JP3369959B2 - Polyester resin composition, method and apparatus for producing molded article - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a crystallized polyester (A), particularly polyethylene terephthalate (A-).
A method for producing a polyester composition by mixing 1) with an amorphous polyester (B), especially an amorphous polyester (B ′), particularly polyethylene isophthalate (B-1), and compositions thereof TECHNICAL FIELD The present invention relates to a method for producing a molded article by using the method and an apparatus used for the method.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Molded products of polyethylene terephthalate, which is a crystallized polyester, especially biaxially stretched molded products, have mechanical strength, rigidity, heat resistance, chemical resistance, oil resistance,
Due to its excellent properties such as transparency, it is often used as a material for films, sheets, containers and the like.

However, the usual molded article mainly composed of polyethylene terephthalate does not have sufficient gas barrier properties. For example, a bottle manufactured from a resin mainly composed of polyethylene terephthalate, when a considerable amount of time has passed since the beverage was filled, in the case of a carbonated beverage, carbon dioxide gas escapes and the gas pressure at the time of filling is not maintained, or The contents were sometimes altered due to oxygen permeation from the outside.

Therefore, in order to improve the gas barrier property of polyethylene terephthalate, it has been proposed to blend polyethylene terephthalate with polyethylene isophthalate (for example, Japanese Patent Publication No. 1-49384).
No. 5-13987, etc.).

Such a composition of polyethylene terephthalate and polyethylene isophthalate or a molded product thereof is mixed in various known methods, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, and the like, followed by an extruder. It is obtained by melt-kneading in a molding machine such as an injection molding machine and molding the kneaded product into a predetermined shape.

Hygroscopic raw material plastics such as polyethylene terephthalate and polyethylene isophthalate used for producing such molded articles must be dried before being put into a molding machine. this is,
This is because if the resin contains a large amount of water, it will be hydrolyzed in the molding machine to lower the molecular weight, and the moldability and the physical properties of the molded product will deteriorate.

In such a drying process, the crystalline polymer can be dried at a high temperature. For example, the glass transition temperature (Tg) of polyethylene terephthalate is usually 70.
The drying temperature is usually 160 ° C or higher.

However, amorphous polymers such as polyethylene isophthalate need to be dried at a low temperature of, for example, about 50 ° C. for a long time because the resins are fused to each other when they are dried at a high temperature.

Further, when trying to blend the polyethylene terephthalate dried at high temperature and the polyethylene terephthalate dried at low temperature as they are, the polyethylene isophthalate is melted by the heat of the polyethylene terephthalate dried at high temperature to form a lump of the resins, and the blender is blended. There is a problem that the inside of the molding machine is clogged with the hopper of the molding machine or the like to affect the operation of the molding machine, or a certain amount of amorphous polyester is not contained in the molded product even if the molding is successful.

Therefore, when blending with an amorphous polymer, the polyethylene terephthalate resin had to be once cooled to a temperature at which polyethylene isophthalate was not fused before blending.

This method requires a facility for cooling polyethylene terephthalate, a facility for storing cooled polyethylene terephthalate, or the like. Further, in this method, since the raw material polyethylene terephthalate is not preheated, there is a problem that the plasticizing time in the molding machine cannot be shortened and the productivity is lowered.

Further, Japanese Patent Publication No. 4-10407 discloses that
Disclosed is an invention of an automatic feeder for a masterbatch when a masterbatch of a resin containing a high concentration of an additive such as a colorant, a stabilizer, an antistatic agent, a flame retardant is mixed with a resin containing no such additive. Has been done.

However, in this publication, there is no description concerning the mixing of resins having remarkably different melting points or glass transition temperatures, and this Japanese Patent Publication No. 4-10407.
If the device disclosed in the publication is used as it is, it will be clogged in the hopper, the metering time will vary greatly, and stable production and continuous molding cannot be performed.

The problem in producing the above polyester composition is not limited to the mixing of polyethylene terephthalate and polyethylene isophthalate, but other crystalline polyesters and amorphous polyesters even in the amorphous state. It is also a problem that occurs when a composition is prepared by mixing

[0015]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and provides a polyester resin composition excellent in gas barrier property, transparency, heat resistance and the like by an industrially advantageous method. The object of the present invention is to provide a stable manufacturing method.

Another object of the present invention is to provide a method for stably producing a molded article using the polyester resin composition produced as described above by an industrially advantageous method.

[0017]

SUMMARY OF THE INVENTION In the method for producing polyester of the present invention, a resin supply port is provided near one end, and a cylinder having a heating means for plasticizing the supplied resin and the resin supply port are provided. Using a resin melt mixing device having a screw that rotates so that the molten resin moves in the cylinder from the end to the other end, the crystalline polyester (A) in an amorphous state with 99 to 60% by weight is used. A method for producing a polyester resin composition [the total amount of (A) and (B) is 100% by weight] by bringing 1 to 40% by weight of polyester (B) into contact with each other and mixing them in a molten state. Of the amorphous polyester (A) having a temperature higher than the glass transition temperature of the polyester (B) and the polyester (B) in the amorphous state have reached the resin supply port. Of the amorphous polyester (B) at the position where the polyester (A) crystallized on the cylinder side and the polyester (B) in the amorphous state start to come into contact with each other from the position where a substantial thermal influence is exerted on the polyester (B). ) Is introduced into the cylinder from the resin supply port.

Here, the position at which the contact between the crystallized polyester (A) and the amorphous polyester (B) is started can reach the inside of the cylinder before the amorphous polyester (B) is welded. It is preferable that the position is the same, and the amorphous polyester (B) is an amorphous polyester (B ′), and the crystallized polyester (A) is polyethylene terephthalate (A-1). It is preferable that the amorphous polyester (B ′) is polyethylene isophthalate (B-1). Further, a predetermined amount of the amorphous polyester (B) is added to the crystallized polyester (A) being supplied into the cylinder when the screw measures the resin. It is preferable that the polyester (B) in the crystalline state is supplied so as to start contact with the raw material supply portion of the cylinder or inside the cylinder, and both are melt-mixed in the cylinder, and the polyester (B) in the amorphous state is crystallized. The apparatus for supplying the converted polyester (A) has a nozzle for supplying the amorphous polyester (B) to the raw material supply part of the cylinder, and the outer diameter of the thinnest part of the nozzle is the raw material supply port. It is preferably 10 to 85% of the inner diameter, and the lower tip of the nozzle of the feeder for the amorphous polyester (B) is located at the raw material feed section of the cylinder. It is preferable that the lower tip of the nozzle of the supply device for the amorphous polyester (B) is located directly above the screw, and the resin melt kneading device is an extrusion molding machine or an injection molding machine. Is characterized by.

Further, the method for producing a molded article comprising the polyester resin composition of the present invention comprises a cylinder having a resin supply port near one end and a heating means for plasticizing the supplied resin, and the resin. Crystallized polyester (A) 99 was obtained by using a resin melt mixing device having a screw that rotates so that the molten resin moves in the cylinder from the end where the supply port is provided to the other end.
-60% by weight and amorphous polyester (B) 1-40
A method for producing a molded article, which comprises shaping a polyester resin composition [total of (A) and (B) is 100% by weight] into a predetermined shape by bringing the polyester resin composition into contact with and mixing in a molten state, The crystallized polyester (A) having a temperature higher than the glass transition temperature of the crystalline polyester (B) and the amorphous polyester (B) reach the resin supply port, and the amorphous polyester (B ), The amorphous polyester (B) is supplied to a position where the crystallized polyester (A) and the amorphous polyester (B) start to contact each other on the cylinder side from the position where a substantial thermal effect is exerted on Is introduced into the cylinder from the resin supply port.

Here, the amorphous polyester (B)
Is preferably an amorphous polyester (B ′), the crystallized polyester (A) is polyethylene terephthalate (A-1), and the amorphous polyester is
It is preferably polyethylene isophthalate (B-1).

Further, it is preferable that the molded product of the polyester composition is a preform, and it is preferable that the preform is stretch blow-molded to produce a bottle made of the polyester composition.

