linear aliphatic dicarboxylic acid having 8 or less carbon atoms, and sebacic acid having 8 carbon atoms and adipic acid having 6 carbon atoms are particularly preferable.

[Polyester Block Copolymer] In the polyester block copolymer (A), the hard segment (a) is 20 to 80% by weight and the soft segment is 80 to 20% by weight. If the hard segment (a) is more than this, the resulting polyester block copolymer (A) becomes hard and difficult to use. When the soft segment (b) is more than this, the crystallinity of the obtained polyester block copolymer (A) is lowered, molding becomes difficult, and a sticky feeling appears.

The segment lengths of the hard segment (a) and the soft segment (b) of the polyester block copolymer (A) are preferably expressed in terms of molecular weight of 50.
It is 0 to 7,000, more preferably 800 to 5,000.

Although it is difficult to directly measure this segment length, for example, the composition of the polyester of the hard segment (a) and the sosoft segment (b) and the melting point and the melting point of the polyester composed of the components constituting the hard segment (a) It can be estimated from the melting point of the obtained polyester block copolymer (A) using the Flory's equation.

The method for producing such a polyester block copolymer is as follows. A polyester constituting the soft segment (a) and a polyester constituting the hard segment (b) are respectively produced, and both are melt mixed to obtain a polyester having a melting point of the hard segment. There is also a way to keep it low.

Since this melting point changes depending on the mixing temperature and time, it is preferable to add a catalyst deactivator such as phosphorus oxyacid to deactivate the catalyst when the desired melting point is reached. For example, phosphoric acid, phosphoric acid, organic sulfonic acid, etc., which are equimolar or more, preferably 1.2 times or more and less than 3 times the number of metal atoms of titanium or tin compound added as a catalyst, are added.

[Polybutylene terephthalate (B)] Polybutylene terephthalate (B) is a polyester composed of terephthalic acid as a main dicarboxylic acid component and tetramethylene glycol as a main diol component. Mainly means 60 mol% or more, preferably 80 mol% or more of the total dicarboxylic acid component or the total diol component.

A copolymerization component can be copolymerized with the polybutylene terephthalate (B) within a range not impairing transparency.

As the dicarboxylic acid component as a copolymerization component, isophthalic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, phenylmethanedicarboxylic acid, diphenylketonedicarboxylic acid, diphenylsulfidedicarboxylic acid,
Examples thereof include diphenyl sulfone dicarboxylic acid.

As a glycol component as a copolymerization component, ethylene glycol, propylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, neopentyl glycol, cyclohexanedimethanol,
Examples include diethylene glycol, polyethylene glycol, bisphenol A, resorcin, hydroquinone, dihydroxydiphenyl and the like.

Examples of the copolymerizable oxycarboxylic acid component include oxybenzoic acid and hydroxydiphenylcarboxylic acid. A compound having three or more functional groups, such as glycerin, trimethylpropane, pentaerythritol, and trimellitic acid, may be copolymerized as long as the characteristics are not impaired.

The polybutylene terephthalate (B) can be manufactured by a conventionally known manufacturing method.

Polybutylene terephthalate (B) has an intrinsic viscosity of 0.5 to 1.5, preferably 0. 0 when measured with orthochlorophenol as a solvent at a temperature of 35 ° C.
It is 6 to 1.2.

The polybutylene terephthalate (B) is blended in an amount of 0 to 100 parts by weight, preferably 11 to 66 parts by weight, based on 100 parts by weight of the polyester block copolymer (A). If the amount of polybutylene terephthalate (B) is larger than this, the transparency is impaired, and if it is small, the blocking property deteriorates.

[Saturated Fatty Acid Na Salt (C)] In the present invention, a saturated fatty acid Na salt having 16 or more carbon atoms, preferably 16 or more and 35 or less carbon atoms is blended. When a fatty acid partially having an unsaturated bond is used as the fatty acid, the thermal stability is poor. If the saturated fatty acid has less than 16 carbon atoms, bleed-out may occur and the surface of the sheet-shaped molded article may be whitened. If the saturated fatty acid has more than 35 carbon atoms, the affinity with the polymer is poor and the transparency is lowered, which is not preferable. As the saturated fatty acid Na salt (C), Na palmitate and Na montanate are preferable.

The saturated fatty acid Na salt (C) is 0.5 to 5 parts by weight with respect to 100 parts by weight of the resin component consisting of 100% by weight of the ester block copolymer (A) and 0 to 100% by weight of polybutylene terephthalate (B). Parts by weight. If it is less than this, the transparency which is the effect of the present invention does not appear, and if it is more than this, the physical properties such as transparency, moldability and mechanical properties deteriorate.

