JPH02172738A - Polyester laminated body and use thereof - Google Patents

Abstract

PURPOSE:To improve gas barrier properties against oxygen and carbon dioxide by molding a polyester laminated body by laminating a polyalkylene terephthalate layer to a copolyester layer having a specific composition. CONSTITUTION:Copolyester wherein 95-60mol% of a dicarboxylic acid unit is an isophthalic acid component unit, 5-40mol% of said unit is a 2,6-naphthalene dicarboxylic acid component unit and 95-70 mol% of a dihydroxy compound component unit is an ethylene glycol component unit and 5-30mol% thereof is a 1, 3-bis(2-hydroyethoxy) benzene component unit is synthesized according to a melt polycondensation method and a solid phase polycondensation method. This copolyester layer and a polyalkylene terephthalate layer are laminated to form a two-layer laminated body excellent in stretchability, electric insulating properties and mechanical strength.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a polyester laminate molded product and its uses, and more particularly to a polyester laminate molded product with excellent properties such as moldability, mechanical strength, and gas barrier properties, and its use. Regarding usage.

Technical background of the invention and its problems Conventionally, materials for containers for seasonings, oil, beer, alcoholic beverages such as LJ wood sake, soft drinks such as carbonated drinks, cosmetics, detergents, etc. Glass is widely used. Although glass containers have excellent gas barrier properties, they are expensive to manufacture, so the method of storing empty containers after normal use and recycling them is adopted.

However, glass containers are heavy, which increases shipping costs, and they also have problems, such as being easily broken and inconvenient to take out.

To solve these problems, various plastic containers are being used instead of glass containers. Various plastics are used for the bare hands, depending on the type of stored item and its use. Among these plastics, polyethylene terephthalate (P
ET) has excellent heat resistance, Nj9 resistance, gas barrier properties, and transparency, so it is used as a material for containers such as seasonings, soft drinks, detergents, and cosmetics.

However, polyethylene terephthalate cannot be said to be sufficient for beer and carbonated beverage containers, which require the most stringent gas barrier properties among these. , gas barrier by increasing wall thickness
I had to improve my sexuality.

Currently, the demand for polyester containers is on the rise, and in order to further expand these uses, there is a strong desire for polyester with excellent gas barrier properties and melt moldability.

By the way, as a polyester, JP-A-56-8486
No. 6 discloses that the outermost layer and the innermost layer of a multilayer container having a thin wall portion are made of polyester having ethylene terephthalate as a main repeating unit, and that an intermediate layer between these layers reacts a dibasic acid component and a diamine component. The diamine component is m-xylylene diamine or a mixture of m-xylylene diamine and p-xylylene diamine, and the resin constituting the thin portion is formed in at least one direction. A multilayer container that is oriented is disclosed. This publication states that the container retains the excellent mechanical properties, transparency, chemical resistance, etc. of polyester, and also has excellent oxygen gas barrier properties.

In addition, JP-A-58-183243 discloses a two-layer stretch blow-molded bottle body, in which both the inner and outer surface layers are made of polyethylene terephthalate, and the intermediate layer between these two layers is made of a mixture of polyethylene terephthalate and xylylene-based polyamide. has been disclosed.

Furthermore, JP-A-59-67049 discloses a multilayer packaging material comprising a layer made of polyalkylene isophthalate or a copolymer thereof as described above, and a layer made of polyalkylene terephthalate such as polyethylene terephthalate or a copolymer thereof; Molded articles such as bottles are disclosed.

However, in any case, the polyethylene isophthalate described in the above publication contains oligomers with a high melting point, and these oligomers have a problem in that they adversely affect the physical properties of the resulting molded product.

In order to improve the gas barrier properties of PET, isophthalic acid is used as the dicarboxylic acid component, and 1,3-bis(2-hydroxyethoxy)henzene is used together with ethylene glycol as the dihydroquine compound component. A polymerized copolyester has been proposed (see JP-A-58-1 [17617] jj40).
.

By the way, when molding containers etc. from polyester resin, it is necessary to dry the polyester resin before molding, as if this polyester resin contains water, a hydrolysis reaction will occur and the mechanical properties will deteriorate. be. However, isophthalate copolyesters containing a large amount of isophthalic acid as a dicarboxylic acid component have poorer crystallinity than terephthalate copolyesters and also have a lower glass transition temperature (Tg), so they can only be dried at low temperatures.
Therefore, there is a problem in that it takes a long time to dry an isophthalate polyester having a low moisture content. Also, the above isophuta 1
If the -1-based copolyester was dried at a temperature higher than the glass transition temperature, there was a problem that the isophthalate-based copolyesters would form with each other.

Furthermore, drying of polyethylene terephthalate generally takes
Polyethylene terephthalate which has been dried at a temperature of 10 to 160°C or dried at this temperature and an isophthalate copolyester which has been dried at a lower temperature than the above temperature are triblended immediately after drying of both. Then, since the polyethylene terephthalate is not cooled, the resin temperature is considerably high, and the above-mentioned copolyester is heated to a temperature higher than the glass transition temperature by this high IH polyethylene terephthalate. Problems such as deformation of the copolyester pellets, melting of the copolyester pellets, and difficulty in uniformly mixing the two were cited as problems.

