JPH0195129A - Polyhydroxypolyether and its use - Google Patents

Abstract

PURPOSE:To obtain a polyhydroxypolyether having an excellent gas barrier properties, especially oxygen and carbon dioxide barrier properties and transparency, by giving a specified structural formula. CONSTITUTION:A substantially linear polyhydroxypolyether of formula I (wherein R is a divalent arom. hydrocarbon group whose main component is a p-phenylene group; n is a positive member) whose intrinsic viscosity [eta] measured in o-chlorophenol at 25 deg.C is in the range of 0.10dl/g-smaller than 0.3dl/g and content of non-ionic org. halogen is 0.2wt.% or less, is obtd. by reacting a diglycidyl ether of an arom. diol or formula II (wherein R<1> is the same as described above) and an arom. diol of formula III (wherein R<1> is the same as described above) in the presence of a catalyst selected from tert. amines, quar. ammonium compd., tert. phosphine and quar. phosphonium compd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyhydroxy polyether that has excellent transparency and airtightness, that is, airtightness, and has performance suitable as a material for containers, and uses thereof. be.

[Prior Art] JP-A-59-64624 discloses polyalkylene isoheptalates such as polyethylene isophthalate and copolymers thereof, and materials made therefrom as packaging materials having good sparring properties against oxygen and carbon dioxide. A molded article is disclosed.

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

Further, in JP-A No. 59-39547, the innermost layer is made of polyester whose main repeating unit is ethylene terephthalate, the outer layer is made of polyester whose main repeating unit is ethylene iso-7-talate, and the thin part of the container is at least A multilayer container with excellent gas permeation resistance that is oriented in one direction is disclosed.

As a material different from polyester, JP-A-48-362
Publication No. 96 discloses a polyamide with good transparency, which has as a diamine component an ugly-xylylene diamine or a mixture of m-xylylene diamine and p-xylylene diamine, and a specific aliphatic dicarboxylic acid as a dicarboxylic acid component. is disclosed.

The publication states that the polyamide exhibits good impact strength and has excellent processability.
There is no description of its ``subarya'' properties.

JP-A-56-64806 discloses that the outermost layer and the innermost layer are made of polyester having ethylene terephthalate as the main repeating unit, and the middle layer is made of m-xylylene diamine or...-xylylenecyamine and p-xylylene diamine. A multilayer container is disclosed which is made of polyamide having a mixture as a diamine component and in which a portion of the meat 11 is oriented in at least one direction. The publication states that the container has excellent oxygen barrier properties without impairing the excellent mechanical properties, transparency, chemical resistance, etc. of polyester.

In addition, the Journal of Applied Polymer Science (Journal of Applied Polymer Science)
cd Polymer Science), Volume 7, 2135-2144 (1963), the following formula (
A), (0-E-0-CH2-CH-CH2chiX...[1]
The gas barrier properties of homopolyhydroxypolyethers represented by H where E is are disclosed. Its value of oxygen permeability is 0.
5 cc-ail/ 100 in2/ 24 hr/
It is ata+. The lowest water vapor mobility is that of E, which has a value of 100°F and 190%R,H.

3 g-mil/i 00 in2/2 under conditions of
It is 4 hours.

In addition, these homopolyhydroxypolyethers have been disclosed in US Patent No. 2,602,075 (1948, November 2, 1948).
It is stated that it was manufactured by the method disclosed in 6).

According to US Pat. No. 2,602,075, it is described that polyhydroxy polyether can be produced by the reaction of aromatic nols and epichlorohydrin, and in particular, the method for producing the polymer from hydroquinone and epichlorohydrin is described in detail. There is. However, when the polymer in that example is prepared by the method described, the content of organochlorine in the polymer is 0.
The content was 3% by weight or more.