The thermoplastic resin supply device of the present invention is
Means for supplying a crystalline thermoplastic resin (α),
Means for supplying an amorphous thermoplastic resin (β) having a softening temperature or melting temperature lower than that of the thermoplastic resin (α) and a hopper are provided, and the thermoplastic resin is supplied in the vicinity of one end. A cylinder having a mouth and a heating means for plasticizing the supplied thermoplastic resin, and a thermoplastic melted in the cylinder from the end where the thermoplastic resin supply port is provided to the other end. A thermoplastic resin supply device connected to a resin supply port of a resin melt-mixing device having a screw that rotates so that the resin moves, wherein a means for supplying the crystalline thermoplastic resin (α) is provided. A thermoplastic resin (α) supply tank and a nozzle for supplying the thermoplastic resin (α), and the thermoplastic resin (α) is connected through the nozzle so that the thermoplastic resin (α) can be supplied to the hopper, Conclusion For supplying the amorphous thermoplastic resin (β) having a softening temperature or melting temperature lower than that of the thermoplastic resin (α) is a thermoplastic resin (β) supply tank and the thermoplastic resin (β). ) For supplying the thermoplastic resin (β) to the hopper so that the thermoplastic resin (β) can be supplied to the thermoplastic resin supply port through the nozzle. When connecting to the device, the thermoplastic resin (β) supplied from the lower opening end of the nozzle for supplying the thermoplastic resin (β) is not softened or melted by the time it reaches the upper end of the screw, A lower opening end of the nozzle for supplying the thermoplastic resin (β) is provided. Further, this thermoplastic resin supply device, a cylinder having a thermoplastic resin supply port near one end, and a heating means for plasticizing the supplied thermoplastic resin, and the thermoplastic resin supply port are It is preferable to provide a resin melt mixing device having a screw that rotates so that the molten thermoplastic resin moves in the cylinder from the provided end to the other end.

According to the method of the present invention, a high temperature polyethylene terephthalate (A-) obtained by heating and drying the amorphous polyester (B ') among the amorphous polyester (B), especially polyethylene isophthalate (B-1) is used. Amorphous polyester (B) because it is supplied into the cylinder in contact with crystalline polyester, especially polyethylene terephthalate (A-1), at a position that is not affected by the heat from 1) or the heat from the cylinder. Among them, amorphous polyester (B '), especially polyethylene isophthalate (B
-1) does not become lumpy. Further, a crystalline polyester (A) such as polyethylene terephthalate (A-1)
Even when the resin is heated and dried and is hot, a crystalline polyester (A) such as polyethylene terephthalate (A-1) and an amorphous polyester (B) near the resin supply port of the cylinder, among them, the amorphous polyester ( B '), particularly polyethylene isophthalate (B-1), so that amorphous polyester (B') is amorphous polyester (B '), especially polyethylene isophthalate (B-1) The material does not stop the supply of resin. Furthermore, according to the method of the present invention, it is possible to produce a composition and a molded article having high uniformity, the molded article has high properties such as gas barrier properties, and the generation amount of acetaldehyde and the like due to decomposition of the resin is small. .

[0024]

DETAILED DESCRIPTION OF THE INVENTION The method for producing the polyester composition of the present invention and the method for producing a molded article made of the composition will be specifically described below.

The production method of the present invention is a method of producing a polyester resin composition from a crystallized polyester (A) and an amorphous polyester (B). In the present invention, the “crystallized polyester” is a polyester produced through a preliminary crystallization step, and is a polyester produced by a solid phase polymerization reaction, if necessary.

Crystallized Polyester (A) The crystallized polyester (A) used in the present invention is
Usually, it is formed from a dicarboxylic acid component unit derived from a dicarboxylic acid and a component unit derived from a diol, but the polyester (A) crystallized in the present invention
Examples of dicarboxylic acids that form phthalic acid include terephthalic acid, phthalic acid (orthophthalic acid), isophthalic acid, and 2,6-
Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid , Aliphatic dicarboxylic acids such as decanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

These dicarboxylic acids may be ester derivatives thereof. Further, these may be a combination of two or more kinds. The diol units constituting the crystallized polyester (A) have a total of 100 units.
80 mol% ethylene glycol unit
As described above, it is desirable that the content is 85 to 100 mol%.

Examples of other diols capable of forming the crystallized polyester (A) of the present invention include diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, propylene glycol, butanediol, pentanediol. ,
Neopentyl glycol, hexamethylene glycol,
Aliphatic glycols such as dodecamethylene glycol,
Alicyclic glycols such as cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-
Bis (2-hydroxyethoxy) benzene, 1,4-bis (2-
Glycols containing aromatic groups such as (hydroxyethoxy) benzene, bisphenols, hydroquinone, 2,2-
Examples thereof include aromatic diols such as bis (4-β-hydroxyethoxyphenyl) propane.

These diols may be ester derivatives thereof. Further, these diols may be a combination of two or more kinds. Of these, diethylene glycol and cyclohexanedimethanol are preferable as the other diol.

Further, the crystallized polyester (A) used in the present invention has a polyfunctional carboxylic acid having 3 or more carboxyl groups or 3 or more hydroxy groups as long as the object of the present invention is not impaired. It may contain a unit derived from a polyfunctional alcohol, for example, trimesic acid, polyfunctional carboxylic acids such as pyromellitic dianhydride, glycerin, 1,1,1-trimethylolethane,
It may contain units derived from polyfunctional alcohols such as 1,1,1-trimethylolpropane, 1,1,1-trimethylolmethane and pentaerythritol. It may also contain units derived from polyglycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol.

The crystallized polyester (A) used in the present invention is substantially linear, which is confirmed by dissolution of the crystallized polyester (A) in o-chlorophenol.

The crystallized polyester (A) used in the present invention is not particularly limited, for example, at 25 ° C.,
The intrinsic viscosity [η] measured in o-chlorophenol is
It is desired to be 0.5 to 1.0 dl / g, preferably 0.6 to 0.95 dl / g.

Further, this crystallized polyester (A)
The melting point measured by a differential scanning calorimeter (DSC, temperature rising rate 10 ° C / min) is usually 180 to 300 ° C, preferably 210 ° C to 280
℃.

Such a crystallized polyester (A)
Is produced by an esterification or transesterification reaction, a liquid phase polycondensation reaction, and then a solid phase polymerization reaction if necessary.

Such a crystallized polyester (A)
Preferred examples thereof include polyethylene terephthalate (A-1) described below. In the first method for producing a polyester resin composition of the present invention, the crystallized polyester (A) as described above is usually used after a drying step for removing contained water. The temperature of the pellets of the crystallized polyester (A) at this time is usually 100 to 200 ° C., often 130 to 19 ° C.
It is 0 ° C. Then, in the present invention, such a hot pellet is used as it is to produce a polyester resin composition or a molded article.

In the production method of the present invention, the crystallized polyester (A) and the amorphous polyester (B) are mixed. Amorphous Polyester (B) In the present invention, the amorphous polyester (B) means
It is a "polyester produced only by a liquid phase polymerization step without passing through a preliminary crystallization step and a solid phase polymerization step". This polyester is not crystallized and is a transparent pellet.

The polyester (B) also includes an amorphous polyester (B ') such as polyethylene isophthalate (B-1) described later. The amorphous polyester (B) is usually formed of a dicarboxylic acid component unit derived from a dicarboxylic acid and a component unit derived from a diol, but in the present invention, the amorphous polyester ( Examples of dicarboxylic acids forming B) include terephthalic acid, phthalic acid (orthophthalic acid), isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, diphenyl. Aromatic dicarboxylic acids such as dicarboxylic acid and diphenoxyethanedicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid, and alicyclic compounds such as cyclohexanedicarboxylic acid Examples thereof include dicarboxylic acids.

These dicarboxylic acids may be ester derivatives thereof. Further, these may be a combination of two or more kinds. The total amount of the diol units constituting the amorphous polyester (B) is 100
80 mol% ethylene glycol unit
As described above, it is desirable that the content is 85 to 100 mol%.

Examples of other diols capable of forming the amorphous polyester (B) of the present invention include diethylene glycol, triethylene glycol, tetramethylene glycol, trimethylene glycol, propylene glycol, butanediol and pentane. Diol,
Neopentyl glycol, hexamethylene glycol,
Aliphatic glycols such as dodecamethylene glycol,
Alicyclic glycols such as cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-
Glycols containing aromatic groups such as bis (2-hydroxyethoxy) benzene and 1,4- (2-hydroxyethoxy) benzene, bisphenols, hydroquinone, 2,2-bis (4-β-hydroxyethoxyphenyl) propane And aromatic diols.

These diols may be ester derivatives thereof. Further, these diols may be a combination of two or more kinds. Of these, diethylene glycol and cyclohexanedimethanol are preferable as the other diol.