For this reason, it has been desired to develop an isophthalate copolyester that has a high glass transition temperature (TF) and excellent heat resistance.

As such a copolyester with a high glass transition temperature (Tg), an isophthalate copolyester obtained by copolymerizing bis(4-β-hydroxyethoxyphenyl) sulfone has been proposed (Japanese Patent Application Laid-Open No. 16761-1989).
(See Publication No. 7).

As mentioned above, the glass transition temperature (1'g
) is somewhat high depending on t, and besides, the y7 effect is not sufficient, and furthermore, the gas barrier property may deteriorate, coloration may occur, or even monomer components may be liberated, resulting in food hygiene issues.
There was also the problem that I didn't like it.

The present invention aims to solve the problems associated with the prior art as described above, and has excellent formability and stretchability, and gas barrier properties, especially gas barrier properties against oxygen and carbon dioxide gas. Furthermore, it has excellent heat resistance, 11iJ impact resistance, surface properties, transparency, electrical properties, and chemical resistance, and is also high melting! The purpose of this invention is to produce a polyester laminate molded product that does not contain oligomers containing IA (jl).

In addition, the present invention is made of a polyester laminate molded article, which has excellent gas barrier properties, especially gas barrier properties against oxygen and carbon dioxide gas, and has excellent heat resistance, impact resistance, and table IJj.
The objective is to provide a stretch laminate molded product, a preform for a laminate hollow molded product, and a laminate hollow molded product that have excellent properties, transparency, electrical properties, and chemical resistance and do not contain high melting point oligomers. .

Summary of the Invention The polyester laminate molded product according to the present invention is composed of (A) a polyalkylene terephthalate layer and (B) a copolyester layer, and the copolyester layer (B) is made of a copolyester or a sublayer such as the following. 95 to 60 mol% of the dicarboxylic acid component units constituting the copolyester (1) are isophthalic acid component units, and 5 to 40 9 mole percent of the 2,6-naphthalene dicarboxylic acid component units and 9 of the dihydroxy compound component units
5 to 70 mol% is ethylene glycol component unit,
It is characterized in that it contains 5 to 30 mol% of 1,3-bis(2-hydroxyethyxy)benzene component units.

The polyester stretch laminate molded product according to the present invention is composed of (A) a polyalkylene terephthalate layer and (B) a copolyester layer, and this copolyester layer (B)
is composed of a copolyester as shown below, or a copolyester composition consisting of a copolyester as shown below and polyethylene terephthalate, and 95 to 60 mol% of the dicarboxylic acid component units that also constitute this copolyester are isophthalic acid components. and 5 to 40 mol% of the 2,6-naphthalene dicarboxylic acid component units, and 9 of the dihydroxy compound component units.
5 to 70 mol% is ethylene glycol component unit,
and 5 to 30 mol% of the 1,3-bis(2-hydroxyethoxy)benzene component is at position tIt, and the polyalkylene terephthalate layer (A) and the copolyester layer (B) are stretched. It is a feature.

The polyester laminate blow molded preform according to the present invention comprises (A) a polyalkylene terephthalate layer, and (B)
) copolyester layer, and this copolyester layer (B) is made of a copolyester as shown below, or a copolyester composition consisting of a copolyester like the one below and polyethylene terephthalate; 95 to 60 mol% of the constituting dicarboxylic acid component units are isophthalic acid component units, and 5 to 40 mol% are 2,6-naphthalene dicarboxylic acid components! 11, and that 95 to 70 mol% of the dihydroxy compound component units are ethylene glycol component units, and 5 to 30 mol% are at the 114L position of the 1.3-bis(2-hydroxyethoxy)benzene component. It is a feature.

The polyester laminate hollow molded article according to the present invention is composed of (A) a polyalkylene terephthalate layer and (B) a copolyester layer, and this copolyester layer (B) is made of a copolyester as shown below or as below. dicarboxylic acid component 111 constituting this copolyester.
- position is 95 to 60 mol% isophthalic acid component units, 5 to 40 mol% is 2,6-naphthalene dicarboxylic acid component units, and 95 to 70 mol% of the dihydroxy compound component units are ethylene glycol components. unit, and is characterized by being 5 to 30 mol% of 1,3-bis(2-hydroxyethoxy)benzene component units.

Since the polyester laminate molded article according to the present invention is composed of the above-mentioned specific layers, it has excellent gas barrier properties, particularly against oxygen and carbon dioxide, and
It has excellent heat resistance, impact resistance, surface properties, transparency, electrical properties, and chemical resistance, and contains almost no high melting point oligomers.