Also, the Journal of Applied Polymer Science
Poly IIler Science) + No. 78
．． 2145-2152 (1963), the following formula (B
) OHOH -R, -0CH2CHCH20-R2-OCH2CHC
H20-. . . . (B) where R2 is (however, R1 and R2 are not the same), a copolyhydroxypolyether represented by the following is disclosed. The maximum oxygen permeability is C1″1°, and both values are 5 g-ml/100 i
n2/24 hr/at+a. The lowest water vapor mobility was 4 [1-ml / 100 in2 / 24 h] under the conditions of 100"F', 90% R, H,
It is r. However, there is no description of the halogen content in these copolyhydroxypolyethers, and although the manufacturing method is described as being based on the above-mentioned US Pat. No. 2,602,075, there is no detailed description.

Furthermore, JP-A-56-100828 discloses that a linear hydroquinone phenoxy polymer produced from hydroquinone and epichlorohydrin by interfacial polymerization is characterized by strong impermeability to oxygen and carbon dioxide. ing. However, there is no description regarding the halogen content contained in the hydroquinone phenoxy polymer. The hydroquinone phenoxy polymer was manufactured according to the method described in the above patent publication and the result showed that the content of organic chlorine atoms was 0.3% by weight or more, which was higher than that of the polyhydroxy polyether of the present invention. Ta.

It has also been found that the hydroquinone phenoxy polymer also has the disadvantage of devitrification under high humidity. That is, when the hydroquinone phenoxy polymer was left in the form of a press sheet under a high humidity gaseous atmosphere or immersed in water, a phenomenon in which the transparency was impaired was observed.

Furthermore, epihalohydrin is reacted with dihydric 7-ethers in advance to produce diglycidyl ethers of dihydric phenols or their low polymers, and then further dihydric phenols are reacted to produce resins. A method for doing so is also disclosed in Japanese Patent Publication No. 28-4494. However, this publication does not disclose homopolyhydroxy polyethers of hydroquinone.

[Problem to be solved by the invention 1 The object of the present invention is to improve the sparring properties, especially the oxygen and carbon W
An object of the present invention is to provide a polyhydroxy polyether having excellent barrier properties against LFF and transparency.

Another object of the present invention is to provide a svalier property-imparting agent consisting of a polyhydroxy polyether as described above.

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

[Means and effects for solving the problems] According to the present invention, the above-mentioned objects and advantages of the present invention are as follows: represents a divalent aromatic hydrocarbon group, where n is a positive number.

A substantially linear polyhydroxy polyether represented by
．． 3 dR/g and is achieved by polyhydroxypolyethers characterized by a content of nonionic halogens in the range of 0.2% by weight or less.

Further, according to the present invention, the above objects and advantages of the present invention are as follows:
-Formula [N i0CH2CHCH20-R')n ----[11
In the formula H1, R' represents a divalent aromatic hydrocarbon group containing a 9-phenylene group as a main component, and n is a positive number. ] Substantially linear polyhydroxypolyethers having the intrinsic viscosity [η1 of 0.10 dj2/g to 0
．． This is achieved by using a svalier property-imparting agent made of polyhydroxypolyether characterized by a nonionic organic halogen content of less than 3 dN/g and a content of 0.2% by weight or less.

The polyhydroxy polyether of the present invention is produced by the method described below. That is, (a) - formula [
n]...[I[] [In the formula, R1 represents a divalent aromatic hydrocarbon group containing a p-phenylene group as a main component. ] Diglycidyl ether of an aromatic diol represented by (b) - Formula [11[] % formula % [] [wherein R1 represents the same group as above]] It is produced by a method characterized in that the reaction is carried out in the presence of at least one catalyst selected from triamines, quaternary ammonium compounds, tertiary phosphines, and quaternary phosphonium compounds.

In the above method, the diglycidyl ether of aromatic diol used as one of the raw materials is represented by the above formula [Irl. In the above formula [I[], R' represents a divalent aromatic hydrocarbon group containing an 11-phenylene group as a main component. That is, R1 is an I)-7 2-dylene group, or a combination of a p-7 2-dylene group mainly consisting of a p-phenylene group and a divalent aromatic hydrocarbon group other than the +1-7 22-ylene group. It can be a mixed group. Aromatic hydrocarbon groups other than p-phenylene may be present in a proportion of 50 mol % or less, preferably 40 mol % or less, based on the p-phenylene group. The divalent aromatic hydrocarbon group other than p-phenylene can be, for example, the following.