Further, the amorphous polyester (B) used in the present invention contains a polyfunctional carboxylic acid having 3 or more carboxyl groups or 3 or more hydroxy groups as long as the object of the present invention is not impaired. It may contain a unit derived from a polyfunctional alcohol having, for example, trimesic acid, polyfunctional carboxylic acids such as pyromellitic dianhydride, glycerin, 1,1,1-trimethylolethane,
It may contain units derived from polyfunctional alcohols such as 1,1,1-trimethylolpropane, 1,1,1-trimethylolmethane and pentaerythritol.

Further, polyglycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol may be contained. The amorphous polyester (B) used in the present invention is substantially linear, which is confirmed by dissolution of the amorphous polyester (B) in o-chlorophenol.

The amorphous polyester (B) used in the present invention is not particularly limited, but for example, 25 ° C. thereof,
The intrinsic viscosity [η] measured in o-chlorophenol is
It is desired to be 0.5 to 1.0 dl / g, preferably 0.6 to 0.95 dl / g.

Further, this amorphous polyester (B)
The melting point measured by a differential scanning calorimeter (DSC, heating rate 10 ° C / min) is usually 180 ° C to 3 ° C when the melting point is observed.
It is in the range of 00 ° C, preferably 210 ° C to 280 ° C. The amorphous polyester (b) melts or flows at a temperature lower than that of the polyester (A).

Polyester (B) in such an amorphous state
Can be produced by an esterification or transesterification reaction or a liquid phase polycondensation reaction. Amorphous Polyester (B ') The amorphous polyester (B') used in the present invention is
It is a "polyester produced only in the liquid phase polymerization step without passing through the pre-crystallization step and the solid phase polymerization step", and the pellets are crystallized even if the temperature is raised at 10 ° C./min with a differential thermal analyzer. No temperature or melting point is observed, and it shows fluidity at a lower temperature than the polyester (A).

The amorphous polyester (B ') is usually formed of a dicarboxylic acid component unit derived from a dicarboxylic acid and a component unit derived from a diol, but in the present invention, it is in an amorphous state. Examples of dicarboxylic acids that form the polyester (B ') are terephthalic acid,
Phthalic acid (orthophthalic acid), isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,
5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid,
Aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid and other aliphatic dicarboxylic acids, cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, etc. Is mentioned.

These dicarboxylic acids may be ester derivatives thereof. Further, these may be a combination of two or more kinds. Further, the diol units constituting the amorphous polyester (B ') have a total of 10 units.
When it is 0 mol%, it is desirable to contain the ethylene glycol unit in an amount of 80 mol% or more, preferably 85 to 100 mol%.

Examples of other diols capable of forming the amorphous polyester (B ') of the present invention include diethylene glycol, triethylene glycol, tetramethylene glycol, trimethylene glycol, propylene glycol, butanediol, pentanediol. , Neopentyl glycol, hexamethylene glycol, dodecamethylene glycol and other aliphatic glycols, cyclohexanedimethanol and other alicyclic glycols, 1,3-
Bis (2-hydroxyethoxy) benzene, 1,2-bis (2-
Glycols containing aromatic groups such as (hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, bisphenols, hydroquinone, 2,2-bis (4-
and aromatic diols such as β-hydroxyethoxyphenyl) propane.

These diols may be ester derivatives thereof. Further, these diols may be a combination of two or more kinds. Of these, diethylene glycol and cyclohexanedimethanol are preferable as the other diol.

Further, the amorphous polyester (B ') used in the present invention contains a polyfunctional carboxylic acid having 3 or more carboxyl groups or 3 or more hydroxy groups as long as the object of the present invention is not impaired. It may contain a unit derived from a polyfunctional alcohol having, for example, trimesic acid, polyfunctional carboxylic acids such as pyromellitic dianhydride, glycerin, 1,1,1-trimethylolethane, 1,
It may contain units derived from polyfunctional alcohols such as 1,1-trimethylolpropane, 1,1,1-trimethylolmethane and pentaerythritol.

Further, it may have a unit derived from a polyglycol such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Amorphous polyester (B ') used in the present invention
Is substantially linear, which is confirmed by the dissolution of the amorphous polyester (B ') in o-chlorophenol.

The amorphous polyester (B ') used in the present invention is not particularly limited, but for example, 25 ° C. thereof,
The intrinsic viscosity [η] measured in o-chlorophenol is
It is desired to be 0.5 to 1.0 dl / g, preferably 0.6 to 0.95 dl / g.

With respect to the amorphous polyester (B '), the crystallization temperature and the melting point are not observed under the condition of the temperature rising rate of 10 ° C./min even when the differential scanning calorimeter is used as described above.

Examples of the amorphous polyester (B ') include polyethylene isophthalate (B-1) described later. In the production method of the present invention, for example, polyethylene terephthalate (A-1) and polyethylene isophthalate (B
-1) can be mixed.

Polyethylene terephthalate (A-1) Polyethylene terephthalate (A- ) used in the present invention
1) consists of a dicarboxylic acid unit derived from terephthalic acid or its ester derivative and a diol unit derived from ethylene glycol or its ester derivative.

This polyethylene terephthalate (A-
The dicarboxylic acid unit constituting 1) has a total of 10 units.
When it is 0 mol%, it contains terephthalic acid units in an amount of 80 mol% or more, preferably 85 to 100 mol%.

Specific examples of other dicarboxylic acids capable of forming polyethylene terephthalate (A-1) used in the present invention include phthalic acid (orthophthalic acid), isophthalic acid and 2,6-naphthalene. Dicarboxylic acid,
Aromatic dicarboxylic acids such as 2,7-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid And the like, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

These dicarboxylic acids may be ester derivatives thereof. Further, these may be a combination of two or more kinds. Of these, isophthalic acid is preferable as the other dicarboxylic acid.

Polyethylene terephthalate (A-
It is desirable that the diol unit constituting 1) contains an ethylene glycol unit in an amount of 80 mol% or more, preferably 85 to 100 mol% when the total of the units is 100 mol%.

Examples of other diols capable of forming the polyethylene terephthalate of the present invention include diethylene glycol, triethylene glycol, tetramethylene glycol, trimethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, Aliphatic glycols such as hexamethylene glycol and dodecamethylene glycol, alicyclic glycols such as cyclohexanedimethanol,
Glycols and bisphenols containing aromatic groups such as 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, and 1,4-bis (2-hydroxyethoxy) benzene , Hydroquinone, and aromatic diols such as 2,2-bis (4-β-hydroxyethoxyphenyl) propane.

These diols may be ester derivatives thereof. Further, these diols may be a combination of two or more kinds. Of these, diethylene glycol and cyclohexanedimethanol are preferable as the other diol.

Further, the polyethylene terephthalate (A-1) used in the present invention has a polyfunctional carboxylic acid having 3 or more carboxyl groups or 3 or more hydroxy groups as long as the object of the present invention is not impaired. May contain units derived from polyfunctional alcohols, for example, trimesic acid, polyfunctional carboxylic acids such as pyromellitic dianhydride, glycerin, 1,1,1-trimethylolethane, 1,1,1-trimethylol It may contain units derived from polyfunctional alcohols such as propane, 1,1,1-trimethylolmethane and pentaerythritol.

It may also contain units derived from polyglycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol.
Polyethylene terephthalate (A- used in the present invention
1) is substantially linear, which is confirmed by the dissolution of polyethylene terephthalate in o-chlorophenol.

The polyethylene terephthalate (A-1) used in the present invention is not particularly limited, but its intrinsic viscosity [η] measured in o-chlorophenol at 25 ° C. is 0.5 to 1. 0 dl / g, preferably 0.6-0.9
It is desirable that it is 5 dl / g.

Polyethylene terephthalate (A-
The melting point measured by a differential scanning calorimeter (DSC, temperature rising rate 10 ° C / min) of 1) is usually 210 to 265 ° C, preferably 220 ° C.
~ 260 ℃, glass transition temperature (Tg) is usually 50 ~ 1
It is desirable that the temperature is 20 ° C, preferably 60 to 100 ° C.

Such polyethylene terephthalate (A-1) is produced by esterification or transesterification reaction, liquid phase polycondensation reaction, and then, if necessary, solid phase polymerization reaction. Further, in the present invention, a crystalline resin such as polybutylene terephthalate or polyamide can be optionally used instead of polyethylene terephthalate (A-1).

