JPH0232152A - Polyester resin composition and use thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polyester resin composition having excellent melt moldability, stretchability, mechanical strength, and gas barrier properties, and having performance suitable as a material for containers, etc. , relates to a stretched molded article, a preform for a stretched hollow molded article, and a stretched hollow molded article using this polyester resin composition.

Glass has been widely used as a material for forming containers for alcoholic beverages such as beer and Japanese sake, soft drinks such as carbonated drinks, seasonings, oils, cosmetics, and detergents. Glass containers have the advantages of excellent transparency, moldability, and gas barrier properties, but they have the problem of high manufacturing costs, and empty containers are usually collected and reused after use. By doing so, costs are reduced.

However, during such collection, glass containers are heavy and transportation costs increase, making it impossible to reduce costs sufficiently. Furthermore, there are problems in that it is easily damaged during transportation and is difficult to remove.

Therefore, plastic containers are increasingly being used in place of glass containers, which have the above-mentioned problems.

The plastic materials used to manufacture such plastic containers basically need to have high levels of properties required during container manufacturing, such as melt moldability and stretchability, and the resulting containers Properties such as mechanical strength and transparency also need to be at a high level.

Polyethylene terephthalate is a material that has these characteristics. Polyethylene terephthalate has excellent transparency and mechanical strength, as well as good moldability, and is basically suitable as a material for plastic containers. .

By the way, in containers for seasonings, detergents, cosmetics, etc., mechanical strength and transparency are often issues, but gas barrier properties are rarely an issue. It can be said that the containers thus prepared have good numerical properties.

However, for example, containers for carbonated drinks and sparkling drinks such as beer bottles are filled with high-pressure carbon dioxide gas, etc., so they have extremely high gas barrier properties to prevent leakage of the gas filled inside. is required. In applications where strict gas barrier properties are required, even polyethylene terephthalate, which has relatively high gas barrier properties among plastic materials, cannot be said to be sufficient. When using polyethylene terephthalate for applications that require high gas barrier properties, such as those that require high gas barrier properties, gas barrier properties must be ensured by increasing the wall thickness of the container, which is disadvantageous in terms of cost. It is.

Currently, the demand for polyester resin containers is increasing, but in order to use polyester resin containers in applications that require extremely high gas barrier properties as mentioned above, it is necessary to It is necessary to impart high gas barrier properties to polyethylene terephthalate without impairing its properties.

In response to such demands, various improvements have been attempted on polyethylene terephthalate.

For example, JP-A-59-64624 discloses polyalkylene isophthalates such as polyethylene isophthalate, copolymers thereof, and molded articles obtained using these polymers or copolymers. Furthermore, JP-A-59-64049 discloses a layer composed of the above-mentioned polyalkylene isophthalate or a copolymer thereof, and a layer composed of polyalkylene isophthalate-1- or a copolymer thereof such as polyethylene terephthalate. A multilayer packaging material and a molded article made therefrom are disclosed. Furthermore, JP-A-59-3
Publication No. 9547 discloses a gas-permeable multilayer container in which the innermost layer is made of polyester whose main repeating unit is ethylene terephthalate, and the outer layer is made of polyester whose main repeating unit is ethylene isophthalate. A multilayer container is disclosed in which gas permeation resistance is improved by orienting the thin wall portion of the container in at least one direction. Also, in Japanese Patent Application Laid-open No. 56-64866,
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 polyamide having 1-xylylene diamine or a mixture of m-xylylene diamine and p-xylylene diamine as the diamine component. A multilayer container is disclosed in which the thinned portion is oriented in at least one direction.

Furthermore, in Japanese Patent Application Laid-open No. 58-183243, two inner and outer surface layers are made of polyethylene terephthalate,
A biaxially stretched blow-molded bottle body is disclosed in which the intermediate layer is made of a mixed material of polyethylene terephthalate and xylylene group-containing polyamide.

As described above, in the prior art, many attempts have been made to improve the gas barrier properties of polyalkylene terephthalate by changing the structure or orientation of polyalkylene terephthalate itself, such as polyethylene terephthalate. Modification does not improve the gas barrier properties of polyalkylene phthalate to the extent that it is suitable as a container material for sparkling beverages.

Therefore, in the case of containers that require high gas barrier properties, such as sparkling beverage containers, the conventional methods used for resin containers to improve gas barrier properties, such as multilayer structures and thick walls, are required. We had no choice but to use technology.

Apart from the above methods, it is known that the gas barrier properties of polyethylene terephthalate can be improved by blending polyhydroxypolyether with polyethylene terephthalate.

For such polyhydroxy polyethers, Jo
Urnal of Applied Polymer
5science, Volume 7, 2135-2144 (19
63) describes the results of studies on the gas barrier properties of homopolyhydroxy ethers represented by the following formula (A).

H ... (A) The above formula (A) In, E is n2/24 hr/aiIl theal.

The polymer with low E also has a water vapor mobility of 3 t −11 under conditions of 100 F, 90% R, Ir,
i1/100in2/24hr.

Also, Journal of Applied Pol
ymer 5science.

Vol. 7, 2145-2152 (1963) shows the results of studies on the gas barrier properties of cobohydroxy polyether represented by the following formula (B).

Among such homohydroxy diethers, the above formula (
In B), R1 is a polymer of 0°5 cc-1il/100. However, in the above formulas (A) and (B), R1 and R2 are not the same.

Among such polyhydroxy polyethers, the polymer with the lowest oxygen permeability has R1 of the following value:
5+r-m+/100in”/241+r/atfl
It is. In addition, for polymerization with low water vapor mobility, the water vapor mobility of R1 is 4 tr -ml/100 in"/ under the conditions of 100F and 9o% R3H.
It is 24 tar.

Such polyhydroxy polyethers can be produced by the reaction of hydroquinone and epichlorohydrin (US Pat. No. 2,602,075 (1948)).
, 11, 26)). However, the polyhydroxy polyether disclosed in this bulletin is an intermediate raw material for producing epoxy resin, and the polyhydroxy polyether obtained according to the manufacturing technology described in this bulletin has epoxy groups in the molecule. have.

Furthermore, Japanese Patent Publication No. 28-4494 discloses that dihydric phenols and shrimp halohydrin are reacted in advance to obtain diglycidyl ethers of dihydric phenols or low polymers thereof, and then diglycidyl ethers of dihydric phenols or low polymers thereof are obtained. Alternatively, a method for producing a resin by further reacting the low polymer with a dihydric phenol has been disclosed.

However, the dihydric phenols used in this invention are mainly bisphenol A, i.e. 2,2-bis(4
-Hydroxyphenyl)propane, and there is no specific disclosure regarding the homopolyhydroxy polyether of hydroquinone.Furthermore, the produced polymer in this invention is mainly a polymer having a certain epoxy equivalent,
Therefore, the polymers produced according to this invention also contain epoxy groups.

Also, U.S. Patent No. 2,615,008 (1951゜1
No. 0.11) discloses a method for producing a high molecular weight epoxy resin by reacting a low molecular weight epoxy resin with a dihydric phenol. And in this method,
It has been shown to use low molecular weight epoxy resins such that the epoxy equivalent weight of the low molecular weight epoxy resin is higher than the phenol equivalent weight of the dihydric phenol. However, the polymer obtained by this method also has epoxy groups.

Also, U.S. Patent No. 3,336,257 (1967°8
, 15) includes a tertiary amine, a quaternary ammonium compound,
N-alkyl acid amide, N,N-dialkyl acid amide,
A method for producing a high molecular weight polyhydroxy polyether by reacting a jepoxy compound and a diphenol in the presence of a catalyst of a urea compound and a thiourea compound is disclosed.

However, this method is a method for producing polyhydroxy polyether containing repeating units derived from bisphenol A, and the polyhydroxy polyether obtained according to this method also has a structure containing epoxy groups.

Furthermore, US Patent No. 3,379,684! 1968.
4゜23), the ratio of epoxy group to phenolic hydroxyl group is 1.0 in a jepoxy compound and a diphenol compound.
A method for producing an addition polymerization product is disclosed by reacting the reaction mixture so that the molecular weight is in the range of 1.2 to 1.2, and it is also disclosed that a tertiary amine is effective as a catalyst for the reaction.

However, the compound obtained by this method is an addition polymer of bisphenols and a jepoxy compound, and the addition polymer thus obtained also has an epoxy group.

Also, U.S. Patent No. 3560605 (1971°2
．． 2) discloses an injection molding composition comprising polyethylene terephthalate and a diglycidyl ether compound.

However, in this composition, the dihydric phenol di- or polyepoxy compound used as the diglycidyl ether compound naturally has an epoxy group, and by utilizing the reactivity of this epoxy group, polyethylene Terephthalate is modified.

Furthermore, U.S. Patent No. 4087479 (1978,
No. 5,2) discloses a thermosetting composition comprising a mixture of a polyester containing a carboxyl group and a polyepoxide compound containing an epoxy group. The amount of epoxy groups in the polyepoxide compound used in this composition is described as 2 to 100 per molecule, and this polyepoxide compound has epoxy groups.

Also, U.S. Patent No. 4267301 (1981゜5
．． 12) and JP-A-56-100828 disclose a linear hydroquinone phenoxy polymer produced from hydroquinone and shrimp halohydrin by an interfacial polymerization method.

However, since this hydroquinone phenoxy polymer is produced by an interfacial polymerization method using shrimp halohydrin in a range of 0.95 to 1.05 equivalents to hydroquinone, the obtained hydroquinone phenoxy polymer has no epoxy groups. have.

As described above, polyhydroxy polyethers or similar compounds disclosed in the prior art are
All of them are polymers with epoxy groups in their molecules. Polyester resin compositions obtained by blending such polyhydroxypolyethers having epoxy groups with other resins such as polyalkylene terephthalate show some improvement in gas barrier properties, but the The epoxy group in the ether reacts with other blended resins such as polyalkylene terephthalate, which tends to cause undesirable side reactions such as crosslinking and gelation. Even if it were obtained, there were problems with the stability of the molding characteristics, such as gel and lumpy foreign matter gradually becoming mixed in as the molding continued for a long time.

An object of the present invention is to provide a polyester resin composition containing a novel polyhydroxy polyether.

Another object of the present invention is to provide a polyester resin composition having excellent gas barrier properties against oxygen and carbon dioxide.

Another object of the present invention is to provide a polyester resin composition that has excellent gas barrier properties, as well as excellent melt moldability and stretchability.

Furthermore, another object of the present invention is to provide a stretched molded article, a preform for a stretched hollow molded article, and a stretched hollow molded article using a polyester resin composition having the above characteristics.

1. The polyester resin composition according to the present invention is a polyester resin composition containing polyalkylene terephthalate and polyhydroxypolyether whose main constituent units are ethylene terephthalate constituent units, wherein the polyhydroxypolyether is It is substantially linear and has an intrinsic viscosity [η] of 0.1 to 2 dJ when measured at 25°C in 0-chlorophenol, which is represented by the following formula (a)! It is characterized by being a polyhydroxy polyether within the range of /r.