When R is an I)-phenylene group as the diglycidyl ether of aromatic diol in i1 [I[] above, it is a diglycidyl ether of hydroquinone represented by the following formula.

Further, examples of the diglycidyl ether of aromatic 7ol that can be used together with the diglycidyl ether of hydroquinone include the following compounds.

\1 \1 The compound of the above formula [II] is HO-R1-OH of the following formula, represented by the above-mentioned formula [1111]...[1] (Here, the definition of R' is the same as above. It can be produced by reacting an aromatic diol (which is the same) with shrimp halohydrin represented by the following formula [IV] (where X is a halogen atom such as fluorine, chlorine, or bromine) in the presence of a basic compound. can.

The diglycidyl ether of the aromatic diol of the formula [I] obtained from the aromatic diol and shrimp halohydrin contains a small amount of monoglycidyl ether of the aromatic diol and shrimp halohydrin, or a low polymer glycidyl ether. I don't mind.

In the above production method, the aromatic diol similarly used as one of the raw materials and the aromatic diol used to produce the diglycidyl ether of the aromatic diol of the above formula [I[] are the aromatic diol of the above formula [1[1 ]. In the above formula [[1[], R'l! It represents a divalent aromatic hydrocarbon group having a p-phenylene group as a main component, and the same groups as those described for the above formula [I[] can be exemplified.

Therefore, compounds of the above formula [1F include, for example, hydroquinone or hydroquinone and other aromatic dihydroxy compounds, such as resorcinol, methylhydroquinone, pyl)'-biphenol, and suphenol A,
and Suphenol F, Bis7E/-L ACP, Bis7E/
Examples include mixtures with L1 bis7er7, 4,4'-nohydroxydiphenyl ether, bisphenol S, and the like.

The above manufacturing method involves reacting the diglycidyl ether of an aromatic diol as described above with an aromatic diol using at least one of a tertiary amine, a quaternary ammonium compound, a tertiary phosphine, or a quaternary phosphonium compound as a catalyst. Implemented by

The usage ratio of aromatic diol diglycidyl ether [■] and aromatic diol [III] is 0.75 to 0.95 mol per 1 mol of aromatic diol when the amount of aromatic diol diglycidyl ether is small; Preferably 0.80~
The ratio ranges from 0.95 mol, more preferably from 0.83 to 0.95 mol, or 1.0 if there is more diglycidyl ether of aromatic diol per mol of aromatic diol.
It is used in a proportion of 5 to 1.25 moles, preferably 1.05 to 1.20 moles, and more preferably 1.05 to 1.18 moles.

Examples of tertiary amines used as catalysts include triethylamine, t')-n-propylamine, triisopropylamine, tri-butylamine, trisecan-glyptylamine, tri-hexylamine, dimethylbenclamine, diethylbenolamine, Examples include tribenolamine. Examples of quaternary ammonium compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetraisopropylammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbennolammonium hydroxide, and water. A quaternary ammonium hydroxide compound such as ethylbenzylammonium oxide) can be used. Examples of tertiary phosphine include triethylphosphine, )'
)-n-butylphosphine, triphenylphosphine,
Examples include trinonylphenylphosphine. Furthermore, examples of the quaternary phosphonium compound include quaternary phosphonium hydroxide compounds such as tetramethylphosphonium hydroxide.

The amount of these catalysts used is o per mole of aromatic fall;
ooi to 10 mol%, preferably 0.005 to 5 mol%
, more preferably in the range of 0.01 to 1 mol %.