In the method for producing the polyester resin composition of the present invention, the polyethylene terephthalate (A
-1) is usually used after undergoing a step of drying at a temperature not lower than the glass transition temperature. The temperature of the polyethylene terephthalate (A-1) pellets at this time is usually 100.
˜200 ° C., often 130˜190 ° C., and heated to a temperature higher than the glass transition temperature of polyethylene isophthalate (B-1). And in the present invention,
Such a hot pellet is used as it is to produce a polyester resin composition or a molded article.

Polyethylene isophthalate (B-1) Polyethylene isophthalate (B- used in the present invention
1) consists of a dicarboxylic acid unit derived from isophthalic acid or its ester derivative, and a diol unit derived from ethylene glycol or its ester derivative.

This polyethylene isophthalate (B-
The dicarboxylic acid structural unit of 1) has an isophthalic acid unit of 50 mol% or more, preferably 70 mol% or more, and more preferably 80 mol% when the total of the units is 100 mol%.
It is contained in the above amount.

Further, in the polyethylene isophthalate (B-1) used in the present invention, the dicarboxylic acid constitutional unit other than isophthalic acid is 50 mol% or less, preferably 30 mol, as long as the object of the present invention is not impaired. % Or even 20 mol% or less.

Examples of other dicarboxylic acids include phthalic acid (orthophthalic acid), terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, Aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid,
Examples thereof include aliphatic dicarboxylic acids such as azelaic acid and decanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.

These dicarboxylic acids may be ester derivatives thereof. Further, these may be a combination of two or more kinds. The diol constitutional unit of polyethylene isophthalate (B-1) has a total of 100 units.
When the content is mol%, the content of ethylene glycol units is 50 mol% or more, preferably 70 mol% or more, and more preferably 80 mol% or more.

Further, the polyethylene isophthalate (B-1) used in the present invention contains 50 mol% or less, preferably 30 mol% or less, of diol constitutional units other than ethylene glycol as long as the object of the present invention is not impaired. Further, it may be contained in an amount of 20 mol% or less. As the other dicarboxylic acid, terephthalic acid is preferable.

Examples of other diols include aliphatic compounds such as diethylene glycol, triethylene glycol, tetramethylene glycol, trimethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexamethylene glycol and dodecamethylene glycol. Glycols, cycloaliphatic glycols such as cyclohexanedimethanol, 1,2-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) ) Glycols containing aromatic groups such as benzene, bisphenols, hydroquinone, 2,2-bis (4-
and aromatic diols such as β-hydroxyethoxyphenyl) propane.

These diols may be ester derivatives thereof. Further, these diols may be a combination of two or more kinds. Of these, 1,3-bis (2-hydroxyethoxy) benzene and diethylene glycol are preferable as the other diol.

Further, the polyethylene isophthalate copolymer (B) used in the present invention is polyethylene terephthalate (A-) as long as the object of the present invention is not impaired.
It may contain a unit derived from a polyfunctional carboxylic acid having 3 or more carboxyl groups as shown in 1) or a polyfunctional alcohol having 3 or more hydroxy groups. The unit derived from the polyfunctional carboxylic acid and / or the unit derived from the polyfunctional alcohol are each independently 0.05 to 0.4 mol%, preferably 0.1 to 0.35 mol%, and more preferably 100 mol% of the dicarboxylic acid unit. May be contained in an amount of 0.2 to 0.35 mol%.

The intrinsic viscosity [η] of polyethylene isophthalate (B-1) used in the present invention measured at 25 ° C. in o-chlorophenol is 0.5 to 0.95 dl / g, preferably 0.6. It is desirable that the value is ˜0.90 dl / g.

Polyethylene isophthalate (B-
The glass transition temperature measured by the differential scanning calorimeter 1) (DSC, temperature rising rate 10 ° C / min) is usually 40 to 120 ° C, preferably 50 to 100 ° C.

Polyethylene isophthalate (B of the present invention
-1) is the above-mentioned polyethylene terephthalate (A-1)
It can be manufactured by the same manufacturing method as. Also,
In the present invention, instead of polyethylene isophthalate (B-1), amorphous resins such as polycarbonate and polyester polycarbonate resins can be optionally used.

In the method for producing the polyester resin composition of the present invention, the polyethylene isophthalate (B
-1) is usually used after undergoing a process of drying at a temperature below the glass transition temperature after washing with water.

Polyester Resin Composition The polyester resin composition produced by the first method of the present invention contains 99 to 60% by weight, preferably 98 to 70% by weight, of the crystallized polyester (A) in an amorphous state. It is produced by mixing the polyester (B) in an amount of 1 to 40% by weight, preferably 2 to 30% by weight. In the present invention, the total amount of the crystallized polyester (A) and the amorphous polyester (B) is 100% by weight.

The polyester resin composition produced by the second method of the present invention is a crystallized polyester (A) 99.
-60% by weight, preferably 98-70% by weight and amorphous polyester (B ') 1-40% by weight, preferably 2-
It is produced by mixing in an amount of 30% by weight. In the present invention, the total amount of the polyester (A) and the amorphous polyester (B ') is 100% by weight.

The polyester resin composition produced by the method of the present invention includes other resins, heat resistance stabilizers, weather resistance stabilizers, antistatic agents, lubricants, release agents, nucleating agents, pigments, pigment dispersants. Alternatively, various compounding agents such as dyes which are added to ordinary polyesters can be added within a range that does not impair the object of the present invention.

Method for producing polyester resin composition In the method of the present invention, the crystallized polyester (A) and the amorphous polyester (B) are mixed using a resin melt mixing device.

Crystallized polyester (A) supplied here (polyethylene terephthalate (A-1), etc.)
Is usually dried at a high temperature, and the temperature of the pellets of the crystallized polyester (A) is usually 10
Amorphous polyester (B) reaching 0-200 ℃
It is heated to a temperature higher than the glass transition temperature of.

As shown in FIG. 1, the resin melt mixing apparatus used in the method of the present invention has a resin supply port 11 near one end and a heating means for plasticizing the supplied resin. The cylinder 1 goes from the end where the cylinder 12 and the resin supply port 11 are provided to the other end.
Screw 1 that rotates so that the molten resin moves inside
3 is a resin melt-mixing apparatus having No. 3. Examples of such a resin melt mixing device include an extruder such as a single-screw extruder and a twin-screw extruder, and an injection molding machine.

The resin supply port 11 is usually provided with a hopper 14, and the crystallized polyester (A) is supplied from this hopper 14 through the resin supply port 11 to the resin melting and kneading device. That is, in the method of the present invention, the crystallized polyester (A) dried at high temperature is introduced into the hopper 14, and is supplied from the hopper 14 into the cylinder 12 through the raw material supply port 11 of the cylinder 12. .

On the other hand, the amorphous polyester (B) is
If the temperature of melt flow is low and the contact time between the above and high temperature polyethylene terephthalate is long, it tends to soften and form agglomerates. It may not be supplied inside. Also, the formation of such agglomerates can result in a non-uniform composition.

Therefore, in the present invention, the amorphous polyester (B) having a low melting and flowing temperature is heated by the crystallized polyester (A) dried at a high temperature, and further the resin is added thereto. By the heat from the melt-kneading device, the polyester (B) in the amorphous state is supplied so as to start contact with the crystallized polyester (A) on the cylinder side of the position where a thermal effect can be substantially exerted.

In FIG. 1, the amorphous polyester (B) supply port is arranged above the portion where the hopper 14 is joined to the resin supply port 11 of the resin melt kneader, that is, immediately above the cylinder. It is shown.

That is, in FIG. 1, in addition to the device for supplying the crystallized polyester (A) to the hopper 14, a supply device 15 for the amorphous polyester (B) is provided. 16. A nozzle 16 is extended from the lower end of the nozzle 16. The tip of the nozzle 16 is in an amorphous state slightly above the bottom of the hopper 14, that is, where the hopper 14 and the resin supply port 11 of the resin melt kneader are joined. The polyester (B) is extended to a position where it can be supplied. The nozzle extending from the supply device 15 is preferably thermally insulated.

The shape of the nozzle 16 is not particularly limited,
The cross section may be circular or polygonal. Further, the lower opening end may spread like a trumpet. Further, the thickness of the nozzle 16 may change midway. Also, as shown in FIG.
A heavy pipe structure and a heat insulating structure can also be used. further,
For example, the nozzle 16 can be cooled by interposing a cooling medium 17 such as water between the inner wall and the outer wall of the double pipe.

The outer diameter of the nozzle 16 is not particularly limited as long as it is smaller than the inner diameter of the raw material supply port 11 of the resin melt kneader.
For example, the outer diameter of the lower opening end is preferably 10 to 85% of the inner diameter of the raw material supply port 11 of the cylinder 12.