Leaf ... (a) However, in the above formula (a), A'1 and Ar2 each independently represent a monovalent aromatic hydrocarbon having 6 to 15 carbon atoms other than HO-Ar or HO-Ar. represents a group, A" represents a p-phenylene group, and n represents a positive integer.

Moreover, the stretched molded article of the polyester resin composition according to the present invention is a stretched molded article of a polyester resin composition containing polyalkylene terephthalate and polyhydroxypolyether whose main constitutional units are ethylene terephthalate constitutional units, The hydroxy polyether is represented by the following formula (a), is substantially linear, and has an intrinsic viscosity [η] of 0.1 to 0.1 as measured at 25°C in O-chlorophenol.
It is characterized by being a polyhydroxy polyether within a range of 2 dj/g.

d.I! It is characterized by being a polyhydroxy polyether within the range of /g.

0H... (a) However, in the above formula (a), Ar' and Ar2 each independently represent HO-Ar or a monovalent aromatic hydrocarbon group with 6 to 15 carbon atoms other than HO-Ar. Representation,
A" represents a p-phenylene group, and n represents a positive integer.

Further, the preform for a stretched hollow molded body of a polyester resin composition according to the present invention is a stretched hollow molded body of a polyester resin composition containing polyalkylene terephthalate and polyhydroxy polyether whose main constitutional unit is ethylene terephthalate constitutional unit. A preform for use in a polyhydroxy polyether, the polyhydroxy polyether is represented by the following formula (a), is substantially linear, and has an intrinsic viscosity [η] of 0.1 to 2011 as measured at 25°C in O-chlorophenol.
... (a) However, in the above formula (a), Ar1 and Ar2 each independently represent HO-Ar or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms other than HO-Ar,
A" represents a p-phenylene group, and n represents a positive integer.

Furthermore, the stretched hollow molded article of the polyester resin composition according to the present invention contains ethylene terephthalate structural units,
A stretched hollow molded article of a polyester resin composition containing polyalkylene terephthalate and polyhydroxy polyether as main constituent units, wherein the polyhydroxy polyether has a substantially linear shape represented by the following formula (a). It is characterized by being a polyhydroxypolyether whose intrinsic viscosity [η] measured in 0-chlorophenol at 25° C. is within the range of 0.1 to 26 j/l.

θN ... (a) However, in the above formula (a), Ar1 and Ar2 each independently represent HO-Ar or a monovalent aromatic hydrocarbon group with 6 to 15 carbon atoms other than HO-Ar. ,
Ar represents a p-phenylene group, and n represents a positive integer.

The polyhydroxy polyether used in the polyester resin composition of the present invention has both ends blocked, so the polyester resin composition of the present invention containing this polyhydroxy polyether has excellent gas barrier properties and moldability. Both are excellent. Therefore, a stretched molded article, a preform for a stretched hollow molded article, and a stretched hollow molded article obtained using the resin composition of the present invention have excellent molding specific heat stability and good gas barrier properties.

(Hereinafter, blank space) 1 Dish Ejuro Head] Hereinafter, the polyester resin composition, stretched molded product, preform for stretched hollow molded product, and stretched hollow molded product according to the present invention will be explained in detail.

First, the polyester resin composition of the present invention will be explained.

The polyester resin composition of the present invention is basically a composition consisting of a specific polyoxydroxypolyether and polyalkylene thirephthalate-1.

The hydroxy polyether used in the polyester resin composition of the present invention has a substantially linear shape represented by the following formula (a), and has an intrinsic viscosity [η] measured at 25°C in 0-chlorophenol within a specific range. It is an end-capped polyhydroxy polyether.

0■ ... (a) However, in the above formula (a), A" and ^"2 are,
Each independently, HO-Ar or HO-HO-Ar
represents m aromatic hydrocarbon groups having 6 to 15 carbon atoms, and A" represents the above p-phenylene group, and n
hails positive integers.

And, the 0-
Intrinsic viscosity [η] measured in chlorophenol at 25°C
is in the range of 0.1 to 2dj/ir.

Such polyhydroxy polyether can be used, for example, as follows.

First, a hydroxyether compound represented by the following formula (al) is prepared. This compound can then be prepared by reacting with an aromatic monoalcohol having 6 to 15 carbon atoms in the presence of a specific catalyst.

It is an arbitrary number selected from numbers, and is usually an integer from 8 to 600. Further, Arc' and Ar02 are groups selected from a glycidyl group and HO-Ar, respectively, and A'01 and Aro2 may be the same or different. Also, here A' is p- It is a phenylene group.

In the present invention, compounds in which both ArO and Aro2 are glycidyl groups can be used effectively.

The hydroxyether compound represented by the above formula (al) can be synthesized, for example, by the method shown below.

First, a mononuclear aromatic diol represented by the following formula (I): 1-ro-Ar -OH.(I) [In the above formula (I), Ar is a p-phenylene group. ] and shrimp halohydrin represented by the following formula (n): However,
In the above formula (al), m is a positive integer [the above formula (If)
In the formula, X is a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom. ] in the presence of an alkali metal hydroxide compound, the following formula (Il[)
Hydroquinone diglycidyl ether or hydroquinone diglycidyl ether oligomer is obtained.

However, in the above formula (I), 1 is any number selected from O or a positive integer, and usually this 1 is 0 to 20
is within the range of Further, Ar is a phenylene group.

The mononuclear aromatic diol represented by formula (I) used in the above reaction is preferably hydroquinone, but the aromatic ring of this hydroquinone may have a substituent such as a lower alkyl group, and The mononuclear aromatic diol represented by formula (I>) is most preferably entirely hydroquinone, but within a range that does not impair the properties of the resulting polyhydroxy polyether, for example, 5% by weight of the total weight of hydroquinone used. Other mononuclear aromatic diols such as resorcinol can also be used as long as they are below.

Examples of the shrimp halohydrin represented by formula (n) include shrimp florhydrin, epichlorohydrin, and shrimp bromohydrin. Particularly in the present invention, it is preferable to use epichlorohydrin or ebibromohydrin alone or in combination.

Further, examples of the alkali metal hydroxide compounds used in the above reaction include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.
In the present invention, it is preferable to use sodium hydroxide or potassium hydroxide alone or in combination. Such alkali metal hydroxide compounds are usually solid and are added to the reaction system in a solid state. It can also be added to the reaction system as an aqueous solution.

The usage ratio of the shrimp halohydrin represented by the formula (II) used in the synthesis of the diglycidyl ether or diglycidyl ether oligomer represented by the above formula (III) is based on the usage amount of the mononuclear aromatic diol represented by the formula (I). On the other hand, it is usually 1 to 3 times the mole, preferably 1.1 to 2 times the mole.
．． It is within the range of 8 times the mole. The proportion of the alkali metal hydroxide compound to be used is usually 1 to 3 times the mole, preferably 1 to 3 times the mole of the mononuclear aromatic diol represented by the formula (I>).
．． It is within the range of 1 to 2.8 times the mole.

The reaction conditions for producing the diglycidyl ether or diglycidyl ether oligomer represented by the above formula (III) are such that the mononuclear aromatic diol represented by the formula (I) and the shrimp halohydrin represented by the formula (II) are reacted. For example, mononuclear aromatic diol represented by formula (I) and shrimp halohydrin represented by formula (II) are mixed, an alkali metal hydroxide compound is added, and then the reaction temperature is lowered. It can be produced by setting the reaction time at 60 to 140°C, preferably 70 to 130°C, for 1 to 10 hours, preferably 2 to 8 hours, and carrying out the reaction with stirring.

In addition, in this method, the viscosity of the reaction solution is adjusted to allow the reaction to proceed smoothly, and the alkali metal halide such as sodium chloride, which is a by-product of the reaction, and the target product of this reaction, which is the formula (1) In order to facilitate separation from the diglycidyl ether represented by or its oligomer, a solvent inert to the raw materials used and the desired product may be used as the reaction solvent.

When using a reaction solvent, examples of solvents that can be used include saturated hydrocarbons such as n-decane and decahydronaphthalene; benzene, toluene, xylene, trimethylbenzene;
Tetramethylbenzene, ethylbenzene, cumene, n
- aromatic hydrocarbons such as butylbenzene, tetrahydronaphthalene and naphthalene; methyl ethyl getone;
Examples include ketones such as methyl isobutyl ketone, 2-hexanone, cyclohexanone and acetophenone; amides such as N,N-dimethylacetamide and tomethyl-2-pyrrolidone; and sulfoxides such as dimethyl sulfoxide. The desired product in the above reaction, the diglycidyl ether represented by formula (III) or its oligomer, has high solubility in ketones, so
By using ketones as a reaction solvent, the desired product can be obtained in high yield. When these reaction solvents are used, these reaction solvents have the formula (III)
It is usually used in an amount of 3 parts by weight or less, preferably 2 parts by weight or less, and more preferably 1 part by weight or less, per 1 part by weight of diglycidyl ether or oligomer thereof.

After the mononuclear aromatic diol represented by formula (I>) and the shrimp halohydrin represented by formula (n) are reacted as described above, alkali metal halides such as sodium chloride produced by the reaction are separated. Separation of this alkali metal halide can be carried out using known methods such as separation or passing.Also, if an excess of shrimp halohydrin is used in the above reaction, unreacted shrimp halohydrin can be removed by distillation or other methods. Further, when a reaction solvent is used, the reaction solvent is removed using a method such as distillation.

By removing the alkali metal halide, unreacted shrimp halohydrin, reaction solvent, etc. in this manner, diglycidyl ether represented by the following formula (II) or its oligomer can be obtained.

However, in the above formula (III), Ar is a p-phenylene group. In addition, J is an arbitrary number selected from 0 or a positive integer, and this value is determined by the formula (
It is determined by the ratio of the mononuclear aromatic diol represented by I> and the epi-octalohydrin represented by formula (If). That is, mononuclear aromatic diol 1 represented by formula (I)
The value of 1 becomes smaller as the usage ratio of ebihalohydrin expressed by formula (II) to mole increases, and the value of 1 becomes smaller, and the formula (
When the usage ratio of shrimp halohydrin represented by II) exceeds 2 times the mole, hydroquinone glycidyl ether in which 1 is substantially 0 can be obtained.

The value of 1 in the above formula (III) means that the value of 1 in the above formula (al
) is generally smaller than the value of m in the intermediate.

In addition, in the diglycidyl ether represented by formula (I) or its oligomer separated as described above,
Mononuclear aromatic diol represented by formula (I) or shrimp halohydrin represented by formula (II), which is a manufacturing raw material,
Alternatively, a small amount of monoglycidyl ether, which is a reaction product of the mononuclear aromatic diol and the shrimp halohydrin, may be contained, and even a small amount of such a compound may reduce the reactivity in the next step. There are almost no

By further reacting the thus obtained diglycidyl ether represented by formula (III) or its oligomer with a mononuclear aromatic diol represented by formula (I) in the presence of a basic catalyst, for example, A hydroxyether compound represented by formula (al), which is a raw material for producing polyhydroxypolyether, can be produced.

