JPS62106925A - Polyhydroxy polyether and its use - Google Patents

Abstract

PURPOSE:To obtain a polyhydroxy polyether excellent in gas barrier property, melt moldability and drawability, by using a linear polyhydroxy polyether having a specified intrinsic viscosity and a specified melt viscosity as a component. CONSTITUTION:A polyhydroxy polyether represented by formula I (wherein R<1> is a p-phenylene-based bivalent aromatic hydrocarbon group and n is a number) and having an intrinsic viscosity [eta] of 0.9-2dl/g and a melt viscosity which lies in the range of 10<3>-10<5>P as determined by extrusion through a nozzle 30mm in length and 1.0mm in diameter under conditions of 240 deg.C and a shear rate of 10sec<-1>. Said polyhydroxy polyether can be obtained by reacting an aromatic diol diglycidyl ether of formula II (wherein R<1> is a p-phenylene- based bivalent aromatic hydrocarbon group) with an aromatic diol of formula III in the presence of a catalyst such as a tert. amine or quat. ammonium compound or a tert. phosphine.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a polyester material having excellent /8 melt moldability, excellent mechanical strength, transparency and gas barrier properties, and having performance suitable as a material for containers. This invention relates to hydroxy polyethers and their uses.

[Prior Art] Glass has been widely used as a material for containers for seasonings, oils, beer, alcoholic beverages such as Japanese sake, soft drinks such as carbonated drinks, cosmetics, detergents, and the like.

However, although glass containers have excellent gas barrier properties, they are expensive to manufacture, so empty containers are usually collected after use.
A method of circular reuse is adopted. however,
Glass containers are heavy, which increases shipping costs, and they also have drawbacks such as being easily damaged and inconvenient to handle.

In order to overcome the aforementioned disadvantages of glass containers, there is a growing shift from glass containers to various plastic containers. Various plastics are used as materials depending on the type of stored item and its intended use. Among these plastic materials, polyethylene terephthalate has excellent gas barrier properties and transparency, and is therefore used as a material for containers for seasonings, soft drinks, detergents, cosmetics, and the like. However, polyethylene terephthalate is still not sufficient for beer and carbonated beverage containers, which require the most stringent gas barrier properties (although polyethylene terephthalate does not have enough wall thickness to be used in these containers). Currently, the demand for polyester containers is increasing, and in order to expand their use, polyester containers with excellent gas barrier properties and melt moldability must be improved. Polyester is in high demand.

JP-A-59-64624 discloses polyalkylene isophthalates such as polyethylene isophthalate, copolymers thereof, and molded articles formed therefrom as packaging materials having good gas barrier properties against oxygen and carbon dioxide. ing.

Japanese Unexamined Patent Publication No. 59-670 filed by the same applicant as the above application
Publication No. 49 discloses a multilayer packaging material consisting of a layer made of a polyalkylene isophthalate or a copolymer thereof as described above and a layer made of a polyalkylene terephthalate such as polyethylene terephthalate or a copolymer thereof, and a molded product made thereof, such as a bottle. There is.

Furthermore, JP-A-59-39547 discloses that the innermost layer is made of polyester whose main repeating unit is ethylene terephthalate, the outer layer is made of polyester whose main repeating unit is ethylene isophthalate, and the thinner part of the container is at least A multilayer container with excellent gas permeation resistance that is oriented in one direction is disclosed.

As a material different from polyester, JP-A-48-362
Publication No. 96 discloses a highly transparent product containing m-xylylene diamine or a mixture of m-xylylene diamine and p-xylylene diamine as the diamine component and a specific aliphatic dicarboxylic acid as the dicarboxylic acid component. A polyamide is disclosed. Publication G describes that the polyamide exhibits good impact strength and excellent processability, but there is no mention of its gas barrier properties.

JP-A-56-64866 discloses that the outermost layer and the innermost layer are made of polyester having ethylene terephthalate as the main repeating unit, and the middle layer is made of m-xylylene diamine or m-xylylene diamine and p-xylylene diamine. A multilayer container is disclosed which is made of a polyamide containing a mixture as a diamine component and whose thin wall portion is oriented in at least one direction. The publication states that the container has excellent oxygen barrier properties without impairing the excellent mechanical properties, transparency, chemical resistance, etc. of polyester.

Furthermore, JP-A-58-183243 discloses a biaxially stretched blow-molded bottle body in which two inner and outer surface layers are made of polyethylene terephthalate and an intermediate layer is made of a mixed material of polyethylene terephthalate and xylylene group-containing polyamide. has been done.

Also, Journal of Applied Pol
ymer 5science.

Volume 7, 2135-2144 (1963),
The following formula (c), 1000 -E -0-CIl2-CIl-
C112-3-7---(c) Here, E is CH3, and gas barrier properties of homopolyhydroxyether I are disclosed. Lol! The most elementary permeability is 0.5
cc-rQil/ 100 in /24 hr/at
It is m. The one with the lowest water vapor mobility is E, H3, 90! Under the conditions of X R, H, 5t<-mil/
It is 1001n2/24hr.

Also, Journal of ApT)liend P
olymerScience, Volume 7, 2145-2
152 (1965), discloses the gas barrier properties of a cobohydroxy polyether represented by B r CHs B r (wherein R1 and R2 are not the same). The highest value of oxygen permeability for CH3 is 5 g-mA'/IQ Oin/24
hr, /'atm. The one with the lowest water vapor mobility has R as CH=.

4g-mg/l 001n under conditions of 90% R,H,
/24hr.

Furthermore, regarding polymers made from hydroquinone and epichlorohydrin, there is an old US Patent No. 26020.
No. 75 (1948, 11, 26). However, the polymer in that example has an intrinsic viscosity of 0.2 to 0.8 as determined in traresol.
However, it is difficult to say that the polymer is linear and has a sufficiently extended molecular weight.

Furthermore, JP-A-56-100828 discloses that a linear hydroquinone phenoxy polymer produced from hydroquinone and epihalohydrin by interfacial polymerization is characterized by strong air permeability to oxygen and carbon dioxide. ing.

However, the hydroquinone phenoxy polymer is also described to have an intrinsic viscosity in the range of 0.45 to 0.9 measured in a 60:40 (volume ratio) mixed solvent of phenol and tetrachloroethane; As with the patent, it is difficult to say that the molecular weight has been sufficiently increased.