If the outer diameter of the lower open end is smaller than 10% of the inner diameter of the raw material supply port 11, the amorphous polyester (B) cannot be supplied and cannot be fed steadily into the cylinder at the tip of the nozzle. If it is more than 85%, the crystallized polyester (A) may be clogged in the raw material supply port 11.

The amorphous polyester (B) supplied from the nozzle 16 starts contact with the crystallized polyester (A) at the raw material supply port 11 of the cylinder 12 or inside the cylinder 12, but the screw 13 The closer to, the better. That is, if the crystallized polyester (A) and the amorphous polyester (B) can come into contact with each other as described above, the tip opening (lower opening end) of the nozzle 16 may be above the raw material supply port 11. It is good, but it is usually located at the raw material supply port 11, and the position closer to the screw 13 is preferable unless the driving of the screw 13 is disturbed. It is preferably just above the screw 13. The nozzle 16 may be positioned before or after the polyester (A) is charged into the hopper, but it is usually set before the polyester (A) is charged.

The amorphous polyester (B) is prepared by mixing the crystallized polyester (A) and the amorphous polyester (B) with a screw.
It is discharged from the lower opening end of the nozzle and is put into the molding machine.

It should be noted that, on the upstream side of the nozzle, an amorphous polyester (B) storage part as shown in FIG. 2 and the amorphous polyester (B) are quantitatively transferred from the storage part to the nozzle. It is preferable to have a mechanism.

This mechanism will be described below by taking polyethylene terephthalate (A-1) and polyethylene isophthalate (B-1) as examples. As a mechanism for transferring to such a storage unit and a nozzle, for example, a storage unit as shown in FIG. 2 and a transfer mechanism using air can be exemplified, but polyethylene isophthalate (B-1) is quantitatively transferred. Any mechanism is possible if possible.

Since the distance between the screw 13 and the position where the polyethylene terephthalate (A-1) and the polyethylene isophthalate (B-1) start contacting each other is short, the polyethylene terephthalate (A-1) dried at high temperature is used. ) And the non-crystalline polyethylene isophthalate (B-1) are contacted with each other before the polyethylene isophthalate (B-1) does not weld, but both reach the inside of the cylinder, so that the resins are lumped together during the process. Never be.

Further, another embodiment of the manufacturing method of the present invention will be described with reference to FIG. In this method for producing a polyester resin composition, for example, as shown in FIG.
8, an air carrier 29, a cyclone 30, and a nozzle 16 for supplying polyethylene isophthalate (B-1) are used. In this device, in the supply port 11, in FIG. 2, a storage hopper 27 of polyethylene isophthalate (B-1) and a quantitative transport device 2 are mounted on a bed of a dedicated caster 33 having a control panel 32 of the device.
8 and an air carrier 29 are arranged so that the main body of the automatic feeder can move freely on the floor.

The storage hopper 27 is fixed on the bed of the caster 33 by the columns 34, and the discharge port is provided with a cut gate type supply mechanism 35 which works in conjunction with the fixed quantity transport device 28.

The quantitative transportation device 28 is arranged below the storage hopper 27, and the weight measuring mechanism 36 for measuring the weight of polyethylene isophthalate (B-1) supplied from the storage hopper 27.
And circuit means for converting the measured value into an electric signal to open and close the cut gauge, and circuit means for controlling the transfer amount of polyethylene isophthalate (B-1). The spring feeder 37 is adapted to be capable of supplying polyethylene isophthalate (B-1) intermittently or continuously depending on the type of the resin melt kneading device. The rotation speed of the spring feeder 37 is controlled based on the measuring speed, and polyethylene isophthalate (B-1) is used.
Is supplied in a fixed amount. The polyethylene isophthalate (B-1) from the storage hopper 27 to the quantitative transportation device 28 may be supplied by, for example, a screw feeder, a rotary feeder, air transfer, etc., in addition to the cut gate. Further, there are a volume type and a weight type as a measuring method of polyethylene isophthalate (B-1), but it is possible to adopt the weight type in order to cope with a density change of polyethylene isophthalate (B-1). preferable. Further, a screw feeder, a table feeder, or the like can be used instead of the above spring feeder, but a spring feeder is preferable in consideration of cleaning and handling.

The air carrier 29 is connected to a pipe 39 and a hopper 40 for guiding the pipe 39 to receive the polyethylene isophthalate (B-1) transported from the quantitative transport device 28.
It consists of an ejector mechanism 41. Ejector mechanism 4
Reference numeral 1 is a mechanism for sucking and ejecting air into the pipe 39 using compressed air supplied from a compressor (not shown). Instead of this ejector mechanism, a blower used in a general air transport machine is used. Can also be used.

The cyclone 30 is integrated with the mixer 31, is arranged on the resin melting and kneading device and is detachably fixed, and has an inlet 42 for polyethylene isophthalate (B-1) air-conveyed on its side surface and an upper portion. Air outlet 23, polyethylene isophthalate (B-
It has the drop port of 1). By performing air-solid separation using the cyclone 30, polyethylene isophthalate is less likely to fly around inside the hopper 31, and the contact with the polyethylene terephthalate (A-1) can be performed smoothly.

A nozzle 16 for supplying polyethylene isophthalate (B-1) enters the inside of the hopper 31 and is opened so that the polyethylene isophthalate (B-1) can be supplied from the tip.

The polyethylene isophthalate (B-1) separated from the air by the cyclone 30 falls on a predetermined amount of polyethylene terephthalate (A-1),
While moving through the resin supply port 11, polyethylene terephthalate (A-1) and polyethylene isophthalate (B-
1) begins to contact.

In the method of the present invention, the raw materials other than polyethylene terephthalate (A-1) and polyethylene isophthalate (B-1) are polyethylene terephthalate (A-1) and / or polyethylene isophthalate (B-1). Either of them may be blended and supplied, or may be supplied separately from (A) and (B). For example, powdery ingredients such as magnesium stearate (eg:
The lubricant, etc.) is usually added in advance to the polyethylene isophthalate (B-1) and supplied, and by doing so, the polyethylene isophthalate (B-1) becomes difficult to fuse.

The above explanation applies to polyethylene terephthalate (A-1) and polyethylene isophthalate (B-
1) As an example, in the present invention, a crystallized polyester (A) can be used in place of the polyethylene terephthalate (A-1), and a polyethylene isophthalate (B-1) can be used. In place of), an amorphous polyester (B) or an amorphous polyester (B ′) can be used.

Method for producing molded article of polyester resin composition
Method Furthermore, the method for producing a resin molded article comprising the polyester composition of the present invention is characterized by including the above-mentioned step of producing the polyester composition.

The composition obtained by melt-kneading by the above-mentioned method is usually granulated or crushed into a pellet or powder form, and the pellet or powder is put into another molding machine to obtain a desired molding. You can get the goods. Alternatively, melt kneading and molding may be carried out by one molding machine without going through the form of pellets or powder.

That is, in the method for producing a polyester resin molded product of the present invention, an injection molding machine or an extrusion molding machine is used as the resin melt kneading device, and the vicinity of the raw material supply port provided at one end of these molding machines is used. Then, the polyester (A) crystallized as described above (polyethylene terephthalate (A-1) and the like) and the amorphous polyester (B) and the amorphous polyester (polyethylene isophthalate (B-1) and the like ( B ′) etc.) so that they are in contact with each other, and while melting and kneading both components with these molding machines, the molten resin is sent to the other end of the molding machine in which the mold of the desired shape is arranged, and the other end A molded product is manufactured by pouring the molten resin composition into the mold from.

The composition of the present invention can be used in various shapes such as films, sheets and containers, but it is particularly preferable to use it in the bottle preform 51 as shown in FIG. it can.

For the bottle 52, the polyester resin composition preform obtained by the above method can be manufactured according to the conventionally known biaxial stretch blow molding. For example, a preform obtained by injection molding or a preform obtained by bottoming one end of a pipe obtained by extrusion molding is stretch blow-molded in a mold. The heating temperature of the preform during stretch blow molding is preferably 30 ° C to 120 ° C.

The draw ratio at this time is 6 in area draw ratio.
-15 times, preferably 8-14 times. The temperature of the blowing fluid is 10 to 400 ° C, preferably 20 to 300 ° C.

The blow fluid includes air, nitrogen, steam, water and the like, and preferably air is used. The bottle thus obtained is heat-set after the biaxial stretch blow molding to further improve the heat resistance, so that the crystallinity of the bottle body is 25 to 60%, preferably 25 to 50%. be able to.