The mononuclear aromatic diol represented by the formula (I) used here is the mononuclear aromatic diol used when producing the diglycidyl ether or its oligomer represented by the above formula (If[), and is usually uses hydroquinone.

In addition, as the diglycidyl ether or its oligomer represented by the above formula (III), diglycidyl ether and oligomer of diglycidyl ether can be isolated and used individually, or diglycidyl ether and diglycidyl ether can be used individually. It can also be used as an oligomer mixture.

Examples of basic catalysts that can be used in the above reaction include tertiary amine compounds, quaternary ammonium compounds, tertiary phosphine compounds and quaternary phosphonium compounds.

Examples of the tertiary amine compound used as the above catalyst include triethylamine, tri-n-butylamine, tri-iso-10-pylamine, tri-n-butylamine, tri-secondary-butylamine, tri-n-hexylamine, dimethylbenzylamine, diethylbenzyl Mention may be made of amines and tribenzylamines. Examples of quaternary ammonium compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetraisopropylammonium hydroxide, tetra-n-butylammonium hydroxide, and trimethylbenzylammonium hydroxide. and triethylbenzylammonium hydroxide. Further, examples of the tertiary phosphine compound include triethylphosphine, tri-n-butylphosphine, triphenylphosphine, and trinonylphenylphosphine. Furthermore, examples of the quaternary phosphonium compound include quaternary phosphonium hydroxide compounds such as tetramethylphosphonium hydroxide. Such catalysts can be used alone or in combination.

In the above reaction, the proportion of mononuclear aromatic diol represented by formula (I) is usually 0.5 to 1.5 to 1 mole of diglycidyl ether represented by formula (III) or its oligomer. Mol, preferably 0°6-1.
4 mol, particularly preferably in the range from 0.7 to 1.3 mol. In addition, in these usage ratios, if the amount of hydroquinone used is equal mole or less to hydroquinone diglycidyl ether or its oligomer, -valent aromatic Since the proportion of group hydrocarbon groups increases, it is generally preferable because the terminal reactivity can be kept lower.

In addition, the proportion of the basic catalyst used in the above reaction is usually 0.00 to the diglycidyl ether represented by the above formula (III) or its oligomer. ooi to 10 mol%, preferably 0.005 to 5 mol%, particularly preferably 0.01 to 1 mol%.

Further, the reaction between the diglycidyl ether represented by the above formula (I) or its oligomer and the mononuclear aromatic diol represented by the formula (I) can be carried out without using a reaction solvent, but the reaction system A reaction solvent can also be used to adjust the viscosity and make the reaction proceed smoothly. In this case, examples of the reaction solvent that can be used include the reaction solvent used when producing the diglycidyl ether represented by the above formula (I[). Further, the amount of the reaction solvent used in this case is usually 3 parts by weight or less, preferably 2 parts by weight or less, and more preferably It is 1 part by weight or less.

Further, the reaction temperature when producing the hydroxyether compound represented by the above formula (al) can be set appropriately, but for example, when a reaction solvent is not used, it is usually 90 to 180°C, preferably 100°C. ~17
Within the range of 0°C, and when using a reaction solvent, usually 80 to 250°C, preferably 100 to 220°C.
The temperature is set within the range of °C. Furthermore, this reaction can be carried out under any pressure condition: normal pressure, increased pressure, or reduced pressure. Especially when a reaction solvent is used, if the reaction pressure is kept constant, the reaction temperature can be maintained at the boiling point of the reaction solvent at that pressure, so fluctuations in the reaction temperature can be prevented. There are advantages. The reaction time under such reaction conditions is usually in the range of 0.5 to 10 hours.

After carrying out the reaction in this way, for example, the reaction solvent,
By removing unreacted raw materials and the like using a method such as distillation, a droxyether compound represented by the following formula (al) can be obtained as a solid or liquid.

However, in the above formula (al), m is a positive integer, and is usually 8 to 600. Furthermore, Aro and A rol are a glycidyl group and HO-Ar
is a group selected from A rol and A'02,
They may be the same or different, and here Ar
is a p-phenylene group as above. Moreover, such a hydroxyether compound has a substantially linear structure.

In the thus obtained hydroxyether compound represented by formula (al), the structural unit -0-CH-C
A part of H(Oft)-CH2-0-Ar- is formed by the halogen atom released from the raw material epihalohydrin represented by formula (n), and the glycidyl group of the epihalohydrin bonded by β-cleavage. It may have a 1- or 2-bond structure, or a branched structure formed by the reaction of a glycidyl group with an intramolecular hydroxyl group, as long as it is to a small extent.

The terminal groups ArO and ArQ2 of the hydroxyether compound obtained as described above are groups selected from glycidyl group and HO-Ar, respectively. However, ArO and A of the hydroxy ether compound represented by formula (al) obtained by the above reaction
rol is not all HO-Ar, and this hydroxy ether compound contains ArO and Aro
A compound in which at least a portion of l is a glycidyl group is included.

That is, for hydroquinone (I), hydroquinone diglycidyl ether or its oligomer (I)
When the usage ratio of is increased, the glycidyl group reacts with the monovalent aromatic alcohol in the end-capping treatment in the next step, and a polyhydroxypolyether containing a large amount of -valent aromatic hydrocarbon groups as terminal groups is obtained. Therefore, it is numerically preferable from the point of view that the terminal reactivity is low. In any case, in the case of the usage ratio in the above production method, it is impossible to obtain a product completely free of glycidyl groups.

When such a human oxyester compound is blended with, for example, polyethylene terephthalate, the remaining glycidyl groups deteriorate the properties such as molding stability and gas barrier properties of the resulting molded product.

Therefore, when producing the polyhydroxy polyether used in the present invention, the hydroxy ether compound represented by formula (al) obtained by the above reaction is further reacted with an aromatic monoalcohol having 6 to 15 carbon atoms. By reacting in this way, all the glycidyl groups at the ends become aromatic hydrocarbon groups, and the ends are completely blocked.

The aromatic monoalcohol that reacts with the hydroxyether compound represented by the above formula (al) to form the polyhydroxy polyether represented by the formula (a) has a carbon number in the range of 6 to 15, preferably 6 to 12. It is a compound that has one OH group in the molecule. The OH group may be bonded directly to the aromatic ring or may be bonded to the aromatic ring via an alkylene group, etc. It reacts with the glycidyl group remaining at the end of the roxyether compound. Therefore, the aromatic monoalcohol having 6 to 15 carbon atoms used in the present invention has an active group capable of reacting with the glycidyl group in addition to the above-mentioned OH group. I haven't.

Specific examples of such aromatic monoalcohols having 6 to 15 carbon atoms include phenol, cresol, xylenol, ethylphenol, diethylphenol, propylphenol, isobutylphenol, dipropylphenol, diisopropylphenol, butylphenol, and isobutylphenol. , tertiary-butylphenol, dibutylphenol, diisobutylphenol, ditertiary-butylphenol, pentylphenol,
Hexylphenol, pentylphenol, octylphenol, methylethylphenol, methylisobutylphenol, methyltert-butylphenol, phenylphenol, tolylphenol, cumylphenol, methoxyphenol, ethoxyphenol, 10-bioxyphenol, 4°-hydroxyacetophenone, Examples include 3°-human 0xyacetophenone, 2-hydroxyace1-phenone, ethyl-4-hydroxyphenylketone, propyl-4-hydroxyphenylketone, α-naphthol, and β-naphthol. The above-mentioned unreacted aromatic monoalcohol is usually removed by distillation after the completion of the reaction, so considering the removal efficiency by distillation, the aromatic monoalcohol used in the present invention is preferably one with a low boiling point. A compound is preferred, and in this case, a compound having a boiling point of 250° C. or lower is usually used. Among aromatic monoalcohols having such a boiling point, examples of preferred compounds include phenol, cresol, ethylphenol, propylphenol, isobutylphenol, methoxyphenol and ethoxyphenol. However, in the present invention, the unreacted aromatic monoalcohol is obtained by formula (a) without using the distillation operation as described above.
It can also be removed by using a treatment method such as reprecipitating the polyhydroxy polyether represented by the formula. When this method is adopted, there is little difference in the advantages of using aromatic monoalcohols with relatively low boiling points and other aromatic monoalcohols.

The reaction between the hydroxyether compound represented by the above formula (al) and the aromatic monoalcohol is carried out in the presence of a specific catalyst.

The catalyst used in the present invention is a tertiary amine compound,
It is at least one compound selected from quaternary ammonium compounds, tertiary phosphine compounds, and quaternary phosphonium compounds.

The catalyst used in this reaction is a hydroxy ether represented by the formula (al) obtained by reacting the glycidyl ether represented by the formula (I[) or its oligomer with the mononuclear aromatic diol represented by the formula (I>). This catalyst is the same type as the catalyst used to produce the compound.

Therefore, specific examples of catalysts used in producing the polyhydroxy polyether represented by formula (a) include the compounds exemplified in the process of producing the hydroxy ether compound represented by formula (al) above. be able to. Such a catalyst can be used as it is without separating the catalyst used in producing the hydroxyether compound represented by the formula (al), or can be additionally added, After producing the hydroxyether compound represented by the formula (al), the catalyst can be separated and freshly added. Further, the catalyst used in this step and the catalyst used in producing the hydroxyether compound represented by the above formula (al) may be the same compound or may be different compounds.

In the present invention, the aromatic monoalcohol having 6 to 15 carbon atoms is usually 0.1 to 10 mol, preferably 0.5 to 10 mol, per mol of the hydroxyether compound represented by formula (al). It is used in an amount of 5 mol, more preferably 0.6 to 4 mol.

In addition, the catalyst is usually 0.00% with respect to the total of units derived from mononuclear aromatic diols represented by formula (al) and contained in the droxyether compound. ooi~1
It is used in a range of 0 mol%, preferably 0.005 to 5 mol%, more preferably 0.01 to 1 mol%.

In the present invention, the reaction between the droxyether compound represented by the formula (al) and the aromatic monoalcohol is as follows:
Although the reaction can be carried out without using a reaction solvent, in order to adjust the viscosity of the reaction system during the reaction and allow the reaction to proceed smoothly, it is preferable to carry out the reaction using a reaction solvent. For this purpose, a compound of the same type as the reaction solvent used in the production of the hydroxyether compound represented by the above formula (al) can be used. That is,
Solvents such as saturated hydrocarbons, aromatic hydrocarbons, ketones, amides, and sulfoxides as shown in the above specific examples can be used. Among these reaction solvents,
Considering the solubility of the raw material, the droxyether compound represented by the above formula (al), and the product, the polyhydroxy polyether represented by the formula (a), ketones are particularly preferred. Therefore, the reaction solvent used is In this case, the reaction solvent used in producing the hydroxyether compound represented by formula (al) can be used as is, or after removing part or all of this reaction solvent, a new reaction solvent can be used. can also be added.