[Additives] Various additives can be added to the polyester block copolymer resin composition of the present invention within a range not deteriorating the transparency, mechanical properties and weather resistance which are the objects of the present invention. . Examples of the additives include various lubricants such as colorants, ultraviolet absorbers, various stabilizers, antistatic agents, release agents and the like. Usually, these additives are added for the purpose of improving moldability. Further, an amorphous polymer can be blended. Examples of the amorphous polymer include polycarbonate and polyarylate.

[Production Method] The polyester block copolymer resin composition of the present invention can be produced by a conventionally known method. As the method for producing the composition, a method of mixing saturated fatty acid Na salt and other additives with the polymer component in the molten state after the condensation polymerization, and pelletizing each polymer component obtained by the condensation polymerization individually A method in which the saturated aliphatic Na salt and other additives are melt-mixed with the pellets using a screw extruder or the like. Further, all or a part of the components can be blended when the sheet-shaped molded product is molded.

As a method for producing a sheet-shaped molded article from the polyester block copolymer resin composition, the resin composition is melted at a temperature equal to or higher than the melting point, and then the resin in a molten state is discharged from a slit-shaped mouth portion. Then, after being formed into a sheet shape, it is cooled and solidified. In the present invention, the temperature conditions at this time are as follows. T1> Tm + 5 ° C., T1>T2> Tdc 40 ° C. <T3 <80 ° C. [wherein, in the above formula, Tm: melting point (° C.) of resin composition Tdc: crystallization temperature (° C.) T1 of resin composition during temperature decrease T1 : Temperature of the resin composition when discharged from the die (° C) T2: Temperature of the resin composition when in contact with the cooling roll or the cooling plate (° C) T3: Surface temperature of the cooling roll or the cooling plate (° C) Is. ]

In the above manufacturing method, a T-die or I-die film forming machine in which a slit-shaped die is installed at the tip of the extruder is used.

Under the above temperature conditions, when T2 is Tdc or less, transparency is impaired. When T3 is 40 ° C or lower, transparency is excellent, but tackiness occurs in the sheet, and the sheet-shaped molded product is wound around a paper tube having an outer diameter of 12 cm with a tension of 2 kgf,
When the film is rewound after being left for a period of time, blocking may occur to make rewinding difficult, and the transparency may decrease with time. When T3 is 80 ° C. or higher, the sheet is whitened and the transparency is impaired.

[0040]

EXAMPLES In the examples, the production and evaluation of a sheet-shaped molded article were carried out according to the following methods. The raw materials of the composition used for the production of the sheet-shaped molded product are as follows.

[Manufacture of Sheet-Molded Article] A chip-shaped resin having the composition described in the examples is fed into a twin-screw extruder (TEX manufactured by Japan Steel Works).
In (30), the mixture was melt-kneaded, extruded, and pelletized with a strand cutter. Thickness of the pellets was 1 at a take-up speed of 10 m / min while controlling the casting drum temperature with a hot water temperature controller using a 40 mm single-screw extruder T-die.
A sheet-shaped molded product of 00 μm and a width of 28 cm was obtained.

However, in Table 1, the amount of the fatty acid Na salt (unit: phr) is the amount of the fatty acid Na salt based on 100 parts by weight of the total amount of the resin components, and is a unit of parts by weight.

[Blocking Property] The sheet-shaped molded product was wound around a paper tube having an outer diameter of 12 cm with a tension of 2 kgf, left for 24 hours, and then rewound. In this rewinding, the case where it was difficult to rewind due to adhesion was evaluated as [X], and the case where rewinding was possible at a winding tension of 2 kg or less was evaluated as [O].

[Haze] The amount of scattered light (haze:%) of the sheet-shaped molded product was measured with a haze meter manufactured by Nippon Seimitsu Kagaku.

[Weather resistance] Acceleration of ultraviolet deterioration was evaluated according to JIS A-1415 sunshine test method. Temperature 63
It was carried out for 1000 hours in an atmosphere at 50 ° C and a humidity of 50% to evaluate the change in appearance.

[Stainability] Stain resistance was evaluated according to JIS K6902. Coffee was used as the contaminant.

[Intrinsic viscosity] In orthochlorophenol,
It is an intrinsic viscosity measured at 35 ° C.

[Polybutylene terephthalate (PB
T)] Teijin Ltd. polybutylene terephthalate (intrinsic viscosity 0.7) was used.

[Production of Polyester Block Copolymer 1] 175 parts of dimethyl isophthalate, 23 parts of dimethyl sebacate and 140 parts of hexamethylene glycol were subjected to transesterification reaction with a dibutyltin diacetate catalyst and then polycondensed under reduced pressure. An amorphous polyester (a) having an intrinsic viscosity of 1.06 and having no endothermic peak due to the melting of crystals was obtained by the DSC method. To this polyester, a polybutylene terephthalate (a) chip having an intrinsic viscosity of 0.98, which was separately obtained by polycondensation, was dried and added in an amount of 107 parts.
After further reacting at 240 ° C. for 45 minutes, 0.1 part of phenylphosphonic acid was added to stop the reaction to obtain a chip-shaped polyester block copolymer. The polyester block copolymer had a melting point of 190 ° C. and an intrinsic viscosity of 0.93.