The stretch laminate molded product, the preform for a laminate hollow molded product, and the laminate hollow molded product according to the present invention have gas barrier properties, particularly against oxygen and carbon dioxide gas, since they are composed of the specific layer (1 layer) as described above. It has excellent gas barrier properties, excellent heat resistance, impact resistance, surface properties, transparency, electrical properties, and chemical resistance, and contains almost no high melting point oligomers.

DETAILED DESCRIPTION OF THE INVENTION The polyester laminate 113 body, polyester stretch laminate molded product, preform for a polyester laminate molded product, and polyester laminate hollow molded product according to the present invention will be specifically described below.

The polyester laminate molded article according to the present invention is made up of a polyalkylene terephthalate layer (A) and a copolyester layer (B).

The polyalkylene terephthalate layer (A) constituting the polyester laminate molded product of the present invention is formed from polyalkylene terephthalate such as polyethylene terephthalate and polypropylene terephthalate. In the present invention, among these, polyethylene terephthalate!・is preferably used.

The polyethylene terephthalate used in the present invention is a thermoplastic polyester resin having crystallinity, and is composed of dicarboxylic acid component units and dihydroxy compound component units as described below.

In the present invention, the dicarboxylic acid component 1 constituting polyethylene terephthalate is usually 80 mol% or more, preferably 90 mol% or more of the terephthalic acid component 111.
0 position, and the dihydroquine compound component unit is usually 8
The amount is 0 mol % or more, preferably 90 mol 96 or more ethylene glycol component units.

In addition, dicarboxylic acid component 7 other than the terephthalic acid component unit
Specifically, as the 11th position, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-1,
Aromatic dicarboxylic acids such as 4-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid; aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, and undecadicarboxylic acid; hexahydroterephthalic acid, etc. Examples include component units derived from aliphatic dicarboxylic acids and the like.

Examples of dihydroxy compound component units other than ethylene glycol component units include aliphatic dihydroxy compounds such as 1,4-butanediol and neopentyl glycol; aliphatic dihydroquine compounds such as dichlorohexanediol and cyclohexane dimetatool; l,3-bis-
(2-hydroxyethoxy)benzene, 1,4-bis(
2-hydroxyethoxy)benzene, 2,2-bis(4
-β-hydroxye! Examples include component units derived from aromatic dihydroxy compounds such as xyphenyl)propane, bis(4-β-hydroxyethoxyphenyl)sulfone, and bisphenol A.

If m of the terephthalic acid component unit and ethylene glycol component unit is within the above range, polyethylene terephthalate contains the dicarboxylic acid component unit at the 11i position and the dihydroxy compound component unit as described above in addition to the terephthalic acid component unit and the ethylene glycol component unit. may contain. In addition, in the present invention, polyethylene terephthalate is
It may also be used in combination with other polyesters, such as polypropylene ethylene terephthalate.

The molecular weight of the polyethylene terephthalate used in the present invention is not particularly limited as long as it is within a range that allows various molded products such as containers to be manufactured from the resulting polyester laminate molded product. However, in the present invention, 25
The intrinsic viscosity [η] of polyethylene terephthalate determined by IP at °C (hereinafter referred to as IV) is usually
0.6 (1Ω/g or more, preferably 0.8 tel
/ 1 (or more is desirable.

When using polypropylene terephthalate as the polyalkylene terephthalate, for example, propylene glycol may be used in place of the above-mentioned ethylene glycol. In this way? 1 sintered polypropylene terephthalate was al
The intrinsic viscosity [η] determined by l+ is usually 098 to 1.2 d
It is Ω/g. In addition, in the present invention, polypropylene terephthalate may be used in combination with other polyesters.

In the present invention, the copolyester layer (B) constituting the polyester laminate molded product is the following copolyester or copolyester and polyethylene terephthalate).
- formed from a copolyester composition containing h-.

This copolyester is composed of a dicarboxylic acid component unit as shown below and a molecule 1 of a dihydroxy compound I, and is formed by a cocondensation reaction between the corresponding dicarboxylic acid component and a dihydroquine compound component.

The dicarboxylic acid component units constituting the above copolyester are 95 to 60 mol%, preferably 90 to 70 mol%, or isophthalic acid component units, and 5 to 40 mol%, preferably 10 to 30 mol%. B-naphthalene dicarboxylic acid component unit.

An amount exceeding 95 moles of isophthalic acid component units constituting the copolyester is not preferable because the glass transition temperature (-Tg) of the copolyester does not increase much; If the amount of j is too high, the glass transition temperature (Tg) of the copolyester will rise too much, and even if you try to stretch a polyester laminate formed from a copolyester layer and a polyalkylene terephthalate layer, the stretching of the copolyester layer will be too high. This is undesirable as it reduces performance.

In the present invention, since the 2,6-naphthalene dicarboxylic acid component unit derived from the rigid comonomer component is D'H-treated as a constituent unit of the copolyester, the glass transition temperature of the copolyester becomes high. tA!
Low content of point oligomers, gas barrier for laminates
maintain a high level of sexuality.