Furthermore, there is also a method for producing a resin by reacting dihydric phenols with shrimp halohydrin in advance to produce diglycidyl ethers of dihydric phenols or their low polymers, and then further reacting them with dihydric phenols. , disclosed in Japanese Patent Publication No. 28-4494. However, this publication does not disclose homopolyhydroxy polyethers of hydroquinone, and the polymers produced in the examples are either insoluble or have an epoxide equivalent of 5,600 or less,
Depending on the method, it is difficult to produce a linear high molecular weight hydroquinone phenoxy polymer.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a polyhydroxypolyether having excellent gas barrier properties, particularly excellent barrier properties against oxygen and carbon dioxide gas.

Another object of the present invention is to provide a polyhydroxy polyether with excellent melt moldability and stretchability.

Still another object of the present invention is to provide a stretched molded product of polyhydroxy polyether as described above.

Still another object of the present invention is to provide a polyester laminate molded product comprising a layer of polyhydroxy polyether as described above and a layer of polyalkylene terephthalate whose main constituent is ethylene terephthalate, and a stretched molded product thereof.

Still another object of the present invention is to provide a preform for a blow molded article and a blow molded article comprising a layer of polyhydroxy polyether and a layer of polyalkylene terephthalate as described above.

Further objects and advantages of the present invention will become apparent from the description below.

[Means and effects for solving the problems] According to the present invention, the above-mentioned objects and advantages of the present invention are as follows. It represents a divalent aromatic hydrocarbon group containing a phenylene group as a main component, and n is a positive number. ]
A substantially linear polyhydroxy 6-polyether represented by
Intrinsic viscosity [η] measured at C is 0.9 to 2 dl
/ g, and has a length of 30 mm and a diameter of 1.0 m.
m nozzle at 240℃ and scrubbing speed 10sec-'
The melt viscosity when extruded under the conditions is 10”poise
This is achieved using a polyhydroxy polyether characterized in that the poise is in the range of 105 to 105 poise.

Further, the polyhydroxy polyether of the present invention can be produced, for example, by the method described below.

(EL) General formula (I [wherein R is p-] represents a divalent aromatic hydrocarbon group whose main component is a dihydrocarbon group. Diglycidyl ether of an aromatic diol represented by (b) an aromatic represented by the general formula [1ll] HO-R-0T(...rill) [wherein R4-4 represents the same group as above] produced by a method characterized by reacting a group diol with a tertiary amine, a quaternary ammonium compound, a tertiary phosphine, and a quaternary phosphonium compound in the presence of at least one catalyst selected from .

In the above method, the diglycidyl ether of aromatic diol used as one of the raw materials is represented by the above formula [M]. In the above formula [■], R1 represents a divalent aromatic hydrocarbon group containing a p-phenylene group as a main component. That is, R1 can be a p-phenylene group or a mixed group of a p-phenylene group mainly consisting of a C1p-phenylene group and a divalent aromatic hydrocarbon group other than the p-phenylene group.

Aromatic hydrocarbon groups other than p-phenylene groups may be present in a proportion of 50 mol % or less, preferably 40 mol % or less, based on p-phenylene groups. Examples of divalent aromatic hydrocarbon groups other than p-phenylene include:

H3CH3 etc.

When R is a p-phenylene group, the diglycidyl ether of the aromatic diol of the above formula Cl11 is a diglycidyl ether of hydroquinone represented by the linear formula.

Further, examples of the diglycidyl ether of an aromatic diol that can be used together with the diglycidyl ether of hydroquinone include the following compounds.

The compound of the above formula [■] is an aromatic 1ilJM can be obtained by reacting a group diol with shrimp halohydrin represented by the following formula [■] (where X is a halogen atom) in the presence of a basic compound.

The diglycidyl ether of the aromatic diol of the above formula [㪪] obtained from the aromatic diol and shrimp halohydrin may contain a small amount of halogen atoms derived from shrimp halohydrin, which is the raw material, or the aromatic diol and shrimp halohydrin It may contain a small amount of monoglycidyl ether or low polymer glycidyl ether.

c as shrimp halohydrin used to produce diglycidyl ether of aromatic diol of the above formula [■]
Preferred is, for example, epichlorohydrin or ebibromohydrin.

In the above production method, the aromatic diol similarly used as one of the raw materials and the aromatic diol used to produce the diglycidyl ether of the aromatic diol of the above formula [11] are represented by the above formula Cl9) It is something. The above formula [! 1], R1 represents a divalent aromatic hydrocarbon group containing p-phenylene group as a main component,
Groups similar to those described for f) can be exemplified.

Therefore, compounds of the above formula (bl) include, for example, hydroquinone or hydroquinone and other aromatic dihydroxy compounds such as resorcinol, methylhydroquinone, chlorohydroquinone, bisphenol A, dichlorobisphenol A.

Tetrachlorobisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol AOP,
Mixtures with bisphenol L, bisphenol V, bisphenol S, etc. can be mentioned.

The above production method uses the diglycidyl ether of the above-mentioned aromatic diol and the aromatic diol using at least one of a tertiary amine, a quaternary ammodium compound, a tertiary phosphine, or a quaternary phosphonium compound as a catalyst. It is carried out by reacting using

The usage ratio of diglycidyl ether (n) of aromatic diol and aromatic diol [IID is 0.95 to 0.95 to 1 mole of aromatic diol diglycidyl ether per mole of aromatic diol diglycidyl ether (n) and aromatic diol [IID].
If1 is used in an amount of 1.05 mol, preferably 0.97 to 1.05 mol, more preferably 0.98 to 1.02 mol.

Examples of tertiary amines used as catalysts include triethylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-secondary-butylamine, tri-n-ethylbenzylamine,
Tribenzylamine nat can be opened. Examples of quaternary ammonium compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, detra-n-propylammonium hydroxide, tetraisopropylammonium hydroxide, tetra-n-butylammonium hydroxide, and trimethylpendylammonium hydroxide. quaternary ammonium hydroxide compounds such as triethylbenzylammonium hydroxide, tetramethylammonium chloride
cum, tetraethylammonium chloride, tetra n-chloride
Propylammonium, ifl tetra-n-butylammonium, W tetra-n-amylammonium-4
(1) Methylphenylammonium (1), (I) Limethylbenzylammonium, Triethylbenzylammonium chloride, Tetramethylammonium bromide, Tetraethylammonium bromide, Tetra-n-propylammonium 4, Tetra-lobylammonium bromide, Trimethylcecylammonium bromide, 4)limethylphenylammonium, tl)limethylbenzylammonium, tetramethylammonium iodide, tetraethylammonium iodide, tetra-n-furobylammonium iodide, trimethylphenylammonium iodide, iodide Examples include halogenated quaternary ammonium compounds such as trimethylbenzylammonium. Examples of tertiary phosphines include triethylphosphine, tri-n-butylphosphine, triphenylphosphine,
Examples include trinonylphenylphosphine. , further as a quaternary phosphonium compound +i, for example a quaternary phosphonium hydroxide compound such as tetramethylphosphonium hydroxide.