When using a reaction solvent, the reaction solvent has the formula (al)
It is usually used in a proportion of 311 parts by weight or less, preferably 2 parts by weight or less, and more preferably 1 part by weight or less, per 1 part by weight of the hydroxyether compound represented by.

The reaction between the hydroxyether compound represented by formula (al) and the aromatic monoalcohol having 6 to 15 carbon atoms is usually carried out at 100 to 200°C when a solvent is not used.
, preferably 110 to 190°C, more preferably 12
The temperature is within the range of 0 to 180°C, and when a solvent is used, the temperature is usually 100 to 280°C, preferably 110 to 280°C.
The reaction is carried out at a temperature of 260°C, more preferably within the range of 120 to 250''C.The reaction can be carried out under normal pressure, increased pressure or reduced pressure.The reaction is usually carried out under stirring. It will be completed in 0.5 to 5 hours.

By carrying out the reaction in this manner, a polyhydroxy polyether represented by the following formula (a) is produced.

0 ■ ... (a) However, in the above formula (a), A "1 and Ar" each independently represent a monovalent aromatic hydrocarbon having 6 to 15 carbon atoms other than HO-Ar or HO-Ar. A" represents a p-phenylene group, furthermore, n represents a positive integer, and this n is usually
A value similar to the value of m in l) is shown.

The polyoxydroxypolyether represented by formula (a) produced in this way is removed by distillation or other methods when unreacted aromatic monoalcohol and reaction solvent are used. You can get it by doing this. Note that the reaction solvent or unreacted aromatic alcohol can be removed not only by distillation as described above but also by using other known methods such as reprecipitation.

After removing the reaction solvent or unreacted aromatic alcohol in this way, the polyhydroxy polyether represented by formula (a) is made into a melt, for example, and then extruded into a strand, cooled, and then cut. Pellets of polyhydroxypolynythyl can be obtained by using known methods such as.

The polyhydroxy polyether thus obtained has an intrinsic viscosity of [
By controlling the manufacturing conditions, etc., the intrinsic viscosity [η
] from 0.3 to 1.9 dJ! /', more preferably within the range of 0.4 to 1.8 dJ/g.The number average molecular weight (Mn) of the polyhydroxy polyether having such an intrinsic viscosity [η] is , usually within the range of 1300 to 100.000, preferably 30
00~s0. It is within the range of ooo. A molded article or a stretched molded article of a polyester resin composition containing a polyhydroxy polyether having an intrinsic viscosity [η] of less than 0.1 dJ/sr tends to have reduced mechanical strength.

The polyhydroxy polyether used in the present invention usually has a glass transition temperature of 40 to 80°C, preferably 50 to 70°C.

Furthermore, the polyhydroxypolyether used in the present invention has a weight average molecular weight (MW) and a number average molecular weight (Mn
) (KIWw/Mn) The value indicating the defined molecular weight distribution is usually within the range of 1.5 to 10.

Such polyhydroxy polyethers have a substantially linear structure.

Here, "substantially linear" means that the polyhydroxypolyether has a chain structure with substantially no branching and does not substantially contain a gel-like crosslinked structure (network structure). . Specifically, it means that when 0.5f of polyhydroxypolyether is dissolved in 100ml of O-chlorophenol at 25°C, there is substantially no insoluble component.

The polyhydroxy polyether used in the present invention has a terminal p-hydroxyphenoxy group or a carbon number of 6 to 6.
15 monovalent aromatic hydrocarbon groups. The abundance ratio of the p-hydroxyphenoxy group constituting the terminal group of this polyhydroxypolyether and the monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms is determined when producing the polyhydroxypolyether. It is equal to the abundance ratio of p-hydroxyphenoxy groups and glycidyl groups present in the hydroxyether compound represented by formula (al). That is,
This polyhydroxypolyether is represented by the formula (al), and all the glycidyl groups contained in the droxyether compound react with aromatic monoalcohol and are converted into hydrocarbon groups, so that substantially no glycidyl groups are converted into hydrocarbon groups. Not included.

As described above, the polyhydroxy polyether used in the present invention has p-hydroxyphenyl groups and monovalent aromatic hydrocarbon groups as terminals, but - numerically -
Polyhydroxypolyethers containing a large number of aromatic hydrocarbon groups as terminal groups are preferable in that the terminal reactivity is low.

In addition, such polyhydroxypolyether is produced by β, γ-dihydroxypropioxy groups generated by the reaction between moisture present in the reaction system and glycidyl groups, or groups induced by the above reaction. It may also contain small amounts of polyhydroxy polyethers terminated with .

As mentioned above, the polyhydroxy polyether used in the present invention does not contain any glycidyl groups as terminal groups. The glycidyl group itself is known to be a mutagenic and chromosomal aberration-inducing group. Therefore, the polyhydroxypolyether that does not contain such triggering glycidyl groups is excellent in safety and hygiene, particularly when used in food applications.

Furthermore, the glycidyl group is a highly reactive functional group and is known to easily react with functional groups forming polyesters such as carboxyl groups and hydroxyl groups. Therefore, by using the polyhydroxy polyether that does not contain such highly reactive glycidyl groups, the resin composition of the present invention has excellent stability during molding, and a homogeneous composite material can be obtained. In particular, when used as a gas barrier imparting agent for polyalkylene terephthalate such as polyethylene terephthalate, gelation and scorching during molding are greatly suppressed, ensuring stable molding for a long time, and preventing foreign matter. This gives rise to the advantage that a homogeneous composition or laminate free of oxidants can be obtained.

As mentioned above, the polyhydroxy polyether used in the present invention is produced by reacting its glycidyl terminal end with a monohydric aromatic alcohol.

At this time, the low molecular weight oligomers contained in the polyhydroxy polyether also react with m aromatic alcohols to increase the overall molecular weight, therefore, the polyhydroxy polyether has a lower molecular weight than in the case of the conventional method. It is characterized by a low content of molecular weight oligomers. This ensures long-term stable moldability by reducing volatile components during melt molding of the polyhydroxypolyether, and also improves safety by suppressing elution and desorption of oligomers during actual use. and improved hygiene. Furthermore, since the oligomer contained in the polyhydroxy polyether has been treated with a -valent aromatic alcohol, the content of hydrophilic hydroxyl groups is reduced. Therefore, when the polyhydroxypolyether or its composition or complex such as Nt* is used for food purposes, the dissolution of commonly used contents such as water, alcohol, or acetic acid is suppressed. There are also food safety and hygiene benefits.

By blending the polyhydroxy polyether and polyalkylene terephthalate obtained in this way,
The polyester resin composition of the present invention can be obtained.

The polyalkylene terephthalate used in the present invention is a polyalkylene terephthalate whose main constitutional unit is ethylene terephthalate constitutional unit, and the content of ethylene terephthalate constitutional unit is usually 50 mol%.
As mentioned above, polyethylene terephthalate having a content of preferably 70 mol% or more is preferred.

Therefore, the polyalkylene terephthalate used in the present invention is usually less than 50 mol%, preferably 3.
It may contain a structural unit containing an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit in an amount of less than 0 mol %.

Here, other aromatic dicarboxylic acid component units other than terephthalic acid component units include isophthalic acid,
Mention may be made of component units derived from phthalic acid, naphthalene dicarboxylic acid, and the like. Further, the diol component unit constituting the polyalkylene terephthalate is preferably an ethylene glycol component unit, but the ethylene glycol component unit may contain a small amount of a diol component unit in addition to the ethylene glycol component unit. Other diol component units include, for example, 1.3-propanediol, 1.4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexane dimetatool, 1.4-bis(β-hydroxyethoxy)benzene. , 1,3-bis(β-hydroxyethoxy)benzene, 2,2-bis(4-β-droxyethoxyphenyl)propane and bis(4-
Mention may be made of component units derived from diols having 3 to 15 carbon atoms, such as β-hydroxyethoxyphenyl) sulfone.

Furthermore, in addition to the aromatic dicarboxylic acid component units and the diol component units, the polyalkylene terephthalate may also contain structural units derived from other polyfunctional compounds, if necessary.

Specific examples of the polyfunctional compound forming the component unit derived from the polyfunctional compound include trimellitic acid, trimesic acid, and aromatic compounds such as 3,3°, 5,5°-tetracarboxydiphenyl. aliphatic polybasic acids such as butanetetracarboxylic acid; aromatic polyols such as phloroglucin and 1,2,4.5-tetrahydroxybenzene; glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol and oxypolycarboxylic acids such as tartaric acid and malic acid.

The content of the constituent components in such polyalkylene terephthalate is such that the content of terephthalic acid component units is usually in the range of 50 to 100 mol%, preferably 70 to 100 mol%, and aromatic components other than terephthalic acid component units are contained. The content of group dicarboxylic acid component units is usually in the range of 0 to 50 mol%, preferably 0 to 30 mol%, and the content of ethylene glycol component units is usually in the range of 50 to 100 mol%, preferably The content of diol component units other than ethylene glycol component units is usually 0 to 50 mol%, preferably 0 to 30 mol%, and the polyfunctional compound component is in the range of 70 to 100 mol%. The unit content is usually in the range of 0 to 2 mol%, preferably 0 to 1 mol%.

Further, the intrinsic viscosity [η] of such polyalkylene terephthalate (measured in 0-chlorophenol at 25°C) is usually 0.5 to 1.56 j/g, preferably 0.6 to 1. 2dJ,/g, the melting point is usually in the range of 210 to 265°C, preferably 220 to 260°C, and the glass transition temperature is usually in the range of 50 to 120°C,
Preferably it is in the range of 60 to 100°C.

The polyester resin composition of the present invention can be produced by mixing the polyoxydroxypolyether obtained as described above and polyalkylene terephthalate.

There is no particular restriction on the method of mixing the two, and a method of melt-kneading using a commonly used kneading device or the like can be used.

In the polyester resin composition of the present invention, the blending ratio of polyhydroxybolyether is usually 1 to 100 parts by weight, preferably 2 to 50 parts by weight, particularly preferably 3 parts by weight, based on 100 parts by weight of polyalkylene terephthalate. ~
It is within the range of 30 parts by weight.

In addition, in the polyester resin composition of the present invention, other resins can also be blended within a range that does not impair the properties. Furthermore, the polyester resin composition of the present invention contains nucleating agents, inorganic fillers, lubricants, slip agents, anti-blocking agents, stabilizers, antistatic agents, antifogging agents, pigments, etc. that are usually incorporated into resin compositions. Additives can also be blended.

The polyester resin composition of the present invention can be used in an unstretched state as a molded article in various shapes such as a film, sheet, fiber, container, etc. using a normal molding method.