In the present invention, in addition to the above-mentioned isophthalic acid component + unit and 2,6-naphthalenedicarboxylic acid component unit as the dicarboxylic acid component unit forming fIYi of the copolyester, other units may be used as long as they do not impair the properties of the polyester laminate. dicarboxylic acid component units may be contained. Such other dicarboxylic acid components at the tn position include, in addition to the terephthalic acid component at the 11i position, components 111. I can give an example of the position.

In the present invention, ethylene glycol component units exist as dihydroxy compound component units constituting the copolyester.

Further, in the present invention, in addition to the above-mentioned ethylene glycol component unit, a 1,3-bis(2-hydroxyethoxy)benzene component molecule at the lt position is contained as a dihydroxy compound component unit constituting the copolyester.

In addition to the ethylene glycol component unit, 1,3-bis(
2-Hydroxyethoxy) Hensen component + 1 position, when the 95th to 1st position of the dihydroxy compound component unit is contained
70 mol% preferably 90 to 80 mol 96 are ethylene glycol component units, 5 to 30 mol% preferably 1
0 to 20 mol% is 1,3-bis(2-hydroxyer).
benzene component unit. As dihydroxy compound component units, ethylene glycol component units and 1,
When the 3-bis(2-hydroxyethoxy)benzene component unit is DHed in the above range, the nail content of the high melting point oligomer in the copolyester decreases, and the glass transition temperature (Tg) also decreases. becomes higher.

In addition, in the present invention, as the dihydroxy compound component unit constituting the copolyester, in addition to the above-mentioned ethylene glycol component unit and 1,3-bis(2-hydroxyethoxy) Hensen component unit, Hg properties of the polyester laminate molded product are added. It may contain other dihydroquine compound component units as long as it does not impair the properties of the dihydroquine compound. As the 11th position of such a dihydroquine compound component, the compound component units listed above as dihydroxy compound component units can be exemplified, and among these, those having 3 to 3 carbon atoms
15 dihydroxy compound ingredients! -1i position is preferred.

The above-mentioned copolyester has an intrinsic viscosity [η] of 0.3 to 1.5t measured at 25°C in 0-chlorophenol.
f/g is preferably 06 to 1. If it exceeds .5d, Q/g, melt moldability becomes poor, which is not preferable.

The copolyester used in the present invention has a glass transition temperature (Tg) of usually 68 to 95°C, preferably 70°C.
It is desirable that the temperature is ~80°C.

Isophthalic acid component 11th and ethylene glycol component jl
The glass transition temperature (Tg) of a conventional polyester composed of tIn is about 60 to 70°C, and in comparison, the copolyester used in the present invention has a glass transition temperature (Tg) of about 60 to 70°C. This allows for faster drying. Moreover, when using a composition of polyethylene terephthalate and copolyester for the copolyester layer of a polyester laminate molded product, even if the two are mixed immediately after drying, the copolyesters will not fuse together. few.

The above copolyester can be produced according to the conventionally known polycondensation method employed in the production of polyethylene terephthalate. When producing such a copolyester, regarding the dicarboxylic acid component,
It can also be supplied to the reaction system as a dicarboxylic acid,
It can be supplied as its dialkyl ester, or as its ester, such as bisβ-hydroxyethyl ester of dicarboxylic acid.

Further, the dihydroxy compound component can be supplied to the reaction system in the form of a dihydroxy compound or in the form of a dihydroxy ester of carboxylic acid.

As the catalyst for copolycondensation, conventionally known catalysts used in the production of polyethylene terephthalate can be used. As these catalysts, metals such as antimony, kermanium, titanium, etc. or their compounds can be used. The form of the compound is oxide, hydroxide, I
＼Logenides, inorganic acid salts, organic acid salts, complex salts, double salts, alcoholades, phenolates, etc. are used. These catalysts can be used alone or as a mixture of two or more. These catalysts can be supplied to the reaction system from the initial stage of the esterification reaction or transesterification reaction, or can be fed to the reaction system from the initial stage of the esterification reaction or transesterification reaction, or can be supplied to the reaction system at the stage of the polycondensation reaction. It can also be supplied to the reaction system before T.

Additionally, during copolycondensation, various additives such as transesterification catalysts, diethylene glycol production inhibitors, heat stabilizers, light stabilizers, lubricants, pigments, and dyes used in the production of polyethylene terephthalate can be used. .

As catalysts for these transesterification reactions, metal compounds such as calcium, magnesium, lithium, zinc, conolite, manganese, etc. can be used. The forms of these compounds include oxides, hydroxides, halides,
Inorganic acid salts and organic acid salts are used. Also diethylene glycol cow.

As the formation inhibitor, amines such as I-ethylamine and tributylamine, and quaternary ammonium compounds such as tetrabutylammonium hydroxide and tetrabutylammonium hydroxide can be used. In addition, as stabilizers such as heat stabilizers, phosphoric acid,
Phosphorus compounds such as phosphorous acid, hypophosphorous acid, or esters thereof can be used.