Tetramethylphosphonium chloride, tetra-n-butylphosphonium chloride-tetraphenylphosphonium chloride, a
Tetra-n-butylphosphonium.

Examples include halogenated quaternary phosphonium compounds such as methyltriphenylphosphonium bromide-n-butyltriphenylphosphonium bromide.

The amount of I to be used is 0.001 to 10 mol % per mol of diglycidyl ether of aromatic diol.

Preferably (0.005 to 5 mol%, more preferably 4
It is suitable that it is 0.01-11-1 mol%.

In addition, in the production method described above, in order to stabilize the terminal end of the polyhydroxy polyether product, a small amount of a compound containing one phenolic hydroxyl group can be added for reaction. Examples of compounds containing one phenolic hydroxyl group include phenol, n-cresol, m-cresol, p-cresol, p-t-butylphenol + p-phenylphenol, and p-cumylphenol. can. When using a compound containing one of these phenolic hydroxyl groups.

iIn 0.05 mol 1 per mol diglycidyl ether of ordinary aromatic diol, preferably c: to, o
It is preferable to use bonds containing 5 mol or less, more preferably 2 mol or less of c4 o, o.

Further, in the production method, the viscosity of the system during the C1 reaction is reduced to allow the reaction to proceed suitably.

Inert! 8 solvents can also be used.
1-To close C, an example is n-decane, decahydronaf/
/l nato saturated hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, tetramethylpenguin, ethylbenzene, cumene, n-7' thylbenzene, tetrahydronaphthalene, naphthalene, methyl ayl ketone, Methyl isobutyl ketone, 2-hexanone.

Ketones 1i such as cyclohexanone and acetophenone,
Examples include amides such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone, and sulfoxides such as dimethylsulfoxide. When these solvents are used, they are used in an amount of, for example, 2 parts by weight or less, preferably 1 part by weight or less, and more preferably 0.5 parts by weight or less, per 1 weight part of the polymer normally produced. Before finishing the system, reduce the pressure or
After completion of the reaction, it is separated and removed from the polyhydroxy polyether product by a conventional method such as reprecipitation.

The reaction is usually about 70-200-C-preferably 80-18
It is carried out at 1 grade at 0°C. The reaction is usually carried out under normal pressure or increased pressure, but may also be carried out under reduced pressure if the solvent used for adjusting the viscosity is to be removed. The reaction is usually completed in 0.5 to 10 hours under stirring. After the reaction, the polyhydroxy polyether product is separated and obtained from the reaction system by a method known per se.

Thus, according to the above manufacturing method, as described above, the following formula (1) %Formula % 81 has the same definition as above, and n is a positive number. ) A substantially linear polyhydroxypolyether represented by -c is obtained. In the above formula, the value of n is such that the intrinsic viscosity [η] of the polyhydroxy polyether is 0.9 to 2.
dl/g, length 301, diameter 1.0Lll
The sagging speed is 19S at 240″C compared to the ff+ nozzle.
The melt viscosity when extruded under the conditions of ee is 103p
It is a positive number determined to be in the range of 10 to 10 poise. Intrinsic viscosity and melt viscosity are measured by the methods defined below. "Substantially linear structure" means "substantially consisting of a linear structure or a chain structure having a branched chain", and "C" means not substantially a gel-like crosslinked structure (C network structure). This is confirmed by the fact that the polyhydroxy polyether of the present invention is substantially completely dissolved in the solvent used to measure the intrinsic viscosity.

As mentioned above, the polyhydroxy polyether of the present invention has an intrinsic viscosity of 0.9 to 2 al/lz.

If the intrinsic viscosity is greater than 2 dl/g, the melt-molding edge of the polyhydroxy polyether will deteriorate, and its stretchability will also deteriorate. Also, the intrinsic viscosity is 0
．． When the melt viscosity is less than 9 dl/g, the melt viscosity differs greatly from that of polyalkylene terephthalate, making it difficult to produce a polyester laminate molded product or a preform for a polyester multilayer hollow molded product. The Borich 1'roxy polyether of the present invention is preferably Gio,
It shows an intrinsic viscosity of 9 to 1.8 d11/g.

In addition, as described above, the polyoxybolyether of the present invention was
Melt viscosity when extruded at 40℃ and shear rate of 10scc is 103noise f;
It is in the range of 5υnl+e. Melt viscosity is 10 vni3
When it is larger than e, the melt moldability of the polyhydroxy polyether decreases. Also, the melt viscosity is I
When Q' is smaller than vn+np, it becomes difficult to produce a polyester laminate molded product or a preform for a polyester multilayer hollow molded product. The polyhydroxy polyether of the present invention preferably has a melt viscosity of 1 under the conditions listed below.
, 2X I Q poise or 5X10'pni
Indicates the value of se.

The polyhydroxy polyether of the present invention may have hydroquinone units (-oQoH) or other aromatic diol units (for example) at its terminals, depending on the proportion of the raw material compounds used in its production.

->ΣOH), a glycerin unit (-QCH20HOH20B>, a certain ILJ epoxy group (-0)1-(3H-n■2).The terminal hydroxyl group (-OH) of these \./, or the epoxy It can be converted into a carboxylic acid ester such as an acetate ester (-ococH3) or an ether such as an ethoxy group (-oc2r+5) by a radical or etherification method.The polyhydroxy polyethers of the present invention may have various terminals as described above. is included.

The ratio of the weight average molecule fi (Mw) to the number average molecule ft (pan) of the polyhydroxypolyether C of the present invention (Mw
/Mn) is usually in the range of 1.5 to 10, for example.

The polyhydroxypolyether of the present invention can also be used in an unstretched state as a raw material for molded articles of various shapes such as films, sheets, fibers, containers, and others by ordinary molding methods. Furthermore, even when stretched polyhydroxypolyether is molded into a film, sheet, or container, molded products with excellent gas barrier properties can be obtained. Next, the stretched molded product of polyhydroxy polyether of the present invention will be explained.

The polyhydroxypolyether stretched molded product of the present invention includes a -axially stretched molded product and a biaxially stretched molded product, and the form thereof may be a film, a sheet, or a fiber. Here, when the polyhydroxypolyether stretched molded product is uniaxially stretched, the stretching ratio is usually 1.1 to 10 times, preferably 1.2 to 8 times, particularly preferably 1.5. It is in the range of 7 to 7 times. When the stretched product is biaxially stretched, the stretching ratio in the longitudinal direction is usually 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5. or 6
In the transverse direction, it is usually 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5 to 6 times.