Furthermore, the polyester resin composition of the present invention can also be stretched into shapes such as films, sheets, fibers, containers, etc. By stretching in this manner, gas barrier properties are further improved.

Next, the stretched molded article of the present invention will be explained.

The stretched molded article of the polyester resin composition of the present invention includes -
There are axially stretched molded bodies and biaxially stretched molded bodies, and the form thereof may be any of films, sheets, and fibers.

Any conventionally known method can be adopted as a method for producing a stretched molded article of this polyester resin composition. In general, the vapor-molded product such as a film or sheet formed from the polyester resin composition is used as it is, or after being cooled to a temperature below the glass transition point of the composition and solidified, the composition is heated to a glass transition point or melting point, preferably glass. Stretching treatment is performed at a temperature range of 80° C. higher than the transition point or glass transition point. Further, the heat setting treatment of the stretched molded product is carried out by heating at the above-mentioned stretching temperature or a higher temperature for a certain period of time.

As a method for producing a stretched molded article of this polyester resin composition, when the evaporated molded article is a film or a sheet, an example of a stretching method that can be used is stretching an unstretched film or sheet in a uniaxial direction. method (-axial stretching method), a method of stretching in the longitudinal direction and then further stretching in the transverse direction (biaxial stretching method), a method of simultaneously stretching in the longitudinal and transverse directions (simultaneous biaxial stretching), A method of repeating sequential stretching in any one direction after biaxial stretching;
Examples include a method in which the film is biaxially stretched 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 a space formed by a film or sheet and a mold. Here, the stretching ratio in the case of uniaxial stretching using polyhydroxybolyether is usually 1.1 to 10@, preferably 1.2 to 8 times, particularly preferably 1.5 to 7 times. range. In addition, when producing a molded product by biaxial stretching, the stretching ratio in the transverse direction is usually 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5 to 6 times. range, and in the transverse direction, usually 1°1~8@, preferably 1.2~7 times, particularly preferably 1
．． It is in the range of 5 to 6 times.

Moreover, it is also possible to produce a stretched molded article of these polyester resin compositions in the form of a laminate with other resins.

A method for producing a stretched laminate including a layer made of a polyester resin composition includes laminating a vapor molded product such as a film or sheet of a polyester resin composition with a vapor molded product such as a film or sheet of another resin, and then stretching. Examples include a method of bonding a film or sheet of resin to a stretched molded product of a polyester resin composition.

The stretched molded product of the polyester resin composition obtained in this way has excellent properties such as mechanical strength and gas barrier properties, so it can be used as a film, sheet, tubular body, container, etc.
It can be used in shapes such as bottles.

The polyester stretched hollow molded preform of the present invention is formed from the polyester resin composition described above.

Such a preform for a stretched hollow molded body can be manufactured by a conventionally used method.

For example, the preform for a polyester hollow molded body of the present invention can be obtained by molding a tubular object made of the polyester resin composition.

The polyester stretched hollow molded body of the present invention is a stretched hollow molded body formed from the polyester resin composition.

This stretched hollow molded body can be produced, for example, by stretch-blow molding the preform for the stretched hollow molded body.

The stretched hollow molded product of the present invention may be a -axially stretched molded product or a biaxially stretched molded product. In particular, in the present invention, the mechanical strength of the hollow molded product is improved by biaxially stretching. and gas barrier properties are improved.

In the present invention, the stretching ratio of the stretched hollow molded article can be the same as that of the stretched hollow molded article of the polyester resin composition.

The polyester stretch hollow molded body according to the present invention can be produced by stretch-blow molding the polyester hollow molded body preform. The stretch blow molding method includes a method in which the preform is stretched in the longitudinal direction within the stretching temperature range of the composition, and then further blow molded to stretch it in the transverse direction (
Examples include two-wheel stretch blow molding method).

The hollow molded article made of the polyester resin composition of the present invention has good mechanical strength and gas barrier properties, so it can be used for various purposes.

In particular, the biaxially stretched blow-molded container of the present invention has excellent gas barrier properties, so it can be used not only as a container for seasonings, oils, alcoholic beverages, cosmetics, detergents, etc., but also for colas, cider, beer, etc. Suitable for sparkling beverage containers. That is, by using the stretched molded article of the present invention, the shelf life can be extended without increasing the thickness of the container unlike conventional containers.

(Leaving space below) The polyhydroxypolyether used in the present invention has no glycidyl group at the end of the molecule, and the end is completely capped, so it has very high thermal stability. is in good condition.

Furthermore, by capping the ends in this manner, the excellent properties of polyhydroxypolyether, such as the mechanical strength of polyhydroxypolyether, are not reduced.

Furthermore, since the polyhydroxy polyether used in the present invention does not have a glycidyl group at the end, the reaction is likely to proceed, for example, when molding it in a molten state or when mixing it with other resins. Even when this polydroxypolyether is placed in the same condition, the reaction does not proceed.

The polyester resin composition of the present invention containing a polyhydroxy polyether having such characteristics has very good specific heat stability during molding and also has excellent gas barrier properties. Further, the preform for a stretched hollow molded body obtained using the polyester resin composition of the present invention has excellent moldability.

Therefore, a hollow molded article obtained using such a preform has excellent moldability and particularly excellent gas barrier properties.

[Example] Next, the present invention will be specifically explained using Examples. The polyhydroxypolyethers used in Examples and Comparative Examples were produced as shown in Reference Examples and Comparative Reference Examples, respectively. Furthermore, in Examples, Reference Examples, Comparative Examples, and Comparative Reference Examples, unless otherwise specified, "parts"
The expression "parts by weight" means "parts by weight".

Furthermore, performance evaluation of the polyhydroxy polyether and polyester resin compositions was performed according to the method described below.

The composition of the polyhydroxy polyether was determined by measuring the magnetic resonance spectrum of the polyhydroxy polyether obtained.

The intrinsic viscosity [η] was measured in 0-talolophenol at 25°C.

The glass transition temperature was determined by heating the resulting polyhydroxypolyether until it became molten and fluid, then rapidly cooling it to room temperature, and measuring the resulting resin sample using a differential scanning calorimeter at a heating rate of 10°C/min. It was determined by measuring.

Mechanical properties were measured using an Instron tensile tester according to a conventional method.

Gas barrier property is determined by the oxygen gas permeability coefficient, Mocon (HO
The carbon dioxide permeability coefficient was measured at 25°C using an OXTRAN device manufactured by HOCON, and a PERHATRAN C-IV device manufactured by HOCON, and the evaluation was based on these values. .

The hue was measured using a ND-1001DP color difference meter manufactured by Nippon Denshoku Kogyo ■.

The degree of haze was measured using an NDH-20D type haze meter manufactured by Nippon Heavy Industries Ltd.

2202 parts of hydroquinone and epichlorohydrin were placed in a reaction tank equipped with an 11-dish stirrer, a distillation device equipped with a separator that separates the distillate fraction and returns only the bottom layer to the reaction tank, and a continuous liquid supply device. 663 parts of a 50% aqueous sodium hydroxide solution was added continuously over about 90 minutes while stirring and keeping the temperature of the system at about 65°C, and after the addition was completed, the reaction was continued for an additional 60 minutes.

Furthermore, the temperature of the system was maintained at about 70°C, and the temperature of about 200nm H
50% sodium hydroxide aqueous solution 24 while reducing the pressure to Q.
70 parts were continuously fed over about 120 minutes. At this time, unreacted epichlorohydrin and water were azeotropically distilled, so water was distilled off and epichlorohydrin was returned to the system.

After feeding the 50% aqueous sodium hydroxide solution, the reaction was continued for an additional approximately 60 minutes.

Next, the temperature of the system was raised to about 120° C., and the degree of vacuum of the system was further increased to about 5 H (+) to completely distill off unreacted epichlorohydrin from the system.

After epichlorohydrin was distilled off, the pressure of the system was returned to normal pressure and the temperature was lowered to about 100° C., and a mixture of 5,420 parts of xylene and 7,500 parts of water was added to the reaction solution and stirred thoroughly. This reaction solution was separated into two layers by standing still.

The lower aqueous layer was removed, and 422 parts of a 6% aqueous sodium hydroxide solution was added to the separated upper layer (xylene layer) to make about 7
Stirred at 0°C for about 120 minutes. Since this reaction solution is alkaline, 10% sodium dihydrogen phosphate aqueous solution 15
36 parts were added over about 30 minutes and neutralized at about 90°C.

After neutralization, the temperature of the reaction solution is raised to about 140°C and the pressure of the reaction system is reduced to about 300m+Hq, and the water present in the system is distilled off with xylene by azeotropic distillation to reduce the concentration of the reaction product. A xylene solution with about 70% was obtained. This solution is filtered to separate and remove the sodium chloride precipitated in the reaction solution and a small amount of by-produced gel.

The P solution was heated to about 150° C., and the operation was continued for about 60 minutes under a reduced pressure of about 1 rum H (l) to completely distill off xylene, and the solid content obtained by cooling was pulverized.

The powder thus obtained was 4026 parts, and analysis revealed that the powder had an epoxy equivalent of 135 and an Or/e
The main components are hydroquinone diglycidyl ether with Q (epoxy group content 7.696Q/kg) and an oligomer in which a structural unit derived from one molecule of hydroquinone and one molecule of epichlorohydrin is added to this hydroquinone diglycidyl ether. It turned out to be a powder.

Next, 270 parts of the hydroquinone diglycidyl ether and its oligomer thus produced, 99 parts of hydroquinone, 165 parts of cyclohexanone, and 0.7 part of a 20% aqueous solution of tetraethylammonium hydroxide were added to a mixture equipped with a stirring device and a reflux device. Prepare the reaction tank,
After the inside of the tank was sufficiently purged with nitrogen gas, the temperature was raised to about 150° C. with stirring under a nitrogen atmosphere, and the reaction was carried out for about 120 minutes. Evaporated matter generated at this time was returned to the system by reflux.

Further, without refluxing, the temperature was raised to about 170° C. and the reaction was continued for about 120 minutes. Sampling was performed from the reaction solution obtained in this way, and the collected sample was heated to about 140°C.
Finally, the pressure was reduced to about IIwIIH9, and evaporated substances such as cyclohexanone used as a solvent were removed.
The reaction product was isolated.

As a result of analysis of the isolated reaction product, the intrinsic viscosity [η of this reaction product] was 0.35 dj/r, approximately 90% of the terminal groups were glycidyl groups, and the remaining 10% were p −
It was hydroquinone polyhydroxy polyether, which is a hydroxyphenoxy group.

Next, 59 parts of p-cresol and 2 parts of tetraethylammonium hydroxide were added to the remaining sampled reaction solution.
After adding a mixture with 0.2 parts of a 0% aqueous solution, the mixture was reacted again under reflux at about 170° C. for about 120 minutes with stirring.

After 120 hours, the apparatus was changed so that the reflux components were distilled out of the reaction system, and the temperature was raised from about 170°C to 250°C over about 60 minutes to remove the distillate.