In the present invention, the copolyester is produced by a conventionally known melt polycondensation method, and in some cases by employing a melt polycondensation method followed by a solid phase polycondensation method.

In the melt polycondensation method as described above, a so-called direct polycondensation method can be employed, and a so-called transesterification polycondensation method can also be employed. That is, to explain the melt polycondensation method more specifically, for example, isophthalic acid and 2,6-naphthalene dicarboxylic acid, a dicarboxylic acid containing these as main components, or an ester derivative thereof, ethylene glycol or ethylene glycol and 1.3 -bis(2-hydroxyethyne or its condensate with a dicarboxylic acid, and optionally a polyfunctional compound containing 3 flA+ or more of a carboxyl group or a hydroquine group, preferably 1.00 These labor-saving bright polycondensates are subjected to esterification or transesterification reactions at temperatures of ~280'C, which are then evaporated in vacuo at temperatures above their melting points, preferably from 200 to 300'C. An example of this method is a method in which polycondensation is carried out without stirring under a flow of dust or inert gas.

Further, in the present invention, the copolyester can also be produced by further solid-phase polycondensing the polyester obtained by iHB by the melt polycondensation method as described above to increase the molecular weight.

To specifically explain such a solid 1'1 condensation method, for example, a polyester obtained by a melt polycondensation method is made into fine particles and then heated at a temperature below the melting point, preferably 180 to 240°C.
A method can be adopted in which the material is held under vacuum or under an inert gas flow.

To obtain a copolyester composition from polyethylene terephthalate and copolyester, various known methods can be used. For example, polyethylene A method of mixing terephthalate I. and a copolyester can be mentioned.

In addition, since the glass transition temperature of copolyester is high, even if polyethylene terephthalate and copolyester are mixed immediately after they are dried, the copolyesters are unlikely to fuse together. Therefore, in the present invention,
Polyethylene terephthalate and copolyester can be mixed immediately after drying of both. Furthermore, after mixing in this manner, the mixture may be melt-kneaded using a screw extruder, twin-screw extruder, kneader, remixer, etc., and then granulated or pulverized.

In the copolyester composition thus obtained, polyethylene terephthalate is present in an amount of 50 to 95% by weight, preferably 70 to 9% by weight, based on the total weight of the copolyester composition.
In an amount of 0% by weight, the copolyester has a weight of 50 to 5% by weight of 96
Preferably, the content is 30 to 10% by weight.

If the amount of polyethylene terephthalate is less than 50% by weight, the characteristics of polyethylene terephthalate will not be fully exhibited, which is undesirable.On the other hand, if the amount exceeds 95% by weight, the characteristics of the copolyester will not be fully exhibited, which is undesirable.

It is desirable that the glass transition temperature (Tg) of the copolyester composition produced in this way is usually 75 to 85°C, preferably 80 to 85°C.

Such copolyester compositions have a higher glass transition temperature (T g") than polyester compositions using conventional isophthalate copolyesters,
The obtained copolyester composition can be quickly dried at high temperature, and the polyester laminate molded article of the present invention can be efficiently produced.

In the present invention, the copolyester resin composition includes heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, lubricants, M type agents, pigment dispersants, dyes, etc., which are usually added to the polyester. Various compounding agents can be added within the range that does not impair the purpose of the present invention.

Next, a polyester laminate molded article of the present invention, which is composed of a layer made of polyalkylene terephthalate and a layer made of copolyester as described above, will be explained.

Specifically, this laminate molded product is a two-layer laminate molded product composed of two layers, a copolyester layer and a polyalkylene terephthalate layer, the copolyester layer is an intermediate layer, and both outer layers are the above-mentioned polyalkylene terephthalate layers. A three-layer laminate molded product having a polyalkylene terephthalate layer as an intermediate layer and the above-mentioned copolyester layer as both sides, a copolyester IW and a polyalkylene terephthalate layer on top of which are laminated in an intersecting manner. A multilayer laminate molded product having a four-layer structure or more, in which both outermost layers are composed of polyalkylene terephthalate layers, a laminate molded product having a four-layer structure or more in which copolyester layers and the above-mentioned polyalkylene terephthalate layers are alternately laminated. A multilayer laminate molded product consisting of 11 layers consisting of both outermost layers or copolyester layers, or a 4-layer molded product consisting of 1 layer or more in which the copolyester layer and the above-mentioned polyalkylene terephthalate layer are alternately laminated. Examples include a multilayer laminate molded product in which the outermost layer is composed of a copolyester layer and a polyalkylene terephthalate layer.

The above-mentioned laminate molded product can be used in various shapes such as a trunk-like object, a plate-like object, a tubular object, a hollow object, and a container. This laminated molded product can be manufactured by a conventionally known method.