K (III
The molded article may contain a known inorganic filler, if necessary.
Appropriate amounts of various additives such as lubricants, slip agents, antiblocking agents, stabilizers, antistatic agents, and pigments may be blended.

Any conventionally known method can be adopted as a method for producing the stretched polyhydroxy polyether molded article of the present invention. In general, an original molded body such as a film or Sea 1- formed from the polyhydroxypolyether or a ♀■ composition containing the above-mentioned additives as necessary is used as it is, or once heated to a temperature below the glass transition point. After being cooled and solidified, the reheated material is stretched at a temperature above the glass transition point, preferably at or above the glass transition point by 80° C. higher than the glass transition point.

The stretched molded product of polyhydroxy polyether of the present invention is
For example, when the original molded product is a film or sheet, methods for making M-shaped products include a method of stretching an unstretched film or sheet in a uniaxial direction (--axial stretching), a method of stretching the unstretched film or sheet in the longitudinal direction, and a method of stretching the unstretched film or sheet in the longitudinal direction. A method of further stretching in the transverse direction (biaxial stretching), a method of simultaneously stretching in the longitudinal and transverse directions (biaxial stretching), a method of stretching in the direction of the longitudinal axis and the transverse axis simultaneously (biaxial stretching), and a method of stretching sequentially in any one direction after biaxial stretching. Examples include a method in which the film or sheet is stretched biaxially and then further stretched in both directions, and a so-called vacuum forming method in which stretch-forming is performed by reducing the pressure in the space between the film or sheet and a mold. Moreover, it is also possible to produce a stretched molded product of these polyhydroxypolyethers in the form of a laminate with other resins. Such manufacturing methods include forming an original molded body such as a film or sheet of polyhydroxy polyether with an original molded body such as a film or sheet of other resin in a single layer or multiple layers, and then stretching; Examples include a method of adhering a film or sheet of another resin to a stretched polyether molded product.

Next, a laminate molded product composed of a polyhydroxy polyether layer of the present invention and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate will be described. Specifically, the laminate molded product is a two-layer laminate molded product composed of two layers of the polyhydroxypolyether layer and polyalkylene terephthalate Fi, the polyhydroxypolyether layer is used as an intermediate layer, and the amphoteric side layer is used as the amphoteric side layer. A three-layer laminate molded product having a polyalkylene terephthalate layer,
A three-layer laminate molded product having the polyalkylene terephthalate layer as an intermediate layer and the polyhydroxypolyether layer as both side layers, a laminate having a four-layer structure or more in which the polyhydroxypolyether layer and the polyalkylene terephthalate layer are alternately laminated. A multilayer laminate molded product, the rain fall outer layer of which is composed of the polyalkylene terephthalate layer, a laminate molded product with a four-layer structure or more in which the polyhydroxypolyether layer and the polyalkylene terephthalate layer are alternately laminated. A multilayer laminate molded article whose outer layer is composed of the polyhydroxypolyether layer, the polyhydroxypolyether Nh and the polyalkylene terephthalate F
Examples include a multilayer laminate molded product having a four-layer structure or more in which i is alternately laminated, and the outermost layer is composed of the polyhydroxypolyether layer and the polyalkylene terephthalate layer. The laminated molded product can be used not only for sheet-like objects, plate-like objects, and tube-like objects, but also for various hollow objects, containers, structures of various shapes, and the like. The laminate can be manufactured by a conventionally known method.

The thicknesses of the polyhydroxypolyether layer and the polyalkylene thirefrate layer constituting the laminate molded product are appropriately determined depending on the use of the laminate molded product, and are not particularly limited. When the laminate molded product is the two-layer laminate molded product, the thickness of the polyhydroxy polyether layer is usually 4 to 350μ, preferably 6 to 200μ.
The thickness of the polyalkylene terephthalate layer is between 8 and 600μ, preferably between 10 and 500μ.
within the range of When the laminate molded product is the former of the three-layer laminate molded product, the thickness of the intermediate layer consisting of the polyhydroxy polyether layer is usually in the range of 4 to 350μ, preferably 6 to 200μ, The thickness of each of the outer wound layers of the polyalkylene terephthalate layer usually ranges from 4 to 300 microns, preferably from 5 to 250 microns. 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 8 to 600 mm.
[mu], preferably in the range of 10 to 500[mu], and the thickness of the outer wound layer consisting of the polyhydroxypolyether layer is usually in the range of 4 to 100[mu], preferably 6 to 50[mu]. Even when the laminate molded product is a multilayer laminate molded product having a four-layer structure or more, the thickness of the intermediate layer and the outermost layer made of the polyhydroxypolyether layer, and the thickness of the intermediate layer and the outermost layer made of the polyalkylene terephthalate layer are determined. The thickness of the outer layer can be selected as before.

The polyalkylene terephthalate constituting the laminate molded product of the present invention is a polyester containing ethylene terephthalate as a main constituent unit. The content of ethylene terephthalate structural units in the polyalkylene terephthalate is usually 50 mol% or more, preferably 70 mol% or more. The dicarboxylic acid component units constituting the polyalkylene terephthalate may contain a small amount of other aromatic dicarboxylic acid component units in addition to the terephthalic acid component units. Specific examples of aromatic dicarboxylic acid component units other than terephthalic acid component units include isophthalic acid, fucuric acid, and naphthalene dicarboxylic acid. The diol component units constituting the polyalkylene terephthalate may contain small amounts of other diol component units in addition to ethylene glycol component units. Examples of diol component units other than ethylene glycol component units include 1.
3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexane dimetatool, 1,4-bis(β-hydroxyethoxy)benzene, ■, 3-bis(β-hydroxyethoxy)benzene, Examples include diol component units having 3 to 15 carbon atoms such as 2,2-bis(4-β-hydroxyethoxyphenyl)propane and bis(4-β-hydroxyethoxyphenyl)sulfone.

In addition, the polyalkylene terephthalate may contain a small amount of a polyfunctional compound, if necessary, in addition to the aromatic dicarboxylic acid component unit and the diol component unit. Specifically, the polyfunctional compound component units include trimellitic acid, trimesic acid, 3.3'
, aromatic polybasic acids such as 5,5'-tetracarboxydiphenyl, aliphatic polybasic acids such as butanetetracarboxylic acid, aromatic polyols such as phloroglucin, 1,2,4,5-tetrahydroxybenzene, etc. , glycerin, trimethylolethane, trimethylolpropane, aliphatic polyols such as pentaeryth-17tol, and oxypolycarboxylic acids such as tartaric acid and malic acid.