In the method of the present invention, as the crystalline resin,
In addition to polyethylene terephthalate (A-1), it is possible to use polybutylene terephthalate resin and the like, and as the amorphous resin, use polycarbonate resin, polyester carbonate resin or the like instead of the above-mentioned resin. You can also

Thermoplastic Resin Supply Device and Thermoplastic Resin Supply
Supply-Melt Mixing Device Next, the thermoplastic resin supply device and the thermoplastic resin supply-melt mixing device of the present invention will be described.

The thermoplastic resin supply device of the present invention comprises a crystalline thermoplastic resin (α) and a thermoplastic resin (β) having a different softening temperature or melting temperature from the thermoplastic resin (α).
Is a device for supplying and to the melt mixing device.

As already explained in the case of the above-mentioned method for producing a polyester resin composition, when at least two kinds of thermoplastic resins having different softening temperatures or melting temperatures are supplied to the melt mixing apparatus, moisture absorbed The softening temperature or melting temperature of the crystalline thermoplastic resin (α) that softens or melts at a higher temperature according to various purposes such as removal, and the softening temperature or melting temperature of the amorphous thermoplastic resin (β) that softens or melts at a lower temperature. Attempting to heat-dry at a higher temperature, simply blend the thermoplastic resin (α) at a temperature higher than the softening temperature or melting temperature of the thermoplastic resin (β) with the thermoplastic resin (β), and supply it to the melt mixing device. In that case, agglomerates are formed before reaching the supply port of the melt mixing device, and various problems occur.

Therefore, in such a case, it is necessary to supply the thermoplastic resin (β) to the vicinity of the supply port of the melt-mixing device while avoiding thermal influence from the heated thermoplastic resin (α). There is.

The thermoplastic resin supply apparatus of the present invention will be described with reference to FIG. The thermoplastic resin supply device of the present invention comprises means 53 for supplying a crystalline thermoplastic resin (α) that softens or melts at a higher temperature than the amorphous thermoplastic resin (β). . Supply means 53
Has a supply tank 54 and a nozzle 55 for supplying the thermoplastic resin (α). The nozzle 55 is connected to the hopper 14 so that the thermoplastic resin (α) can be supplied. The connection method is the nozzle 55 and the hopper 1.
4 and 4 may be inseparably connected integrally, or may be detachably connected by some means such as a screw, a bolt and a nut.

Further, also in the case of the supply tank 54 and the nozzle 55, both may be inseparably integrated, or may be detachably connected.
Although FIG. 1 shows the case where the nozzle 55 is connected to the upper flat surface of the hopper 14, the nozzle 55 may be connected to the side surface of the hopper 14.

The thermoplastic resin supply device of the present invention comprises means 56 for supplying an amorphous thermoplastic resin (β) which is softened at a temperature lower than that of the thermoplastic resin (α). The supply means 56 has a supply tank 15 and a nozzle 16 for supplying the thermoplastic resin (β). The nozzle 16 is connected to the hopper 14 so as to supply the thermoplastic resin (β) to the thermoplastic resin supply port 11. The connection method may be such that the nozzle 16 and the hopper 14 are integrally connected in series and the nozzle 16 may be extended inside the hopper 14, or
A hopper 14 having a nozzle 16 that can be connected to an external nozzle 16 therein and an external nozzle 16 can be removed by some means such as a screw, a bolt and a nut so that the inner and outer nozzles abut each other. May be connected as follows.
Alternatively, the external nozzle 16 and the hopper 14 are integrally connected to each other so as to be integrated.
The internal nozzle 16 may be detachably connected to the inside of the unit 4. Alternatively, the nozzle 16 may be configured to be movable up and down so that the position of the lower opening end can be freely positioned.

Further, also in the case of the supply tank 15 and the nozzle 16, they may be inseparably integrated in series, or may be detachably connected. Although FIG. 1 shows the case where the number of the supply means 56 is one, a plurality of the supply means 56 may be provided. When a plurality of supply means 56 are provided, the nozzles 16 connected to each supply tank 15 are provided with the lower open ends of the plurality of nozzles 16 inside the supply port 11 if the inner diameter of the supply port 11 is sufficiently large. It is also possible to combine a plurality of nozzles 16 on the outer side or the inner side of the hopper so that one nozzle 1
A mixture of a plurality of thermoplastic resins (β) may be supplied to the supply port 11 from the lower opening end of 6.

Although FIG. 1 shows the case where the nozzle 16 is connected to the upper flat surface of the hopper 14, the nozzle 16 may be connected to the side surface of the hopper 14. Further, although FIG. 1 shows the case where the supply tank 15 is located on the extension line of the supply port 11, the supply tank 15 need not be located on the extension line of the supply port 11, and in such a case, the nozzle 16 is used. The thermoplastic resin (β) may be supplied directly above or inside the supply port 11.

The shape of the nozzle 16 is not particularly limited, and its cross section may be circular, elliptical or polygonal. Further, the lower opening end may be spread like a trumpet. In addition, the nozzle 16
The thickness of may be changed midway as long as it does not hinder the supply of the thermoplastic resin (β). Further, as shown in FIG. 3, the nozzle 16 can be cooled by having a double pipe structure and a heat insulating structure, or by interposing a cooling medium 17 such as water between the inner wall and the outer wall of the double pipe.

The outer diameter of the nozzle 16 is not particularly limited as long as it is smaller than the inner diameter of the supply port 11 of the resin melting and kneading device, but the outer diameter of the lower opening end is about 85% or less of the inner diameter of the supply port 11. It is preferable.

The outer diameter of the lower opening end is 8 times the inner diameter of the supply port 11.
When it exceeds 5% and the lower opening end of the nozzle 16 is provided in the supply port 11, the thermoplastic resin (α) is easily clogged between the nozzle 16 and the inner wall surface of the supply port 11, and as a result, It becomes difficult to be stably supplied into the cylinder through the supply port 11. Further, when the outer diameter of the lower opening end exceeds 85% of the inner diameter of the supply port 11 and the lower opening end of the nozzle 16 is contained in the hopper 14, the thermoplastic resin (α ) Is difficult to prevent stable supply of
Considering that it is preferable that the lower open end of the nozzle be located closer to the upper end of the screw, even if the lower open end of the nozzle 16 is accommodated in the hopper 14, the thermoplastic resin (α) From the viewpoint of stable supply of the gas, the outer diameter of the lower opening end of the nozzle 16 is 85 times the inner diameter of the supply port 11.
% Or less is preferable.

Incidentally, the outer diameter of the lower opening end of the nozzle 16 is not particularly limited as long as it is within the range in which the inner diameter capable of stably supplying the thermoplastic resin (β) can be secured as described above. As described above, the thermoplastic resin supply device of the present invention has the hopper 14
This hopper 14 is used by being connected to the resin supply port 11 of the resin melt mixing device. The nozzle 16 is located below the nozzle 16 at a position where the thermoplastic resin (β) is not softened or melted by the thermal influence of the thermoplastic resin (α) before reaching the resin supply port 11. It is necessary to provide the open end, and the thermoplastic resin (β) is less susceptible to the thermal influence from the thermoplastic resin (α) as much as possible. When the devices are connected, it is desirable to install them as close to the screw as possible without impairing the rotation of the screw.

Therefore, when the height of the resin supply port 11 is sufficient, the lower opening end of the nozzle 16 may protrude from the lower end of the hopper 14, and when the height of the resin supply port 11 is extremely low. In some cases, the lower open end of nozzle 16 may fit within hopper 14.

The specific position of the lower opening end of the nozzle 16,
That is, the position where the thermoplastic resin (β) can be stably supplied without being affected by the thermal effect of the thermoplastic resin (α) is the temperature of the thermoplastic resin (α) to be supplied and the position of the thermoplastic resin (β). Temperature of softening or melting / flowing, supply ratio of thermoplastic resins (α) and (β), supply speed, outer diameter of lower opening end of nozzle 16, size of inner diameter of supply port 11, and size of entire apparatus However, it cannot be decided unconditionally because it will be affected by such complicated matters.

For example, as the inner diameter of the supply port 11 is smaller, the thermoplastic resin (β) and the thermoplastic resin (α) in the supply port 11 are smaller.
Since it becomes easy to fuse and the supply port 11 is clogged, it is necessary to provide the lower opening end of the nozzle 16 as close as possible to the upper end of the screw.