The thicknesses of the copolyester layer and the polyalkylene terephthalate layer constituting such a laminate molded product are not particularly limited, and can be appropriately determined depending on the use of the laminate molded product. For example, when this laminate molded product is the above-mentioned two-layer laminate molded product, the thickness of the copolyester layer is usually 5.
0 to 500 μm, preferably 50 to 300 μm, and the thickness of the polyalkylene terephthalate layer is 50 to 300 μm.
500 μm, preferably in the range of 50 to 200 μm. Further, when this laminate molded product is the former of the three-layer laminate molded product, the thickness of the intermediate layer made of copolyester is usually 50 to 500 μIT+%, preferably 50 μT+%.
~200 μrn, and the thickness of each of the outer layers of polyalkylene terephthalate is typically 5 μrn.
0-500μIn.

Preferably it is in the range of 50 to 300 μm. Further, when the laminate molded product is the latter of the three-layer laminate molded products, the thickness of the intermediate layer made of the polyalkylene terephthalate layer is usually 50 to 500 μIn.

The thickness is preferably in the range of 50 to 300 μm, and the thickness of both outer layers consisting of the copolyester layer is usually 50 to 500 μm.
m, preferably in the range of 50 to 200 μm. Furthermore, even when the laminate molded product is a multilayer laminate molded product with four layers (D structure or more), the thickness of the intermediate layer and the outermost layer constituted by the copolyester layer, and the thickness of the intermediate layer constituted by polyalkylene terephthalate. And the thickness of the outermost layer can be set in the same manner as described above.

Such a laminated molded product has excellent stretchability and electrical properties, especially 7[
It has excellent properties such as repeated stunning, mechanical strength, transparency, and gas barrier properties.

The above-mentioned laminate can further be made into a stretch molded product.

As a method for manufacturing the polyester stretch laminate molded product of the present invention, any conventionally known method can be employed. Generally, as mentioned above, the original molded body such as a film or sheet obtained by appropriately laminating a polyalkylene terephthalate layer and a copolyester layer is used as it is, or at a temperature below the glass transition point of the polyalkylene terephthalate and copolyester. After cooling and solidifying to a temperature higher than the glass transition point of both, preferably 70-1
Stretch at a temperature range of 00°C.

The polyester stretched laminate molded product of the present invention can be produced by, for example, when the original molded product is a film or sheet, a method of stretching an unstretched film or sheet in the unilateral direction (-axial stretching method), a longitudinal stretching method, A method of stretching in the axial direction and then further in the transverse direction (biaxial stretching method), a method of simultaneously stretching in the longitudinal direction and the direction (simultaneous biaxial stretching method), Examples include a method in which sequential stretching is not repeated in one direction, and a method in which biaxial stretching is performed and then further stretched in both directions.Here, when the above-mentioned original molded body is stretched in one direction, the stretching ratio is ,usually,
It is in the range of 1.1 to 10 times, preferably 1.2 to 8 times, particularly preferably 1.5 to 7 times. In addition, when manufacturing a molded object by biaxial stretching, the stretching ratio is usually
The range is 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5 to 6 times, and in the transverse direction, usually 1.1
~8 times, preferably 1.2 to 7 times, particularly preferably 1.
It is in the range of 5 to 6 times. Note that the stretched laminate molded product thus obtained can also be subjected to heat setting.

The polyester stretch laminate molded product of the present invention has mechanical strength,
It has excellent properties such as transparency, electrical properties, and gas barrier properties. In particular, it is effective for protecting electrical and electronic circuits and preventing corrosion of metals by using it as a coating for electrical components, electronic components, and metal parts. Utilizing its electrical characteristics, it can be used for capacitors, motors, transformers,
Alternatively, it can be used for G effect in applications such as coating electric wires. Furthermore, by taking advantage of its excellent gas barrier properties, it can also be used as a film for food packaging, etc.

The preform for a polyester laminate hollow molded body according to the present invention can be manufactured using the above-described polyester laminate molded body.

For example, the preform for a polyester laminate hollow molded body of the present invention can be formed by molding a tubular polyester laminate body.

The polyester laminate hollow molded body according to the present invention is a stretched hollow molded body formed from the polyester laminate molded body. This stretch hollow molded body can be manufactured, for example, by stretch blow molding the preform for a hollow molded body.

The polyester laminate hollow molded product according to the present invention may be a -axially stretched molded product or a biaxially stretched molded product. Particularly in the present invention, the polyester laminate hollow molded product produced by biaxial stretching has excellent mechanical strength and gas barrier properties.

In the present invention, the stretching ratio of the polyester laminate hollow molded product may be the same as that of the polyester laminate hollow molded product.

The polyester laminate hollow molded body in the present invention can be produced by stretch-blow molding a preform for a polyester laminate hollow molded body as described above. As a stretch blow molding method, the above preform is stretched in the longitudinal axis direction within the stretching temperature range of the former 8-layer laminated body, and then further blow molded to stretch it in the transverse axis direction (biaxial Stretch blow molding method), etc. can be mentioned.