The composition of the constituent components of the polyalkylene thirefrate is:
The content of terephthalic acid component units is usually 50 to 100.
The content of aromatic dicarboxylic acid component units other than terephthalic acid component units is usually 0 to 50 mol%, preferably 0 to 30 mol%. , the content of ethylene glycol component units is usually in the range of 50 to 100 mol%, preferably 70 to 100 mol%, and the content of diol component units other than ethylene glycol component units is usually 0 to 50 mol%, preferably The content of 1·n range and polyfunctional compound component units of 0 to 30 mol% is usually 0 to 2 mol%, preferably O to 1 mol%.
within the range of In addition, the intrinsic viscosity [η] of the polyalkylene terephthalate (at 25°C in 0-chlorophenol)
) is usually 0.5 to 1.5 d! /g, preferably 0.6 to 1.2 d! /g range,
Melting point is usually 210 to 265°C2, preferably 220°C
to 260°C, and the glass transition temperature is usually 5.
It is in the range of 0 to 120°C, preferably 60 to 100°C.

The laminate molded product has excellent properties such as melt moldability, stretchability, mechanical strength, transparency, and gas barrier properties, so it can be used for various purposes.

A stretch laminate molded product of the present invention comprising a polyhydroxy polyether layer and a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit will be described. The stretched laminate molded product of the present invention is formed by stretching the laminate molded product. The stretched laminate molded product includes a -axially stretched molded product and a biaxially stretched molded product, and the shape thereof may be any shape such as a film, sheet, or plate.

As for the stretching ratio of the stretched laminate molded product, the ratio proposed for the stretched molded product of the polyhydroxypolyether can be applied as is, and it is also possible to heat set the stretched molded product.

The stretched laminate molded product of the present invention is obtained by subjecting the original molded product made of the above-mentioned laminate molded product to a stretching treatment in the same manner as the polyhydroxypolyether.

The stretched laminate molded product of the present invention has excellent properties such as mechanical strength, transparency, and gas barrier properties, so it can be used for various purposes.

The preform for a multilayer hollow molded body of the present invention is a preform for a multilayer hollow molded body that has a laminated structure composed of the polyhydroxy polyether layer and a polyalkylene terephthalate layer mainly composed of ethylene terephthalate. Furthermore, it is a preform for a multilayer hollow molded body having the above-mentioned laminated structure. Examples of preforms having a laminate structure include preforms for two-layer laminates exemplified in the laminate molded product of the present invention, similar preforms for three-layer laminates, and similar multilayer laminates having four or more layers. A preform for use can be similarly exemplified. Among these preforms for multilayer hollow molded bodies, there are preforms having a laminated structure consisting of two layers, the polyhydroxy polyether layer and the acid polyalkylene terephthalate layer, and the polyhydroxy polyether as an intermediate layer and both layers. When a stretched multilayer laminate hollow molded body is formed from a preform having a laminate structure composed of three layers of polyalkylene terephthalate, it has excellent mechanical strength, and has properties such as transparency and gas barrier properties. This is preferable because a stretched multilayer hollow molded article with excellent properties can be obtained.

Inorganic fillers, laxatives, and slip agents that are blended with conventional polyesters as necessary in both the polyhydroxy polyether and the polyalkylene terephthalate that constitute the preform for a multilayer hollow molded body of the present invention. , an anti-blocking agent, a stabilizer, an antistatic agent, an antifogging agent, a pigment, and the like may be added in appropriate amounts.

The preform for a multilayer hollow molded body of the present invention is produced by a conventionally known method. For example, the preform for a multilayer hollow molded body of the present invention can be obtained by molding the tubular article having the laminated structure.

The stretched multilayer hollow molded body of the present invention is a stretched multilayer hollow molded body composed of the polyhydroxypolyether layer and the polyalkylene terephthalate layer, and is obtained by stretch-blow molding the preform for the multilayer hollow molded body. Manufactured. The stretched multilayer hollow molded body may be a stretched two-layer hollow molded body composed of the polyhydroxypolyether layer and the polyalkylene terephthalate layer, or may be a stretched two-layer hollow molded body composed of the polyhydroxypolyether layer and the polyalkylene terephthalate layer. It may be a stretched three-layer hollow molded product composed of three layers laminated alternately, or it may be a multilayer of four or more layers composed of the polyhydroxy polyether layer and the polyalkylene terephthalate layer alternately laminated. It may also be a stretched multilayer hollow molded product.

The stretched multilayer hollow molded product may be a uniaxially stretched molded product or a biaxially stretched molded product, but generally a biaxially stretched molded product has excellent mechanical strength and gas barrier properties. suitable. As for the stretching ratio of the stretched multilayer hollow molded article, the stretching ratio described for the stretched polyhydroxypolyether molded article is applied as is.

The stretched multilayer hollow molded body of the present invention is produced by stretch blow molding the preform for the multilayer hollow molded body. Examples of this method include a method (biaxial stretch blow molding) in which a preform at the above temperature is stretched in the vertical axis direction and then further blow molded to stretch it in the horizontal axis direction.

The stretched multilayer hollow molded article of the present invention has excellent mechanical strength, heat resistance, gas barrier properties, and transparency, and can therefore be used for various purposes. In particular, the biaxially stretched multilayer blow-molded container of the present invention has excellent gas barrier properties, so it can be used for seasonings, oil, beer, class 16 such as Japan L West, soft drinks such as cola, cider, and juice, cosmetics, and detergents. It is excellent as a container for beer or carbonated drinks, but especially when used as a container for beer or carbonated drinks, it becomes possible to reduce the wall thickness of the container and extend the shelf life.

Further, when the stretched polyhydroxy polyether molded product of the present invention is a stretched film, these can be specifically used for gas barrier packaging materials, metallized films, and the like.

〔Example〕

Next, the present invention will be specifically explained using examples. In addition, in Examples and Comparative Examples, parts mean parts by weight, and performance evaluation was performed according to the following method.

The composition of polyhydroxypolyether was determined by measuring the magnetic resonance spectrum.

The intrinsic viscosity [η] of the polyhydroxy polyether was measured in 0-chlorophenol at 25°C.

The glass transition temperature of polyhydroxy polyether is determined by heating the resin sample to a melt-flowing state and rapidly cooling it to room temperature using a differential scanning calorimeter at a heating rate of 10°C/10°C.
It was determined by measuring min.