Once no distillate was produced, the reaction system pressure was reduced to a final pressure of about 2 rm HQ.

After reducing the pressure as described above, the mixture was further heated at about 250° C. for about 60 minutes to completely distill off evaporated substances such as cyclohexanone used as a solvent and unreacted p-cresol.

Next, nitrogen gas was introduced into the system to return the pressure of the system to normal pressure, and the 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 resulting pellet was dried at about 50° C. under reduced pressure.

As a result of analyzing the pellet thus obtained, the intrinsic viscosity [η] was 0.37dj! /g, and the glass transition temperature is 60°C. Approximately 90% of the terminal groups are l)-tolyl groups, and the remaining 10% are p-hydroxyphenyl groups, and the glycidyl groups are completely It was hydroquinone polyhydroxy polyether that disappeared.

Further, as a result of examining the hue of the obtained beret, the L value (lightness) was 58.5, and the b value (yellowing degree) was 11.
It was 5.

The thus obtained polyhydroxypolyether was compression molded using a blend molding machine at about 200° C. and 50 kg/− to produce a sheet having a thickness of about 200 μm.

As a result of examining the haze level (HAZE) of this sheet, the haze level was 2.3%, and the sheet had crushed transparency.

As a result of measuring the mechanical properties of this sheet, the tensile strength at break was 410 kg/ai, the tensile elongation at break was 45%, and the tensile modulus was 26000 kt/a1N, indicating that the sheet had excellent strength.

As a result of examining the gas barrier properties of this sheet, the carbon dioxide permeability coefficient was 0.81ml-nm/rrfdaVatl,
Oxygen gas permeability coefficient is 0, 27ml ・rnt+/rd
・It was day -aLn.

270 parts of hydroquinone diglycidyl ether and its oligomer, 1 part of hydroquinone were added to the equipment used in the production of polyhydroxy polyether in Reference Example 1.
After adding 1 part of 0.01 parts, 165 parts of cyclohexane, and 0.7 parts of 20% tetraethylammonium hydroxide aqueous solution, and purging the inside of the tank with nitrogen gas, the temperature was raised to about 140°C with stirring under nitrogen atmosphere for about 60 minutes. Heating was performed.

Next, in the same manner as in Reference Example 1, the reaction was carried out at about 150°C for about 90 minutes and further at about 170°C for about 120 minutes. A small amount of the product was sampled from the reaction solution thus obtained, treated in the same manner as in Reference Example 1, and analyzed. As a result, this reaction product had an intrinsic viscosity [η of 0.47 dj/+; It was found that it is a hydroquinone polydroxy polyether in which about 85% of the terminal groups are glycidyl groups and the remaining about 15% are p-hydroxyphenoxy groups.

A mixture of 56 parts of p-methoxyphenol and 0.2 parts of 20% tetraethylammonium hydroxide in water was added to the remaining sampled reaction solution, and the mixture was heated under reflux at about 170°C for about 120 minutes in the same manner as in Reference Example 1. After reacting, the apparatus was changed so that the reflux was distilled out of the system, and the temperature was raised from about 170°C to about 250°C over about 60 minutes, and the pressure was finally reduced to about 2 tm HQ. Further, the distillate was completely distilled off by holding the mixture under reduced pressure at about 250° C. for about 60 minutes, and the same procedure as in Reference Example 1 was carried out to obtain a pellet.

As a result of analyzing the obtained pellet in the same manner as in Reference Example 1, the intrinsic viscosity [η] was 0.48 dJ/g, and the glass transition temperature was 61°C. In addition, 85% of the terminal groups in this polyhydroxypolyether are p-methoxyphenyl groups, and the remaining approximately 15% are O-hydroxyphenyl groups, making it a hydroquinone polyhydroxypolyether in which the glycidyl groups have completely disappeared. Met.

Also, as a result of examining the hue of the beret, the L value (lightness) was 61.
．． 0, and the b value (yellow coloring degree) was 13.9.

Further, this polyhydroxypolyether was press-molded in the same manner as in Reference Example 1 to produce a press sheet having a thickness of about 200 μm.

The haze (HAZE) of this press sheet was 2.2%. In addition, the mechanical properties of this sheet are tensile strength at break of 43
0 kg/aa, tensile elongation at break 72%, and tensile modulus 28000 kg/cd. Furthermore, as a result of examining the gas barrier properties of this sheet, the carbon dioxide permeability coefficient was 0,
78ml ・+n+/rd ・day Hajll, and the oxygen gas permeability coefficient is 0.26011・+n+/r
rl' day -atn.

Next, this press sheet was simultaneously stretched 3 times in the vertical and horizontal directions using a biaxial stretching device at a temperature of 70 to 85°C and 10 m+/5I3C to obtain a biaxial sheet with a thickness of about 22 μm. An axially stretched film was obtained.

As a result of measuring the mechanical properties of this film, the tensile strength at break was 450+qr/cj, the tensile elongation at break was 33%, and the tensile modulus was 34000 kg/-. Furthermore, as a result of measuring the gas barrier properties of this biaxially stretched film,
Carbon dioxide permeability coefficient is 0.77 m1-wr/rrrdaV
-atrm, oxygen gas permeability coefficient is 0, 23+nl
・nm/rd-day-atl.

11■ 270 parts of hydroquinone diglycidyl ether and its oligomer shown in Reference Example 1, 104 parts of hydroquinone
Using 165 parts of cyclohexanone and 0.7 parts of 20% tetramethylammonium hydroxide aqueous solution, the mixture was heated at about 140°C for about 30 minutes and at about 150°C for about 90 minutes in the same manner as in Reference Example 2.
The reaction was carried out for 0 minutes and then at about 170° C. for about 120 minutes.

The reaction solution thus obtained was sampled and treated in the same manner as in Reference Example 1, and the obtained reaction product was analyzed. As a result, the intrinsic viscosity [η] was 0.54 (Il
l/f, about 80% of the terminal groups were glycidyl groups, and the remaining about 20% were hydroquinone polyhydroxy polyethers, which were p-hydroxyphenoxy groups.

28 parts of phenol and 0.2 parts of a 20% tetraethylammonium hydroxide aqueous solution were added to the remaining sampled reaction solution.
The reaction mixture was again reacted in the same manner as in Reference Example 1, and after the distillate components were distilled off, post-treatment was performed to obtain a pellet of the reaction product.

As a result of analyzing the obtained pellet, it was found that @limiting viscosity [η
] is 0.55 dJ/+r, and the glass transition temperature is 62
It was °C. Approximately 80% of the terminal groups of the obtained polyhydroxypolyether are phenoxy groups, and the remaining approximately 20% are phenoxy groups.
% was p-hydroxyphenyl group, and glycidyl group had completely disappeared.

As a result of examining the hue of the resulting polyhydroxypolyether pellet, the Llia (lightness) was 62.3, and the b value (yellow coloring degree) was 12.7.

Further, this polyhydroxy polyether was press-molded in the same manner as in Reference Example 1 to produce a press sheet having a thickness of about 200 μm.

The haze (HAZE) of this press sheet was 2.5%. Further, as a result of measuring the R mechanical properties of this press sheet, the tensile strength at break was 455 kHz/aJ, the tensile elongation at break was 78%, and the tensile modulus was 29000 kg/-. Furthermore, as a result of investigating the gas barrier properties, the carbon dioxide permeability coefficient was 0.76 [111·m/rd -day -an]
, the oxygen gas permeability coefficient is 0.27 (+11-wr /
rr?・daV ・atll.

Next, this press sheet was biaxially stretched in the same manner as in Reference Example 2 to produce a biaxially stretched film having a thickness of about 22 μm.

As a result of measuring the mechanical properties of this biaxially stretched film, the tensile strength at break was 465 kg/ad, and the tensile elongation at break was 37%.
, and the tensile modulus was 34,000 kg/-. Furthermore, as a result of measuring the gas barrier properties of this biaxially stretched film, the carbon dioxide gas permeability coefficient was 0.75 ml mn/r.
r? -day Hatll, and the oxygen gas permeability coefficient was 0.21 ml·rm/rd-day Hatll.

11 WataruA In Reference Example 1, except that the amount of hydroquinone used was changed to 106 parts, the preparations were made in the same manner, and the reaction temperature and time were further changed to about 140°C for about 60 minutes, about 150°C for about 60 minutes, and about 170°C. A reaction solution of a hydroxyether compound was obtained in the same manner except that the reaction time was kept at ℃ for about 90 minutes.

Next, 24 parts of p-ethylphenol and 0.2 parts of a 20% tetraethylammonium hydroxide aqueous solution were added to the reaction solution.
The reaction was carried out again in the same manner as in Reference Example 1, and after the distillate components were distilled off, the mixture was post-treated to obtain pellets of polyhydroxy polyether.

The intrinsic viscosity [η] of this polyhydroxy polyether is 0
．． 96dj/'sr, and the glass transition temperature was 62°C. Furthermore, about 80% of the terminal groups of this polyhydroxypolyether were p-ethylphenyl groups, the remaining about 20% were p-hydroxyphenyl groups, and the glycidyl groups had completely disappeared.

Further, as a result of examining the hue of this polyhydroxypolyether pellet, the L value (lightness) was 57.5, and the b value (yellow coloring degree) was 13.5.

Further, this polyhydroxy polyether was press-molded in the same manner as in Reference Example 1 to produce a press sheet having a thickness of about 200 μm.

The haze degree (11^z[) of this press sheet was 2.3%. The mechanical properties of this press sheet were a tensile strength at break of 4,901 qr/cj, a tensile elongation at break of 76%, and a tensile modulus of elasticity of 29,000 kg/cd. Furthermore, as a result of investigating its gas barrier properties, the carbon dioxide permeability coefficient was 0.
, 78ml-rm/rd・day Hatom.

Reference Example 5 The preparation was carried out in the same manner as in Reference Example 1 except that the amount of hydroquinone used was 110 parts, and the reaction temperature and time were changed to about 140°C for about 90 minutes, then about 150°C for about 30 minutes.
A reaction solution of a hydroxy ether compound was obtained in the same manner except that the reaction time was for a minute.

After adding a mixture of 40 parts of phenol and 0.2 parts of a 20% tetraethylammonium hydroxide aqueous solution to this reaction solution, the temperature and time during the reaction and distillation of the distillate components were set to 1, About 30 minutes at about 150℃, about 120 minutes at about 170℃, about 250℃ from about 170℃
The reaction and distillation were carried out in the same manner, except that the temperature was raised to ℃ for about 60 minutes and the time at about 250℃ for about 60 minutes, and the post-treatment was carried out in the same manner to obtain pellets of polyhydroxypolyether. Obtained.

The intrinsic viscosity of this polyhydroxy polyether [η is 1
．． 57dj/g, and its glass transition temperature is 63
It was ℃. Furthermore, it was found that about 60% of the terminal groups of the polyhydroxypolyether were phenyl groups, about 40% were p-hydroxyphenyl groups, and the glycidyl groups had completely disappeared.