For example, to manufacture a polyester resin container using the biaxial stretch blow molding method, a parison with a bottom is molded using a normal injection molding machine, or a parison molded using an extrusion molding machine is obtained by making one end of the parison bottomed. The parison was stretched at a temperature of 80 to 120, which is the stretching temperature of a polyester laminate molded product.
℃, preferably 90 to 110'C, by a rod moving in the longitudinal direction in the blow mold and blowing pressurized gas, 1.5 to 3.5 times, preferably 2 to 3 times, in the longitudinal direction. Another example is a method of stretching 2 to 5 times, preferably 3 to 4.5 times, in the transverse direction.

The polyester laminate hollow molded article according to the present invention has excellent transparency and gas barrier properties, and therefore can be used for various applications such as -F1. In particular, the biaxially stretched blow-molded container, which is a polyester laminated hollow molded product according to the present invention, has excellent gas barrier properties and good transparency, so it can be used for containers such as seasonings, ura, alcoholic beverages, cosmetics, detergents, etc. Of course, it can be used as a container for sparkling beverages such as cola, cider, and beer. That is, by using the polyester laminated hollow molded product according to the present invention, the shelf life can be extended without increasing the wall thickness of the container unlike conventional containers, and the transparency of the obtained molded product can be extended. is also excellent. .

Effects of the Invention The polyester laminate molded product, polyester stretched laminate molded product, preform for polyester multilayer hollow forming body, and polyester stretched multilayer hollow molded product of the present invention all have excellent melt moldability, stretch moldability, transparency, and gas barrier properties. Excellent in sex.

[Examples] The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Reference example 1 The copolyester was polymerized as follows.

The following ingredients were added to a 1 liter stainless copper reactor equipped with a stirrer, nitrogen gas inlet, and condenser.

122.5 g of isophthalic acid 177 g of naphthalene dicarboxylic acid 94.8 g of ethylene glycol 24, 4 g of 1,3-bis(2-hydroxyethyne)benzene 038 g of 1.1-)lishydroxymethylpropane 0. 958p-titanyl acetylacetonate 0.0
77 g of 5b203 o,olOg of tetrathorium ethylenediaminetetraacetate 0.027 g of manganese hypophosphite monohydrate reaction mixture at 220° C. for 1 hour under nitrogen atmosphere and then at 240° C.
The mixture was heated for 25 minutes. During this time, water was continuously distilled off. Next, 0.164 g of tris(nonylphenyl)phosphite was added to the mixture in the reactor.

The reaction temperature was raised to 250'C and kept under nitrogen atmosphere for 35 minutes.

The nitrogen gas flow was then stopped and a vacuum of less than 0.4 ml IHg was applied. The reaction was carried out at 275°C with 0.4n+nH
It continued for 4 hours at less than g. The ground copolyester had a solid viscosity of 0.83 dN/g. The glass transition temperature is as high as 73°C, and the permeability of carbon dioxide is 30CC-
mm/lT111-day-aLm, and the gas barrier properties were good.

Reference Examples 2 to 7 Copolyesters having the compositions shown in Table 1 were synthesized in the same manner as in Reference Example 1, sheets were molded from the copolyesters, and gas barrier properties were measured.

The results are shown in Table 1.

Example 1 Polyethylene terephthalate (Ougetsu 1 manufactured by Sangatsu Pet Co., Ltd.) P, T J13 dried at 150°C for 10 hours
5) is press-molded at about 260℃ to a thickness of about 100μ.
Separately, a mixture of 20 parts of the copolyester of Reference Example 1 to 100 parts of the above polyethylene terephthalate was prepared by using an extruder to produce a press sheet of "n".
Melt extrusion at 60'C to 280'C to produce pellets of the composition;
A press sheet having a diameter of about 100 It m was produced by press molding at 0°C. Furthermore, the above press sheet of polyethylene terephthalate and a press sheet of a composition of polyethylene terephthalate and copolyester were superimposed on top, and press molding was performed at about 260°C to form a two-layer, two-layer structure with a thickness of about 600 μm. A laminated sheet was produced. The obtained laminated sheet has good adhesion between the polyethylene terephthalate layer and the composition layer, and has low haze (
IIAZIE) was determined by JPI to be 1.2%. Furthermore, as a result of measuring the gas barrier properties of this laminated press sheet, the carbon dioxide permeability coefficient was 15. 5ml ・m+
*/rrf-day-atffl.

Furthermore, this laminated sheet consisting of the polyethylene terephthalate layer and the composition layer was simultaneously stretched by three times in the vertical axis direction and the horizontal axis direction using a biaxial stretching device to produce a biaxially stretched film. The obtained biaxially stretched film has a thickness of about 5
The film had a thickness of 0 (tm) and was uniformly biaxially stretched. This biaxially stretched film also had good interlayer adhesion between the polyethylene terephthalate layer and the composition layer.

Furthermore, as a result of measuring the physical properties of this biaxially stretched film, the haze (IIAZE) was 0.6%, and the carbon dioxide permeability coefficient was 10. 0m1-mm/rr+” ・day
-It was an ATM.