The melt viscosity of polyhydroxy polyether is determined by Co., Ltd.
240℃ using a thin tube extrusion meter manufactured by Shimabara Seisakusho.
It was measured with

Regarding the gas buyer properties of sheets, stretched films, or stretched bottles made of polyhydroxypolyether or its laminate, the oxygen gas permeability coefficient is
The carbon dioxide permeability coefficient was measured using an OXTRAN device manufactured by
) manufactured by PERMATR-AN C-r
Each sample was stabilized at 25°C using a V-packing apparatus.

Example 1 2202 parts of hydroquinone, hydroquinone diglycidyl ether (epoxy group content 8.98 eq/kg.

Terminal hydroxyl group content 20eq/10g) 44
67 parts of a 20% aqueous solution of tetraethylammonium hydroxide, 13 parts of cyclohexanone, and 169 parts of cyclohexanone were charged into a reaction tank equipped with a stirring device and a reflux device, and the inside of the tank was sufficiently replaced with nitrogen. After reacting at 120°C for about 2 hours, P-cumylphenol 22
The mixture was further heated to about 130°C and reacted for about 1 hour. An increase in the viscosity of the system was observed as the reaction time progressed. Next, this reaction mixture was extracted in the form of a strand from the reaction tank, cooled by immersing it in water, and then cut into pellets.

The pellets were then dried under reduced pressure at approximately 50°C, and then placed in a co-rotating twin-screw extruder with a vent and 30 gates (Co., Ltd.).
manufactured by Plastic Engineering Research Institute, L/D=42),
Extrusion is performed under reduced pressure at a barrel temperature of about 160°C to about 240°C and a residence time of about 20 minutes to remove the solvent cyclo-xanone from the vent, and the 't+?
After cooling, it was cut into pellets. The intrinsic viscosity [η] of the polyhydroxy polyether thus obtained was 0.98 J/g, its glass transition temperature was 63°C, and it had a length of 30 mm, a diameter of 1,0
mm nozzle at 240°C and shear speed IQcm
The melt viscosity when extruded under the conditions is 5 x 10"
It was poise.

Examples 2 to 3 In Example 1, the solvent cyclohexanone was not used, the amounts of hydroquinone diglycidyl ether and cumyl phenol were as shown in Table 1, and the reaction conditions of the reaction tank and twin screw extruder were changed. A pellet-shaped hydroquinone polyhydroxypolyether was produced in the same manner as in Example 1 except that the operating conditions were as shown in Table 1. The intrinsic viscosity [η], the glass transition temperature, and the rubbing speed of the obtained polyhydroxypolyether at 240°C and 10
The melt viscosities when extruded under the conditions of Cm-' were as shown in Table 1.

Examples 4-6 In Example 1, p-cumylphenol was not used, and instead of hydroquinone, the aromatic diols in Table 2 were used as described in Table 2, and in place of hydroquinone diglycidyl ether, Table 2 The reaction in the reaction tank and the operation using the twin-screw extruder were carried out in the same manner as in Example 1, except that the diglycidyl ethers of the aromatic diols described were used as shown in Table 2, to produce each pellet-shaped polyhydroxy polyether. Manufactured. The composition ratio of aromatic diol of the obtained polyhydroxy polyether, the intrinsic viscosity (
η], glass transition temperature and length 30 mm, fM 1.
240°C and shearing speed of 10s from a 0mm nozzle
The melt viscosities when extruded under ec conditions were as shown in Table 2.

Comparative Example 1 2202 parts of hydroquinone, 1851 parts of epihalohydrin
parts, 6000 parts of cyclohexanone, 5100 parts of distilled water,
l-lymethylbenzylammonium chloride, iSo
and 1,792 parts of a 50% sodium hydroxide aqueous solution were charged into a reaction tank, and the reaction was carried out at about 80°C for about 3 hours with stirring, and then at about 95°C for about 3 hours.The viscosity of the reaction system decreased over time. Rose. After the reaction, acetic acid 160
When the reaction system was neutralized by adding 0 parts and allowed to stand, the aqueous layer was separated as a lower layer and the oil layer containing the polyhydroxyboriate produced by the reaction was separated as an upper layer. After removing the aqueous layer and adjusting the viscosity of the oil layer using acetic acid and methyl isobutyl ketone, the resulting polyhydroxy polyether was precipitated by injecting it into a large amount of methanol. After washing with water, it was dried under vacuum at 40°C.

The intrinsic viscosity [η] of the polyhydroxy polyether thus obtained was 0.81 dl/g, the glass transition temperature was 56°C, and the length was 30 mm.
Type 1, when extruded from a 0mm nozzle at 240℃ and with a sliding speed of 10 seconds, the melt viscosity is 8Xl.
It was 02poise.

Example 7 The polyhydroxypolyether of Example 1, which had been dried under reduced pressure at 50°C for 12 hours, was heated to about 200°C using a press molding machine.
Compression molded at 50kg/cut to a thickness of approximately 100mm
A sheet of μ was prepared. This sheet is colorless and has excellent transparency, and its mechanical properties were measured to have a tensile strength at break of 440 kg/crA, a tensile elongation at break of 70%,
The tensile modulus was 29,000 kg/ctA, and the strength was excellent. Furthermore, as a result of investigating its gas barrier properties, the carbon dioxide gas permeability coefficient was O.9.6ml・mm.
/ rrr −day −atm, and the oxygen gas permeability coefficient is 0.26 m1・mm/m −day・a
It was tm. Furthermore, this press sheet was simultaneously stretched three times in the vertical and horizontal directions using a biaxial stretching device at a temperature of about 90°C and a speed of 110 m/sec.
A biaxially stretched film with a thickness of about 11 μm was produced. The results of measuring the mechanical properties of the stretched film showed that the tensile strength at break was 510 kg/cot, the elongation was 30%, and the tensile modulus was 33,000 kg/cm, which were excellent values for a film.

Furthermore, as a result of measuring the gas barrier properties of this biaxially stretched film, the carbon dioxide gas permeability coefficient was 0.90 m/・mm/r
rr ・day −atm , and the oxygen gas permeability coefficient is 0.22 mZ-mm/rd −day −atm
Met.

Examples 8 to 9 In the same manner as in Example 7, except that the polyhydroxy polyether shown in Table 3 was used instead of the polyhydroxy polyether used in the compression molding of Example 7, moldings each having a thickness of about 100 μm were made. A press sheet was produced. All of the obtained press sheets were colorless and had excellent transparency, and the results of measuring their mechanical properties and gas barrier properties were as shown in Table 3. Further, these press sheets were simultaneously stretched three times in the diurnal axis direction and the transverse axis direction using a biaxial stretching apparatus in the same manner as in Example 7 to produce biaxially stretched films each having a thickness of about 11 μm.