Further, as a result of examining the hue of this polyhydroxy polyether pellet, the L value (lightness) was 61.6, and the b value (yellow coloring degree) was 13.1.

Next, using this polyhydroxypolyether, press molding was performed in the same manner as in Reference Example 1 to produce a press sheet having a thickness of about 200 μm.

The palatability ([1^ZE) of this press sheet was 2.0%. As a result of measuring the mechanical properties of Manako's press sheet, the tensile strength at break was 560 kIr/cd, the tensile elongation at break was 86%, and the tensile modulus was 31000 kg/aa.
Met. Furthermore, as a result of investigating its gas barrier properties, the carbon dioxide permeability coefficient was 0.75ml ・m/rd ・day
It was Hatll.

11 dishes 1 Prepare in the same manner as in Reference Example 3 except that the amount of hydroquinone used was changed to 117 parts, and then react in the same manner at about 140°C for about 30 minutes, at about 150°C for about 90 minutes, and at about 170°C for about 120 minutes. A reaction solution of a hydroxyether compound was obtained.

After adding a mixture of 20 parts of phenol and 0.2 parts of a 20% tetraethylammonium hydroxide aqueous solution to this reaction solution, the reaction, distillation of the distillate components, and post-treatment were carried out again in the same manner as in Reference Example 3. Pellets of droxypolyether were obtained.

The intrinsic viscosity [η] of this polyhydroxy polyether is 0
．． 58 dJ/g, and its glass transition temperature is 63
It was ℃. In addition, about 20% of the terminal groups of polyhydroxypolyether are phenyl groups, and the remaining 80% are phenyl groups.
-hydroxyphenyl group, and the glycidyl group had completely disappeared.

Further, the hue of this polyhydroxyboether was examined, and the L value (lightness) was 56.9, and the b value (yellow coloring degree) was 12.8.

Next, this polyhydroxypolyether was press-molded in the same machine as Reference Example 1 to produce a press sheet having a thickness of about 200 μm.

The haze (IAZE) of this press sheet was 2.1%. Further, as a result of measuring the mechanical properties of this press sheet, the tensile strength at break was 460 kr/cd, the tensile elongation at break was 75%, and the tensile modulus was 28,500 kg/-.

Further, using this press sheet, a biaxially stretched film having a thickness of about 22 μm was produced in the same manner as in Reference Example 2.

As a result of measuring the mechanical strength of this film, the tensile strength at break was 480 kr/cd, the tensile elongation at break was 38%, and the tensile modulus was 34,500 kg/-.Furthermore, the gas barrier properties of this biaxially stretched film were measured. As a result, the carbon dioxide permeability coefficient was 0.74 1・tar/rr?・
day ・atn, and the oxygen gas permeability coefficient is 0.24
It was ml-IwlI/nfda'/ ·at+i.

Polyhydroxypolyether was prepared by using the same raw materials in the same proportions as in Reference Example 3 of Mayu Kasami, except that 20 parts of phenol was not used. Get a beret.

The intrinsic viscosity [η] of this polyhydroxy polyether is 0
．． 69dj/+r, and the glass transition temperature was 63°C. Furthermore, the terminal groups of this polyhydroxypolyether were mostly p-hydroxyphenyl groups, but terminal groups such as those obtained by adding the solvent cyclohexanone to glycidyl groups were observed.

Further, as a result of examining the hue of this polyhydroxy polyether, the L value (lightness) was 22.8, and the b value (yellow coloring degree) was 24.8. The hue was very poor compared to that of the original.

Next, this polyhydroxypolyether was press-molded in the same manner as in Reference Example 1 to produce a press sheet having a thickness of about 200 μm.

As a result of measuring the mechanical properties of this press sheet, the tensile strength at break was 450 kg/d, the tensile elongation at break was 52%, the tensile modulus was 30,500 mm/-, and the haze () was 18 Z.
E) was 7.6%, and the transparency was inferior compared to the polyhydroxy polyether of the present invention.

Reference Example 7 The preparation was carried out in the same manner as in Reference Example 3, except that the amount of hydroquinone used was changed to 121 parts, and then the same procedure was carried out at about 140°C for about 30 minutes, at about 150'C for about 90 minutes, and at about 170°C.
The mixture was reacted for about 120 minutes to obtain a reaction solution of a hydroxyether compound.

After adding a mixture of 22 parts of p-cresol and 0.2 parts of a 20% tetraethylammonium hydroxide aqueous solution to this reaction solution, the reaction, distillation of distillate components, and post-treatment were carried out again in the same manner as in Reference Example 3. A pellet of polyhydroxy polyether was obtained.

The intrinsic viscosity [η] of this polyhydroxy polyether is 0
．． It was 33dj/g, and the glass transition temperature was 60°C. Furthermore, about 15% of the terminal groups of the polyhydroxypolyether were p-tolyl groups, the remaining about 80% were p-hydroxyphenyl groups, and the glycidyl groups had completely disappeared.

Moreover, the hue of the pellet of this polyester droxypolyether had an L value (lightness) of 55.4 and a b value (yellow coloring degree) of 16.0.

Next, this polyhydroxypolyether was press-molded in the same manner as in Reference Example 1 to produce a press sheet having a thickness of about 200 μm. The haze degree fHA2E) of this press sheet was 2.0%.

Reference Example 8 The same procedure as in Reference Example 3 was repeated except that 165 parts of methyl isobutyl getone was used instead of cyclohexane and the reaction system was operated under pressure at about 140"C for about 30 minutes.
The reaction was carried out at 50°C for about 90 minutes and then at about 170°C for about 120 minutes to obtain a reaction solution of a hydroxyether compound.

Add 4,4゛-hydroxyacetophenone 41 to this reaction solution.
After adding a mixture of 2 parts and 0.2 parts of a 20% tetraethylammonium hydroxide aqueous solution, the system was reacted in the same manner as in Reference Example 3, except that the operation was again performed under pressure. First, the distillate component was changed to be able to be distilled off under pressure, and then the temperature was increased from about 170°C to about 250°C for about 60°C.
The temperature was increased over 0 minutes, and the pressure of the system was gradually lowered, and the pressure was further reduced to distill off the distillate components.

Next, the distillate components were completely distilled off by operating at about 250° C. under a final reduced pressure of about 2 tm HQ, and then Reference Example 3 was prepared.
The same post-treatment as above was carried out to obtain polyhydroxypolyether pellets.

The intrinsic viscosity [η] of this polyhydroxy polyether is 0
．． It was 57 dJ/r, and the glass transition temperature was 61°C. Furthermore, about 85% of the terminal groups of this polyester hydroxypolyether were p-acetylphenyl groups, the remaining about 15% were p-hydroxyphenyl groups, and the glycidyl groups had completely disappeared.

Further, the hue of the polyhydroxypolyether pellets had an L value (lightness) of 61.3 and a bi (yellow coloring degree) of 11.4.

Next, this polyhydroxypolyether was press-molded in the same manner as in Reference Example 1 to produce a press sheet having a thickness of about 200 μm.

The haze (HAZE) of this press sheet was 1.8%. Furthermore, as a result of measuring the mechanical strength of this press sheet, the tensile strength at break was 470 kg/d, the tensile elongation at break was 70%, and the tensile modulus was 27000 kg/-.
Furthermore, as a result of examining the gas barrier properties, the carbon dioxide gas permeability coefficient was 0.81 m1·m/rd·day-atn.

1. 2202 parts of hydroquinone and 2406 parts of epichlorohydrin were placed in a reaction tank equipped with a distillation device equipped with a stirrer, a separator that returns only the upper layer to the reaction tank when the distillate fraction is separated, and a continuous supply device. part and cyclohexanone 36
120 parts of a 50% aqueous sodium hydroxide solution was added while stirring and maintaining the temperature of the system at about 70°C, and then the temperature of the system was raised to about 100°C while stirring for about 60 minutes.
Do not raise the temperature to ℃.

2168 parts of a 50% aqueous sodium hydroxide solution was fed to this system over about 90 minutes. At this time, water was distilled off along with cyclohexanone, so after liquid separation, only cyclohexanone was returned to the reaction tank. 50% of such operations
After the sodium hydroxide aqueous solution was supplied, the test was continued for about 60 minutes.

Next, 5000 parts of water was supplied to this system, and after stirring, the system was allowed to stand to separate into two layers, the aqueous layer was removed, and the reaction solution was washed. Such water washing operation was repeated two more times.

Next, 406 parts of 10% sodium dihydrogen phosphate aqueous solution was added to this reaction solution, and after stirring at about 60'C for about 15 minutes, 5000 parts of water was further added to this system, stirred, and left to separate. Such a washing operation was performed one more time without liquid washing.

After washing, distillation was performed under reduced pressure at about 90°C to azeotropically distill off water and the solvent cyclohexanone. This distillation operation was continued until the water in the system was distilled off and the distillate was no longer separated into two phases.

A portion of the cyclohexanone solution of the reaction solution thus obtained was collected, and the solvent cyclohexanone was distilled off under high vacuum at approximately 110"C. As a result, the concentration of the reactant in this reaction solution was 66.5%. In addition, as a result of analyzing the reactant from which this cyclohexanone was removed, it was found that
It has an epoxy equivalent of 310g/eQ (contains epoxy!
It was found to be an oligomer of hydroquinone diglycidyl ether (3.23 eq/ksr).

Next, 932 parts of the oligomer solution of hydroquinone diglycidyl ether obtained in this manner, 97 parts of hydroquinone, and 0.9 parts of tri-n-butylamine were charged into the reaction tank for producing polyhydroxy polyether shown in Reference Example 1. , about 30 minutes at about 150°C, then about 17
A reaction solution of a hydroxyether compound was obtained in the same manner as in Reference Example 1 except that the reaction was carried out at 0° C. for about 120 minutes.

The reaction solution thus obtained was sampled in the same manner as in Reference Example 1, and the distillate fraction such as the solvent cyclohexane was
The reaction product was investigated by distillation under reduced pressure at 40°C, and the intrinsic viscosity [η] was 0.56 dj/g, and about 90% of the terminals were hydroquinone polyhydroxy polyether with glycidyl groups. I found out something.

Next, a mixture of 52 parts of phenol and 0.3 parts of tri-n-butylamine was added to this system, and further Reference Example 1
Similarly, heating at about 170°C for about 120 minutes, raising the temperature from about 170°C to about 250°C over about 60 minutes and reducing the pressure, heating at about 250'C for about 60 minutes, and finally about After the reaction and the distillate components were distilled off by reducing the pressure to 2 + m HQ, the mixture was further post-treated in the same manner as in Reference Example 1 to obtain pellets of polyhydroxy polyether.