[Production of Polyester Block Copolymer 2] 125 parts of dimethyl isophthalate, 54 parts of dimethyl sebacate, and 140 parts of hexamethylene glycol were transesterified with a dibutyltin diacetate catalyst and polycondensed under reduced pressure. A polyester having an intrinsic viscosity of 1.06 was obtained.
This polyester was blocked in the same manner as in Reference Example 1 to obtain a chip-shaped polyester block copolymer.

[Production of Polyester Block Copolymer 3] 28 parts by weight of dimethyl terephthalate, 18 parts by weight of tetramethylene glycol, and 40 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 1400 are transesterified by a conventional method, and then the pressure is reduced. Polymerization reaction was performed below to obtain a chip-shaped polyester block copolymer. The intrinsic viscosity of the polyester block copolymer was 1.41.

[Thermoplastic Urethane Resin] Miractolan E385 manufactured by Nippon Miractolan Co., Ltd. was used.

[Examples 1 to 4 and Comparative Examples 1 to 6] Table 1
A sheet-shaped molded article having the composition described in 1. was produced according to the above method, and the characteristics were evaluated by the above method. The results are shown in Table 1.
In Examples and Comparative Examples, Tm (melting point of resin composition), Tdc (crystallization temperature of resin composition at the time of temperature decrease),
Table 1 shows T1 (temperature of the resin composition when discharged from the die), T2 (temperature of the resin composition when in contact with the cooling roll or the cooling plate), and T3 (surface temperature of the cooling roll or the cooling plate). It was as described in.

[0054]

[Table 1]

In Examples 1 to 4, excellent transparency, weather resistance,
The stainability was good.

When the molding temperature conditions were changed as in Comparative Example 1, problems such as decreased transparency and development of tackiness occurred.

When the blending amount of PBT was large, the flexibility was lowered and the transparency was greatly lowered.

When a polytetramethylene glycol block copolymer, which is widely used, is used as the polyester block copolymer, the transparency and the weather resistance and stain resistance are poor.

Comparative Example 4 was a case where the fatty acid Na salt was not added, but the transparency was not expressed.

In Comparative Example 5, polyurethane was used, but it was excellent in transparency but was inferior in weather resistance and discolored to dark brown.

Comparative Example 6 is a saturated fatty acid Na salt, which is Na of myristic acid in which the straight chain portion of the saturated fatty acid has 12 carbon atoms.
This is the case when salt is added. When the surface of the sheet was observed after aging, white turbidity and fatty acid bleedout were observed.

[0062]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a sheet-shaped molded article having excellent transparency, non-adhesiveness, weather resistance and stain resistance. This sheet-shaped molded product has a characteristic that it does not generate dioxins when it is incinerated and has a low environmental load.

Claims (2)

(57) [Claims] 1. A. 20 to 80% by weight of a hard segment which is polybutylene terephthalate having terephthalic acid as an acid component of 60 mol% or more and tetramethylene glycol as a diol component of 60 mol% or more, and an aromatic dicarboxylic acid of 60 mol% or more As a component, carbon number 5
100% by weight of a polyester block copolymer (A) composed of 80 to 20% by weight of a soft segment, which is a polyester having a long-chain diol of 12 as a diol component, and B. 100 parts by weight of a resin component consisting of 0 to 100% by weight of polybutylene terephthalate (B) and C.I. A saturated fatty acid Na salt (C) having 16 or more carbon atoms is contained in an amount of 0.5 to 5 parts by weight with respect to 100 parts by weight of a resin component, and a haze of a sheet-shaped molded product having a thickness of 100 μm is 1
A sheet-like molded product molded from a polyester block copolymer resin composition, which is 0% or less. 2. Production of a sheet-shaped molded product in which a resin composition is melted at a temperature equal to or higher than a melting point, a molten resin is discharged from a slit-shaped die part, molded into a sheet, and then cooled and solidified. The method for producing a sheet-shaped molded article according to claim 1, wherein each temperature condition satisfies the following conditions. T1> Tm + 5 ° C., T1>T2> Tdc 40 ° C. <T3 <80 ° C. [where, in the above formula, Tm: melting point of the resin composition Tdc: crystallization temperature of the resin composition at the time of temperature decrease T1: discharge from the die part The temperature T2 of the resin composition at the time of: is the temperature T3 of the resin composition when it comes into contact with the cooling roll or the cooling plate: the surface temperature of the cooling roll or the cooling plate. ]