Examples 2-3. Comparative Examples 1 to 4 Press sheets,
A biaxially stretched film was obtained. II a z of what was obtained
e, carbon dioxide gas permeability coefficients are as shown in Table 2.

Example 4 First, injection molding of the polyethylene terephthalate in Example] was carried out, and then 1.00 parts of the polyethylene terephthalate in Example] was mixed with 20 parts of the copolyester of Reference Example 1 by 717° injection molding. The inner layer consists of a polyethylene terephthalate layer, and the outer layer consists of a composition layer of copolyester and polyethylene terephthalate I, each having a thickness of about 1.6+.
A preform of nn was produced. Then, this preform was heated to 85 to 95°C using a far-infrared heating device, and then stretched using a stretch blow molding machine to a reduction of 2.5 times (width) and about 4.3 times horizontally to form a minimum The polyethylene terephthalate layer in the thick part is about 150 μm, and the composition layer is about 1
A two-layer stretched bottle with a diameter of 50 μm and an internal volume of about 1 g was molded. Next, the transparency of the side of this stretched bottle was adjusted to ii [
As a result of setting l+, the cloudiness (+IAZE)'' is 1.596
Met. Second, as a result of measuring the gas barrier properties of the medium bottle, the carbon dioxide permeability was 2.0 ml.
/day-bottle-aiIIIl was there.

Comparative Example 5 The polyethylene terephthalate layer in Example 1 was injection molded to produce a preform consisting only of the polyethylene terephthalate layer and having the same thickness (approximately 3.2 mm) as the preform in Example 5. This preform was then stretch-blown in the same manner as in Example 5 to produce a stretched bottle having a minimum wall thickness of approximately 300 μm and an internal volume of approximately 1 g.

The haze (llAZ17) of the side surface of this stretched bottle was measured and found to be 4.5%. In addition, the carbon dioxide gas permeability of this stretched bottle is 2.0ml/day-bo.
It was a ttle-arm.

Claims (1)

[Claims] 1) A laminate molded product is composed of (A) a polyalkylene terephthalate layer and (B) a copolyester layer, and this copolyester layer (B) is made of a copolyester such as the following:
Or, it consists of a copolyester composition consisting of a copolyester and polyethylene terephthalate as shown below, in which 95 to 60 mol% of the dicarboxylic acid component units constituting this copolyester are isophthalic acid component units, and 5 to 40 mol% is a 2,6-naphthalene dicarboxylic acid component unit, and 95 is a dihydroxy compound component unit.
A polyester laminate molded article, characterized in that ~70 mol% is ethylene glycol component units, and 5 ~ 30 mol% is 1,3-bis(2-hydroxyethoxy)benzene component units. 2) The stretched laminate molded product is composed of (A) a polyalkylene terephthalate layer and (B) a copolyester layer, and this copolyester layer (B) is composed of a copolyester as shown below or a copolyester as below. Consisting of a copolyester composition consisting of polyethylene and terephthalate, 95 to 60 mol% of the dicarboxylic acid component units constituting this copolyester are isophthalic acid component units, and 5 to 40 mol% are 2,6-naphthalenedicarbone. is an acid component unit, and 95 is a dihydroxy compound component unit.
~70 mol% are ethylene glycol component units, and 5 to 30 mol% are 1,3-bis(2-hydroxyethoxy)benzene component units, and the polyalkylene terephthalate layer (A) and the copolyester layer (B)
A polyester stretched laminate molded article, characterized in that the polyester is stretched. 3) A preform for a laminated hollow molded body is composed of (A) a polyalkylene terephthalate layer and (B) a copolyester layer, and this copolyester layer (B) is made of the following copolyester or the following. Consisting of a copolyester composition consisting of a copolyester and polyethylene terephthalate, 95 to 60 mol% of the dicarboxylic acid component units constituting this copolyester are isophthalic acid component units, and 5 to 40 mol% are 2,6- 95 naphthalene dicarboxylic acid component units, and 95 dihydroxy compound component units.
A preform for a polyester laminate blow molded body, characterized in that ~70 mol% is ethylene glycol component units, and 5 ~ 30 mol% is 1,3-bis(2-hydroxyethoxy)benzene component units. 4) The laminated hollow molded body is composed of (A) a polyalkylene terephthalate layer and (B) a copolyester layer, and this copolyester layer (B) is made of the following copolyester or the following copolyester. 95 to 60 mol% of the dicarboxylic acid component units constituting this copolyester are isophthalic acid component units, and 5 to 40 mol% are 2,6-naphthalenedicarboxylic acid component units. component unit, and 95 of the dihydroxy compound component unit.
A polyester laminate hollow molded article characterized in that ~70 mol% of the polyester component units are ethylene glycol component units, and 5 to 30 mol% of the polyester component units are 1,3-bis(2-hydroxyethoxy)benzene component units.