As a result of analyzing the obtained pellet, the intrinsic viscosity [η] was found to be 0.
．． 54, and the glass transition temperature was 61°C. In addition, about 90% of the terminal group of polyhydroxypolyether
% were p-phenyl groups, and glycidyl groups had completely disappeared. Furthermore, the hue of the polyhydroxy polyether pellets was measured and the result was [1 (lightness) was 64.6]
The b value (yellow coloring degree) was 13.2.

Furthermore, the obtained polyester droxypolyether was press-molded in the same manner as in Reference Example 1 to produce a press sheet having a thickness of about 200 μm.

The haze (HARE) of this press sheet was 1.9%. In addition, as a result of measuring the mechanical properties of this sheet,
Tensile strength at break is 4451qr/cd, tensile elongation at break is 7
4%, and the tensile modulus was 290001qr/cJ.

Furthermore, as a result of measuring the gas barrier properties of this press sheet, the carbon dioxide barrier properties were 0.77+nl・rm/d.
-day -atrt.

In the method for producing hydroquinone diglycidyl ether oligomer shown in Reference Example 9, the same procedure as Reference Example 9 was carried out, except that the amount of epichlorohydrin used was 2128 parts.
A solution of hydroquinone diglycidyl ether oligomer was obtained.

Hydroquinone diglycidyl ether oligomer was isolated and investigated by sampling from this solution and distilling off cyclohexanone. As a result, its concentration in the reaction solution was 70.4%, and its epoxy equivalent was 1120.
g/13Q (epoxy content 0, 89eQ/kir)
It turned out to be.

Next, 318 parts of the solution of the hydroquinone diglycidyl ether oligomer thus obtained, 9.2 parts of hydroquinone, and 0.9 parts of a 40% tetrabutylammonium hydroxide aqueous solution were mixed in the same manner as in Reference Example 9 for producing polyhydroxy polyether. was charged into a reaction tank, and then heated at about 150°C for about 30 minutes in the same manner as in Reference Example 9, and then heated at about 170°C for about 30 minutes.
The mixture was heated at 0° C. for about 120 minutes to obtain a reaction solution of a hydroxyether compound.

After adding a mixture of 8 parts of phenol and 0.3 parts of 40% tetrabutylammonium hydroxide aqueous i to this reaction solution, the reaction and distillate components were distilled off in the same manner as in Reference Example 1, followed by post-treatment. A pellet of polyhydroxypolyether was obtained.

As a result of analyzing the obtained pellet, the intrinsic viscosity EηJ was 0.
．． 67 dJ/g, and its glass transition temperature is 63
It was °C. Moreover, about 90% or more of the terminal groups of this polyester-droxypolyether were phenyl groups, and the glycidyl groups had completely disappeared.

Furthermore, as a result of measuring the hue of this polyhydroxy polyether, the L value (lightness) was 66.2, and the b value (yellow coloring degree) was 11.9.

Polyethylene terephthalate (manufactured by Mitsui PET Resin ■, Mitsui PET J125) 1 dried at 150°C for 10 hours
00 parts by weight was mixed with 10 parts by weight of the polyhydroxy polyether of Reference Example 1 which had been vacuum dried at 50°C for 12 hours, and this mixture was molded using an extruder at a temperature of 250°C.
Pellets of a composition of polyethylene terephthalate and polyhydroxy polyether were prepared by melt extrusion at ~290°C, cooling, and cutting. Further, press molding was performed using this pellet to produce a press sheet having a thickness of about 100 μm. The obtained press sheet was colorless. In addition, the mechanical properties of a press sheet of this composition were measured and the results showed that the tensile strength at break was 440 kf/-1 and the elongation was 78.
%Met. Furthermore, as a result of measuring the gas barrier properties of this press sheet, the carbon dioxide gas permeability coefficient was 19 ml・n
m/rd-day-attx and the oxygen gas permeability coefficient is 3,5+nl ・nm/rd-day Ha
It was tll.

Next, the press sheet of this composition was simultaneously stretched three times in the longitudinal and transverse directions using a biaxial stretching device to produce a biaxially stretched film.

The obtained biaxially stretched film has a thickness of about 11 μm,
It was stretched uniformly with little thickness unevenness. As a result of measuring the mechanical properties of this biaxially stretched film, the tensile strength at break was 1480 kg/cd, the elongation was 52%, and the tensile modulus was 38000 kt/-. In addition, the carbon dioxide gas permeability coefficient of this stretched film is 8.2Iul・1lII/rr
r-daV-atll.

Except for using a composition produced by using the polyethylene terephthalate or polyhydroxypolyether shown in Table 1 in the proportions shown in Table 1 instead of the polyethylene terephthalate or polyhydroxypolyether in Example 1. The thickness was approximately 10 mm in the same manner as in Example 1.
A 0 μm press sheet was produced. The mechanical properties and carbon dioxide gas permeability coefficient of the pressed sheet of the obtained composition are shown in Table 1.
It was as described.

Next, using press sheets of these compositions, simultaneous biaxial stretching was performed in the longitudinal and transverse directions to 3 times each in the same manner as in Example 1 to produce a stretched film. The films each had the average thickness shown in Table 1, and all were uniformly stretched. Furthermore, the mechanical properties and carbon dioxide gas permeability coefficients of these biaxially stretched films were as shown in Table 1.

Press molding was performed using the polyethylene terephthalate of Example 1 to produce a press sheet having a thickness of approximately 100 μm. The mechanical properties of this press sheet were as follows: tensile strength at break was 480 kt/- and elongation was 82%. In addition, the gas barrier property has a carbon dioxide permeability coefficient of 24 m1/rt.
It was r-day-aug.

Further, this press sheet was simultaneously biaxially stretched three times in the vertical axis direction and the horizontal axis direction in the same manner as in Example 1 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 1550k.
g/cd, elongation 55%, and tensile modulus 46000k
g/ali. In addition, the gas barrier property of this biaxially stretched film has a carbon dioxide permeability coefficient of 15 ml/rm/
It was rrr-day Hatll.

The mixture of polyethylene terephthalate and polystyrene polyether in Example 3 was extruded using an extruder equipped with a T-die at a barrel temperature of 160 to 280°C to obtain a product with a thickness of about 80 μm. An extruded sheet was produced. The mechanical properties of the extruded sheet of this composition are tensile strength at break of 477 k+r/d<machine direction) to 452 kg/ad.
(perpendicular to flow) and elongation 80% (flow direction) ~6
6% (in the direction perpendicular to the flow), and the carbon dioxide permeability coefficient of this extruded sheet was 17 ml mr/nf-
It was dayall. Furthermore, the extruded sheet of this composition was sequentially stretched first twice in the horizontal axis (perpendicular to the flow) direction and then three times in the longitudinal axis (flow) direction at a temperature of about 85 to 100°C using a biaxial stretching device. The average thickness is about 13
A biaxially stretched film having a diameter of μm was produced. The mechanical properties of the biaxially stretched film of this composition are tensile strength at break of 1650.
kt/=i (flow direction) ~1540kg/cd (
(direction perpendicular to the flow), elongation 45% (direction of flow) to 35% (
perpendicular to the flow) and tensile modulus 52,000 kg/c
d (flow direction) to 45000 kg/cd (perpendicular to the flow direction).

The carbon dioxide permeability coefficient of this biaxially stretched film is 8.0.
ml.++m/rrr-day-ati.

Example 10 The mixture of polyethylene terephthalate and polyhydroxypolyether in Example 3 was injection molded at a molding temperature of 270°C using an injection molding machine to produce a preform (cold parison) with a thickness of 3.2 cm. did. Then,
Approximately 2.5 times the length and approximately 4 times the width using a biaxial stretch blow molding machine
A stretched bottle with an internal volume of about 1J was formed by biaxial stretching. The carbon dioxide permeability of this stretched bottle is 2.0+nl/
It was a day-bottle-atl.

The polyethylene terephthalate used in Example 1 was injection molded to produce a preform consisting only of a polyethylene terephthalate layer and having the same thickness as the preform of Example 10 (approximately 3.2 mm). Next, this preform was stretch-blown in the same manner as in Example 10, and the internal volume was 1.
．． 1! A stretched bottle was produced. Furthermore, as a result of measuring the carbon dioxide gas permeability of this stretched bottle, it was found to be 4.0 ml/
It was a day Hbottle Hatl.

Claims (4)

[Claims] (1) A polyester resin composition containing a polyalkylene terephthalate whose main constituent unit is ethylene terephthalate constituent unit and a polyhydroxypolyether, wherein the polyhydroxypolyether is a substantially linear polyether represented by the following formula (a). and in o-chlorophenol 2
A polyester resin composition characterized by being a polyhydroxy polyether whose intrinsic viscosity [η] measured at 5°C is within the range of 0.1 to 2 dl/g; ▲There are mathematical formulas, chemical formulas, tables, etc.▼・...(a) [However, in the above formula (a), Ar^1 and Ar
^2 is each independently HO-Ar or HO-A
represents a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms other than r, Ar represents a p-phenylene group, and n represents a positive integer]. (2) A stretched molded product of a polyester resin composition containing polyalkylene terephthalate and polyhydroxypolyether whose main constituent units are ethylene terephthalate constituent units, wherein the polyhydroxypolyether is represented by the following formula (a) , is substantially linear and has an intrinsic viscosity [η] of 0.1 to 0.1 as measured at 25°C in o-chlorophenol.
Stretched molded product of a polyester resin composition characterized by being polyhydroxy polyether within the range of 2 dl/g; ▲There are numerical formulas, chemical formulas, tables, etc.▼...(a) [However, the above formula ( In a), Ar^1 and Ar
^2 is each independently HO-Ar or HO-A
represents a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms other than r, Ar represents a p-phenylene group, and n represents a positive integer]. (3) A preform for a stretched hollow molded article of a polyester resin composition containing polyalkylene terephthalate and polyhydroxypolyether whose main constituent units are ethylene terephthalate constituent units, wherein the polyhydroxypolyether has the following formula (a ), which is substantially linear and whose intrinsic viscosity [η] measured in o-chlorophenol at 25°C is within the range of 0.1 to 2 dl/g. Preform for stretched hollow molded body of polyester resin composition; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) [However, in the above formula (a), Ar^1 and Ar
^2 is each independently HO-Ar or HO-A
represents a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms other than r, Ar represents a p-phenylene group, and n represents a positive integer]. (4) A stretched hollow molded article of a polyester resin composition containing polyalkylene terephthalate and polyhydroxypolyether whose main constituent units are ethylene terephthalate constituent units, the polyhydroxypolyether comprising:
It has a substantially linear shape represented by the following formula (a), and has an intrinsic viscosity [η] of 0.
Stretched hollow molded product of a polyester resin composition characterized by being polyhydroxy polyether within the range of 1 to 2 dl/g; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) [However, In the above formula (a), Ar^1 and Ar
^2 is each independently HO-Ar or HO-A
represents a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms other than r, Ar represents a p-phenylene group, and n represents a positive integer].