The mechanical properties and gas barrier properties of the obtained biaxially stretched film were as shown in Table 3.

Comparative Example 2 Polyethylene terephthalate (manufactured by Mitsui PET Resin Co., Ltd., Mitsui PET J 1) dried at 150°C for 10 hours
25) to a thickness of approximately 100 μm.
A press sheet was produced. The mechanical properties of this press sheet were a tensile strength at break of 475 kg/c+a and an elongation of 80%. In addition, the gas barrier property has a carbon dioxide gas permeability coefficient of 25mf-mm/rd-day, an oxygen gas permeability coefficient of 4.6ml-mm/rd-day
・It was an ATM.

Furthermore, as in Example 1, this press sheet was simultaneously biaxially stretched three times in the longitudinal and transverse directions to produce a biaxially stretched film having a thickness of about 11 μm. The mechanical properties of this biaxially stretched film are tensile strength at break of 1530 k
g/cIa, elongation 50% and tensile modulus 4600
It was 0 kg/crA. In addition, the gas barrier property of this biaxially stretched film is that the carbon dioxide permeability coefficient is 16mf.
・mm/rd ・day -atm %Oxygen gas permeability coefficient 2.5m1-mm/m -day -atm
Met.

Comparative Example 3 The polyhydroxypolyether of Comparative Example 1, which had been dried at 50° C. for 12 hours, was compression molded in the same manner as in Example 7 to produce a press sheet with a thickness of about 100 μm.

The results of measuring the mechanical properties of this press sheet were that the tensile strength at break was 360 kg/ctM, the elongation was 80%, and the tensile strength at break was 23000 kg/cnl.

Furthermore, as a result of measuring its gas barrier properties, the carbon dioxide permeability coefficient was 1.9 ml・mm/rd-day.
・ATM, and oxygen gas permeability coefficient is 0.37m
f-mm/rd-day・atm.

Further, in the same manner as in Example 7, this press sheet was simultaneously biaxially stretched three times in the vertical axis direction and the horizontal axis direction using a biaxial stretching apparatus. As a result, the average thickness was approximately 11μ
A biaxially stretched film was obtained, but the film thickness was found to be uneven in the range of approximately 9 to 14 μm. Therefore, using the same polyhydroxy polyether, the thickness was approximately 2
A press sheet of 00μ was prepared and then biaxially stretched in the same manner as for a press sheet with a thickness of about 100μ. In this case, the average thickness was about 22μ.
A biaxially stretched film with a small thickness could be produced. The mechanical properties of the biaxially stretched film include tensile strength at break of 390
kg/crd, elongation 30% and tensile breaking strength 27
000 kg/c++I. In addition, as a result of measuring the gas barrier properties of this biaxially stretched film, the carbon dioxide permeability coefficient was 1.6 *l・mm/resistance・day・a
It was tm.

Examples 10 to 12 Press sheets were produced in the same manner as in Example 7, except that the polyhydroxypolyether shown in Table 4 was used instead of the polyhydroxypolyerthyl used in the compression molding of Example 7. All of the obtained press sheets had excellent light resistance, and the results of measuring their mechanical properties and gas barrier properties were as shown in Table 4. Next, as in Example 7, these press sheets were simultaneously stretched three times in the vertical axis direction and the horizontal axis direction using a biaxial stretching apparatus to produce a biaxially stretched film.

All of the obtained films had an average thickness of about 11 microns, and their mechanical properties and gas barrier properties were as shown in Table 4.

Example 13 The polyhydroxy polyether of Example 2 was prepared using an extruder equipped with a T-die at a barrel temperature of about 160°C to about 2°C.
Extrusion molding was performed at 50° C. to produce an extruded sheet with a thickness of about 80 μm. The mechanical properties of this extruded sheet are tensile strength at break of 520 kg/crA (machine direction) to 47
0 kg/ant (perpendicular to flow), elongation 83
% (direction of flow) to 72% (direction perpendicular to flow) and tensile modulus of elasticity of 33000 kg/crA (direction of flow) to 32000 (direction perpendicular to flow).

Also, the carbon dioxide permeability coefficient of this extruded sheet is 0.93m
It was 1-mm/m・day-atm.

Furthermore, this extruded sheet was stretched to approximately 85 mm by using a biaxial stretching device.
A biaxially stretched film having an average thickness of about 13μ by sequentially stretching twice in the transverse axis (perpendicular to the flow direction) and then three times in the longitudinal axis (flow) direction at a temperature between °C and about 100'C. was created. The mechanical properties of this biaxially stretched film include tensile strength at break of 680 kg/ant (direction of flow) to 560 kg/ct (direction perpendicular to flow), elongation of 28% (direction of flow) to 26% (perpendicular to flow), and tensile strength at break of 42000+r/cnl (flow direction) to 41000kg/cut (perpendicular to flow direction)
Met.

In addition, the carbon dioxide gas permeability coefficient of this biaxially stretched film is 0.8
It was 7mf-mm/rd・day・atm.

Example 14 A press sheet of the polyhydroxy polyether of Example 2 and a press sheet of the polyhydroxy polyether of Comparative Example 2 were overlapped to produce a further press sheet. The adhesion between the polyhydroxypolyether layer and the polyethylene terephthalate layer of this multilayer press sheet was good. Furthermore, this multilayer press sheet was simultaneously biaxially stretched under the same conditions as in Example 8 to produce a biaxially stretched film having an average thickness of 17μ. The thickness of the polyhydroxy polyether layer of this biaxially stretched film was about 8μ, and the thickness of the polyethylene terephthalate layer was about 9μ. Furthermore, the adhesion between the polyhydroxy polyether layer and the polyethylene terephthalate layer of this biaxially stretched film was also good.

As a result of measuring the mechanical properties of this laminated biaxially stretched film, the tensile strength at break was 1020 kg/cn! , elongation 40% and tensile modulus 29000 kg/ctA.

Furthermore, the carbon dioxide permeability coefficient of this biaxially stretched film is 1.
It was 9+af-mm/rd・day・atm.

Example 15 First, the polyethylene terephthalate in Comparative Example 2 was injection molded, and then the polyhydroxy polyether in Example 2 was injection molded again to form a polyethylene terephthalate layer and a polyhydroxy polyether layer, each of which Preforms each having a thickness of about 1.6 mm were produced.

Next, this preform is heated to 85 to 95°C using a far-infrared heating device, and stretched to about 2.5 times in length and 4.3 times in width using a stretch blow molding machine to achieve the minimum wall thickness. A stretched bottle having a polyethylene terephthalate layer of about 150μ and a polyhydroxypolyether layer of about 150μ and an internal volume of about 1β was molded. Next, we measured the carbon dioxide permeability of this stretched bottle and found it to be 0.55 mj/da.
y-bottle-atm, and the oxygen gas permeability is 0.17 mZ/day-bottle-atm.
It was m.