Although the specific position of the lower opening end of the nozzle 16 cannot be unconditionally determined, it is as described above, but the height of the hopper 14 is 30 to 200 cm, and the supply port 1 is provided.
If the inner diameter of 1 is in the general range of 4 to 20 cm, the lower open end of the nozzle 16 is preferably provided within about 15 cm from the upper end of the screw, more preferably within 7 cm, and most preferably. Within 2 cm.

Further, the thermoplastic resin supply device of the present invention can be used in the mode as shown in FIG. The thermoplastic resin supply-melt mixing apparatus of the present invention has the thermoplastic resin supply apparatus of the present invention described above and a thermoplastic resin supply port near one end, and plasticizes the supplied thermoplastic resin. And a resin having a screw for rotating the molten thermoplastic resin so that the molten thermoplastic resin moves in the cylinder from the end where the thermoplastic resin supply port is provided to the other end. The device is connected via the lower open end of the hopper and the resin supply port of the melt mixing device. The connecting method is not particularly limited.

[0135]

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited thereto.

In the present invention, "carbon dioxide gas barrier property" and "acetaldehyde concentration" described in the following examples.
Was measured as follows. [Measurement Method of Carbon Dioxide Barrier Property of Bottle] After measuring the weight of the molded product bottle, the molded bottle was replaced with carbon dioxide gas. The amount of dry ice that the internal pressure of the bottle became 5 atm was quickly put in the bottle, and the bottle was tightly capped and shaken vigorously to vaporize the dry ice. Calculate the weight of carbon dioxide in the bottle from the weight of the bottle sealed and the weight of the bottle and wire before measurement. Two
Stored in an atmosphere of 3 ± 1 ° C and the bottle carbon dioxide gas amount is 82.
The number of days to reach 5% was calculated.

[Measurement of content of acetaldehyde] About 2 g of a test piece was sampled from a polyester molded product and frozen and crushed by a freeze crusher manufactured by SPEX. 1 g of the obtained polyester powder is put in a vial bottle, 2 ml of distilled water is added, and water and the polyester powder are mixed well. After closing the cap, the vial bottle is heated at 120 ° C. for 1 hour. After heating, it was cooled in ice water, and acetaldehyde dissolved in water was measured by gas chromatography.

[0138]

Example 1 Resin A1 (polyethylene terephthalate homopolymer; 160 ° C., dried at 160 ° C. for 4 hours;
IV = 0.82 dl / g) was put into the hopper of the injection molding machine (IS-75E manufactured by Toshiba Machine Co., Ltd.) without cooling. Resin B1 {dicarboxylic acid unit (isophthalic acid 90
Mol%, terephthalic acid 10 mol%), diol unit (ethylene glycol 85 mol%, 1,3-bis (2-hydroxyethoxy) benzene 15 mol%, dicarboxylic acid 1
Polyethylene isophthalate composed of 0.32 mol% of 1,1,1-trimethylolpropane with respect to 00 mol%; IV = 0.82 dl / g, glass transition temperature: 62
℃} and magnesium stearate are mixed in advance,
It was supplied from the nozzle (double tube structure) shown in FIG. At this time, the distance (a) from the lower opening end of the nozzle to the position directly above the screw having a diameter of 36 mm was set to 2 cm, and the molding temperature was 28.
Molded at 0 ° C and molding cycle of 30 seconds to obtain resin A1.
Of 90% by weight, 10% by weight of resin B1 and 150 ppm of magnesium stearate were used to obtain a preform made of a polyester resin composition. By contacting the resin B1 with the resin B1 as described above, the resin B1
Did not form a lump in the supply port, and a uniform resin composition could be produced, and a preform having a uniform composition was formed from this resin composition. The weight of the composition per polyfoam was 60 g.

Next, an infrared heater attached to the molding machine was used to heat the preform so that the surface temperature of the central portion of the body was 100 to 110 ° C., and LB-01 manufactured by CORPOPLAST was used.
Stretch blown with a molding machine to obtain an internal volume of 150 as shown in FIG.
A 0 ml blow bottle for carbonated beverages was molded.

During stretching, the blow mold was kept at room temperature, and the bottle was contacted with the mold for 5 seconds and taken out. The molding cycle at this time was 60 seconds, and the area stretching ratio was 11 times. The physical properties of the obtained bottle are shown in Table 1.

[0141]

Example 2 Same as Example 1 except that resin A2 (polyethylene terephthalate having 2 mol% of isophthalic acid units in 100 mol% of dicarboxylic acid, IV = 0.82 dl / g) was used in place of resin A1. The bottles were prepared as described above, and the physical properties of each bottle were evaluated in the same manner as in Example 1. By contacting the resin A1 with the resin B1 as described above, the resin B2
No. 1 did not form a lump in the supply port, and a preform in which the resins were uniformly dispersed was formed. The results are shown in Table 1.

[0142]

Example 3 Instead of the resin B1, a resin B2 {polyethylene isophthalate comprising dicarboxylic acid units (isophthalic acid 90 mol%, terephthalic acid 10 mol%) and diol units (ethylene glycol 100 mol%); IV = 0.
A bottle was prepared in the same manner as in Example 1 except that 82 dl / g, glass transition temperature: 65 ° C.} was used, and the physical properties of each bottle were evaluated in the same manner as in Example 1. Resin A as described above
By bringing the resin B2 into contact with No. 1, the resin B2 did not form a lump in the supply port, and a preform in which the resins were uniformly dispersed was formed. The results are shown in Table 1.

[0143]

Example 4 A bottle was prepared in the same manner as in Example 1 except that the resin A1 was changed to 80% by weight and the resin B1 was changed to 20% by weight. evaluated. The resin B1 is added to the resin A1 as described above.
By contacting with each other, the resin B1 did not become a lump in the supply port, and a preform in which the resins were uniformly dispersed was formed. The results are shown in Table 1.

[0144]

[Example 5] In Example 1, instead of the resin B1,
Resin B3 {polyethylene isophthalate composed of dicarboxylic acid unit (isophthalic acid 98 mol%, terephthalic acid 2 mol%) and diol unit (ethylene glycol 100 mol%); IV = 0.65 dl / g, liquid phase polymerized product} A bottle was prepared in the same manner as in Example 1 except that the physical properties of each bottle were evaluated in the same manner as in Example 1. By contacting the resin B1 with the resin B3 as described above, the resin B3
3 did not form a lump in the supply port, and a preform in which the resins were uniformly dispersed was formed. The results are shown in Table 1.

[0145]

[Example 6] In Example 1, instead of the resin B1,
Resin B4 {polyethylene naphthalate of diol unit (ethylene glycol 100 mol%); IV = 0.61d
1 / g, liquid phase polymerized product} was used to prepare a bottle in the same manner as in Example 1, and the physical properties of each bottle were evaluated in the same manner as in Example 1. By contacting the resin B1 with the resin B4 as described above, the resin B4 did not form a lump in the supply port, and a preform in which the resins were uniformly dispersed was formed. The results are shown in Table 1.

[0146]

COMPARATIVE EXAMPLE 1 90% by weight of the resin A1 and 10% by weight of the resin B1 used in Example 1 were dry blended and charged into an injection molding machine to try molding. The resin A1 and the resin B1 were in a rugged shape.

[0147]

[Comparative Example 2] In Example 1, the resin B1 was supplied by setting the supply position of the resin B1 at a position of a distance of 15 cm immediately above the screw. The resin B1 is blocked in the supply port 11 or at the tip of the nozzle. Since only A1 was supplied to the injection molding machine, molding was stopped.

[0148]

Reference Example The glass transition temperature (Tg) and melting point (mp) of resins A1, A2, B1, B2, B3 and B4 are as follows.

[0149]

[Table 1]

[0150]

[Table 2]

[0151]

According to the method for producing a polyester composition of the present invention, the high temperature dried crystallized polyester (A) (polyethylene terephthalate (A-1), etc.)
Is an amorphous polyester (B), polyethylene isophthalate (B-1) (amorphous polyester (B ')
Etc.), even if the resin is put into a molding machine without being once cooled to a temperature not higher than the glass transition temperature, the resin is not welded to each other to form a lump, and the composition can be stably produced.

Therefore, the cooling equipment for the crystallized polyester (A) or the equipment for storing the cooled one can be omitted, and the cost reduction can be expected. Further, since the raw material is charged in a preheated state, the plasticizing time in the molding machine can be shortened and the productivity is improved.