Comparative Example 4 The same polyethylene terephthalate layer used in Example 15 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 of Example 15. This preform was then stretch-blown in the same manner as in Example 15 to produce a stretched bottle having a minimum wall thickness of approximately 300 μm and an internal volume of 11. Furthermore, as a result of measuring the carbon dioxide gas permeability and oxygen gas permeability of this stretched bottle, the results were 4.0+a
Z/day ・bottle-atm and 1.1m
f/day-bottle-atm.

Example 16 First, polyethylene terephthalate in Comparative Example 2 was
The polyhydroxypolyether of Example 2 was melted using one extruder, and the polyhydroxypolyether of Example 2 was melted using another extruder.
Supplied into two types and three layers of pipes, polyethylene terephthalate/polyhydroxypolyether/polyethylene terephthalate (thickness approx. 1.2 mm/1.2 mm)
/1.2mm) is extruded, cooled with water, and has an outer diameter of 24.8mmφ and a thickness of 3.6+nn.
A three-layer pipe with + was obtained.

Next, this pipe was cut, one end was heated and melted to process the bottom, and the other end was similarly heated and melted to process the spout to obtain a preform with a total length of 16.5 cm and a weight of approximately 50 g. Ta. Next, a biaxial stretch blow molding machine (LBO1 manufactured by COI POPLAST) was used.
The internal volume is 1.57! A multilayer container (polyethylene terephthalate/polyhydroxy polyether/polyethylene terephthalate - about 120μ/about 120μ/about 120μ) was obtained. Next, the carbon dioxide gas permeability of this multilayer container was measured and was 0.68 mZ/day-bottle・atm, and the oxygen gas permeability was measured to be 0.22 m
/day-battle-atm. Next, we recently conducted a drop test using 0°C water, and as a result, the multilayer container did not break when dropped from a height of 1 m. Further, delamination of each layer was not observed.

〔Effect of the invention〕

The polyhydroxy polyether of the present invention has excellent melt moldability, stretch moldability, transparency and gas barrier properties,
The polyester laminate molded article of the present invention and the preform for a polyester multilayer hollow molded article are both excellent in stretch moldability, transparency, and gas barrier properties. Both have excellent transparency and gas barrier properties.

Claims (6)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, R^1 is a divalent aromatic hydrocarbon group whose main component is p-phenylene group and n is a positive number. ] in o-chlorophenol at 25°C.
The intrinsic viscosity [η] measured in is in the range of 0.9 to 2 dl/g, and when extruded from a nozzle with a length of 30 mm and a diameter of 1.0 mm at 240°C and a shear rate of 10 sec^-^1 A polyhydroxy polyether having a melt viscosity in the range of 10^3 poise to 10^5 poise. (2) General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼... [I] [In the formula, R^1 is a divalent aromatic hydrocarbon group whose main component is p-phenylene group and n is a positive number. ] in o-chlorophenol at 25°C.
The intrinsic viscosity [η] measured in is in the range of 0.9 to 2 dl/g, and when extruded from a nozzle with a length of 30 mm and a diameter of 1.0 mm at 240°C and a shear rate of 10 sec^-^1 A stretched molded article of polyhydroxy polyether, characterized in that the melt viscosity thereof is in the range of 10^3 poise to 10^5 poise. (3) A polyester laminate molded product composed of a polyalkylene terephthalate layer (A) whose main constitutional unit is ethylene terephthalate and a polyhydroxypolyether layer (B), wherein the polyhydroxypolyether has the general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] [In the formula, R^1 represents a divalent aromatic hydrocarbon group whose main component is a p-phenylene group, and n is a positive is the number of ] in o-chlorophenol at 25°C.
The intrinsic viscosity [η] measured in is in the range of 0.9 to 2 dl/g, and when extruded from a nozzle with a length of 30 mm and a diameter of 1.0 mm at 240°C and a shear rate of 10 sec^-^1 A polyester laminate molded article comprising a substantially linear polyhydroxy polyether having a melt viscosity in the range of 10^3 poise to 10^5 poise. (4) A polyester stretch laminate formed from a polyalkylene terephthalate layer (A) containing ethylene terephthalate as a main constituent unit and a polyhydroxypolyether layer (B), wherein the polyhydroxypolyether has the general formula [I ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I] [In the formula, R^1 represents a divalent aromatic hydrocarbon group whose main component is p-phenylene group, and n is It is a positive number. ] in o-chlorophenol at 25°C.
The intrinsic viscosity [η] measured in is in the range of 0.9 to 2 dl/g, and when extruded from a nozzle with a length of 30 mm and a diameter of 1.0 mm at 240°C and a shear rate of 10 sec^-^1 1. A polyester stretch laminate molded article, which is a substantially linear polyhydroxy polyether having a melt viscosity in the range of 10^3 poise to 10^5 poise. (5) A preform for a polyester multilayer blow molded article having a laminated structure composed of a polyalkylene terephthalate layer (A) whose main constituent unit is ethylene terephthalate and a polyhydroxypolyether layer (B), Ether has the general formula〔I〕▲
There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I] [In the formula, R_1 represents a divalent aromatic hydrocarbon group whose main component is p-phenylene group, and n is a positive number. be. ] in o-chlorophenol at 25°C.
The intrinsic viscosity [η] measured in is in the range of 0.9 to 2 dl/g, and when extruded from a nozzle with a length of 30 mm and a diameter of 1.0 mm at 240°C and a shear rate of 10 sec^-^1 1. A preform for a polyester multilayer blow molded article, which is a substantially linear polyhydroxy polyether having a melt viscosity in the range of 10^3 poise to 10^5 poise. (6) A polyester multilayer hollow molded article having a laminated structure composed of a polyalkylene terephthalate layer (A) whose main constituent unit is ethylene terephthalate and a polyhydroxypolyether layer (B), wherein the polyhydroxypolyether , general formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I] [In the formula, R^1 is a divalent aromatic hydrocarbon group whose main component is p-phenylene group. and n is a positive number. ] in o-chlorophenol at 25°C.
The intrinsic viscosity [η] measured in is in the range of 0.9 to 2 dl/g, and when extruded from a nozzle with a length of 30 mm and a diameter of 1.0 mm at 240°C and a shear rate of 10 sec^-^1 1. A polyester multilayer hollow molded article, which is a substantially linear polyhydroxy polyether having a melt viscosity in the range of 10^3 poise to 10^5 poise.