The obtained polyester composition or molded product is excellent in gas barrier property, transparency, heat resistance and the like. In addition, stable continuous molding can be performed without clogging in the hopper and variation in the metering time unlike the case of using the conventional master batch automatic feeder. Further, the proportion of the amorphous polyester in the molded product is present in a fixed amount in every molded product, and the variation is very small.

Further, the method for producing a polyester composition shown in the present invention is a composition of other crystalline resin and an amorphous resin, wherein the amorphous resin is mixed with the temperature at which the crystalline resin is introduced into the molding machine. It can also be applied when the temperature is higher than the glass transition temperature of the resin.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing an example of a raw material supply device used in the method of the present invention.

FIG. 2 is a diagram schematically showing another example of the raw material supply device used in the method of the present invention.

FIG. 3 is a diagram schematically showing an example of a nozzle portion of the raw material supply device shown in FIG.

FIG. 4 is a diagram schematically showing a bottle which is an example of a molded product manufactured by the method of the present invention.

[Explanation of symbols]

11 ... Raw material supply port 12 ... Cylinder 13 ... Screw 14 ... Hopper 15 ... Polyethylene isophthalate (B-1) supply device 16 ... Nozzle 27 ... Storage hopper 28 ... ..Quantitative transportation device 29 ... Air carrier 30 ... Cyclone 31 ... Hopper 32 ... Device control panel 33 ... Special caster 34 ... Post 35 ... Cut gate type supply mechanism 36 ... Metering mechanism 37 ... Spring feeder 38 ... Quantitative transportation device 39 ... Piping 40 ... Hopper 41 ... Ejector mechanism 51 ... Preform 52 ... Bottle 53 ... Means 54 for supplying thermoplastic resin (α) ... Thermoplastic resin (α) supply tank 55 ... Thermoplastic resin (α) supply pipe (nozzle) 56 ... Thermoplastic resin (β ) Means for supplying

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI B29L 22:00 B29L 22:00 (72) Inventor Hisashi Kaneko 2-3-13 Kyobashi, Chuo-ku, Tokyo Toyo Ink Manufacturing Co., Ltd. In-house (72) Inventor Satoru Nishikawa 2-3-3 Kyobashi, Chuo-ku, Tokyo Toyo Ink Mfg. Co., Ltd. (56) Reference JP-A-2-173058 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B29C 31/00-31/10 B29C 45/00-45/84 B29C 47/00-45/96 B29C 49/00-49/80 C08L 67/00-67/02

Claims (16)

(57) [Claims] 1. A cylinder having a resin supply port near one end and having heating means for plasticizing the supplied resin, and from the end where the resin supply port is provided to the other end. Crystallized polyester (A) 99 to 60% by weight using a resin melt mixing device having a screw that rotates so that the molten resin moves in the cylinder.
And 1 to 40% by weight of the amorphous polyester (B) are mixed and mixed in a molten state to produce a polyester resin composition [total of (A) and (B) is 100% by weight]. And the crystallized polyester (A) at a temperature higher than the glass transition temperature of the amorphous polyester (B) and the amorphous polyester (B) reach the resin supply port. The amorphous polyester (B) is at a position where the polyester (A) crystallized on the cylinder side and the amorphous polyester (B) start to come into contact with each other from the position where the polyester (B) can exert a substantial thermal effect. ) Is introduced into the cylinder from the resin supply port. 2. The position at which the contact between the crystallized polyester (A) and the amorphous polyester (B) is started can reach the inside of the cylinder before the amorphous polyester (B) is welded. The method for producing a polyester resin composition according to claim 1, wherein 3. The method for producing a polyester resin composition according to claim 1 or 2, wherein the amorphous polyester (B) is an amorphous polyester (B '). 4. The crystallized polyester (A) is polyethylene terephthalate (A-1), and the amorphous polyester (B ') is polyethylene isophthalate (B-).
It is 1), The manufacturing method of the polyester resin composition of Claim 3 characterized by the above-mentioned. 5. A predetermined amount of the amorphous polyester (B) is added to the crystallized polyester (A) being supplied into the cylinder at the same time when the screw measures the resin. 2. The amorphous polyester (B) is supplied so as to start contact with the raw material supply part of the cylinder or inside the cylinder, and both are melt-mixed in the cylinder. A method for producing the polyester resin composition according to claim 1. 6. An apparatus for supplying the amorphous polyester (B) to the crystallized polyester (A) has a nozzle for supplying the amorphous polyester (B) to a raw material supply section of a cylinder. The method for producing a polyester resin composition according to claim 1, wherein the outermost diameter of the thinnest portion of the nozzle is 10 to 85% of the inner diameter of the raw material supply port. 7. The method for producing a polyester resin composition according to claim 1, wherein a lower tip portion of the nozzle of the amorphous polyester (B) feeder is located in the raw material feed portion of the cylinder. . 8. The method for producing a polyester resin according to claim 1, wherein a lower tip portion of a nozzle of a supply device for the amorphous polyester (B) is located right above the screw. 9. The method for producing a polyester resin composition according to claim 1, wherein the resin melt-kneading device is an extrusion molding machine or an injection molding machine. 10. A cylinder having a resin supply port near one end and having heating means for plasticizing the supplied resin, and from the end where the resin supply port is provided to the other end. Crystallized polyester (A) 99 to 60% by weight and amorphous polyester (B) 1 to 40% by weight using a resin melt mixing device having a screw that rotates so that the molten resin moves in the cylinder. And a polyester resin composition [100% by weight of (A) and (B) are mixed together in a molten state by contacting with the above, and the molded product is shaped into a predetermined shape. The crystallized polyester (A) at a temperature higher than the glass transition temperature of the polyester (B) and the amorphous polyester (B) reach the resin supply port, and the amorphous polyester (B) The amorphous polyester (B) is supplied to the position where the crystallized polyester (A) and the amorphous polyester (B) start to come into contact with each other from the position where the substantial thermal effect is exerted on the cylinder. A method for producing a molded article made of a polyester resin composition, characterized in that the polyester resin composition is introduced into the cylinder through a resin supply port. 11. The method for producing a molded product comprising a polyester resin composition according to claim 10, wherein the amorphous polyester (B) is an amorphous polyester (B '). 12. The crystallized polyester (A) is polyethylene terephthalate (A-1), and the amorphous polyester is polyethylene isophthalate (B-1). A method for producing a molded article comprising the polyester resin composition according to claim 1. 13. The method for producing a molded product made of the polyester resin composition according to claim 10, wherein the molded product of the polyester composition is a preform. 14. The method for producing a molded article made of the polyester resin composition according to claim 10, wherein the preform is stretch blow-molded to produce a bottle made of the polyester composition. 15. A means for supplying a crystalline thermoplastic resin (α), and an amorphous thermoplastic resin (β) having a softening temperature or melting temperature lower than that of the thermoplastic resin (α).
And a hopper, and has a thermoplastic resin supply port near one end,
A cylinder having heating means for plasticizing the supplied thermoplastic resin and a thermoplastic resin melted in the cylinder from the end where the thermoplastic resin supply port is provided to the other end A thermoplastic resin supply device connected to a resin supply port of a resin melt mixing device having a screw that rotates to, wherein the means for supplying the crystalline thermoplastic resin (α) is a thermoplastic resin ( α) supply tank and thermoplastic resin (α)
And a nozzle for supplying the thermoplastic resin (α) through the nozzle so that the thermoplastic resin (α) can be supplied to the hopper, and has a softening temperature or melting temperature higher than that of the crystalline thermoplastic resin (α). The means for supplying the low amorphous thermoplastic resin (β) has a thermoplastic resin (β) supply tank and a nozzle for supplying the thermoplastic resin (β), and the thermoplastic resin (β) is supplied through the nozzle. The resin (β) is connected to the hopper so that the resin (β) can be supplied to the thermoplastic resin supply port, and the thermoplastic resin (β) is supplied when the thermoplastic resin supply device is connected to the resin melt mixing device. The lower opening end of the nozzle for supplying the thermoplastic resin (β) to the position where the thermoplastic resin (β) supplied from the lower opening end of the nozzle for softening or melting does not reach the upper end of the screw. Thermoplastic resin supply apparatus characterized by being provided. 16. The thermoplastic resin supply device according to claim 1, which has a thermoplastic resin supply port near one end, and
A cylinder having heating means for plasticizing the supplied thermoplastic resin and a thermoplastic resin melted in the cylinder from the end where the thermoplastic resin supply port is provided to the other end And a resin melt-mixing device having a screw that rotates in a vertical direction.