In addition, in the above production method, when the molar amount of the glycidyl ether of the aromatic diol is larger than the molar amount of the aromatic diol, one 7 A small amount of a compound containing an enolic hydroxyl group can be added and reacted. These compounds containing one phenolic hydroxyl group include 7 ethyl, 0-cresol, 1-cresol, p-cresol, pt-butyl 7 ethyl,
+1-7 dinylphenol, p-cumylphenol, p
-Methoxy7er/-er, etc. can be exemplified. When using a compound containing one of these phenolic hydroxyl groups, it is usually used in an amount of 0.25 mol or less, preferably 0.20 mol or less, more preferably 0.18 mol or less per 1 mol of aromatic diol. It is preferable that

Furthermore, in the production method, an inert solvent may be used in order to reduce the viscosity of the system during the reaction and allow the reaction to proceed suitably. Examples of such solvents include saturated hydrocarbons such as n-decane and decahydronaphthalene, and aromatic solvents such as benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, ethylbenzene, cumene, n-butylbenzene, tetrahydronaphthalene, and naphthalene. group hydrocarbons, ketones such as methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, 7cetophenone, amides such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone, sulfoxides such as dimethyl sulfoxide, etc. can be given. When using these solvents, for example, 2 parts by weight of the polymer usually produced.
The amount used is not more than 1 part by weight, preferably not more than 1 part by weight, and more preferably not more than 0.5 part by weight. It is separated and removed from the polyhydroxy polyether product by a conventional method.

The reaction temperature is usually 70-300°C, preferably 80-270°C.
It is carried out at a temperature of °C. The reaction is usually carried out under normal pressure or increased pressure, but may also be carried out under reduced pressure in cases such as removing the solvent used for viscosity adjustment. The reaction is usually completed in 5 to 10 hours at 0° under stirring. After the reaction,
The polyhydroxy polyether product is separated and obtained from the reaction system by a method known per se.

Thus, according to the above manufacturing method, as described above, a substantially straight line represented by the following formula [11 % formula % [] (wherein the definition of R1 is the same as above, and n is a positive number) A polyhydroxy polyether of the form is obtained. In the above formula, the value of n is the intrinsic viscosity of the polyhydroxypolyether [η1 is 0.10dj2/g
It is a positive number determined to be between 0.3 dA/g and less than 0.3 dA/g. Intrinsic viscosity and melt viscosity are measured by the methods defined below. The term "substantially linear structure" means that it consists essentially of a linear or branched chain structure, and it means that it is not substantially a gel-like crosslinked structure (network structure).

This is confirmed by the fact that the polyhydroxy polyether of the invention is substantially completely dissolved in the solvent in which the intrinsic viscosity is measured.

As described above, the polyhydroxy polyether has a 0.
10clj! /g to less than 0.3 dN/bi. If the intrinsic viscosity is less than 0.10 dβ/g, it may be difficult to continuously take out the polyhydroxy polyether in the form of a strand from an extruder or the like, or it may be difficult to continuously take it out into chips using a cutter. It becomes difficult to perform the operations, and the operability decreases. The polyhydroxy polyether is preferably 0.1
3di/g to less than 0.3dl/g, more preferably 0.3di/g to less than 0.3dl/g.
15dβ/8~0.3dj! It exhibits an intrinsic viscosity of less than /g.

The polyhydroxy polyether of the present invention contains organic chlorine in a range of 0.2% or less, preferably 0.15%.
It is in the following range. The method for producing the polyhydroxy polyether of the present invention is a method that can reduce the content of organic chlorine, and the range of the content of organic chlorine in the above range is the one in which the purity of the digrinnorether of aromatic nol is good. This is usually easily achieved by using

Here, the nonionic organic halogen is a halogen element that is present in the polyhydroxypolyether by covalent bonding, and its amount is determined by the combustion flask method (S
It can be determined by subtracting the content of inorganic halogen (free ionic halogen) determined by silver nitrate titration method or the like from the total halogen content determined by chOniHer method or the like.

The polyhydroxypolyether of the present invention has a hydroquinone unit, phosphorus unit (-0CH2CHCH20H), or a phosphorus unit (-0CH2CHCH20H) at the end thereof, depending on the proportion of the raw material compounds used in its production. These terminal hydroxyl groups (-08) can be converted into carboxylic acid esters such as acetate esters (-0COCII) or ethers such as ethoxy groups (-0C2H5) by a conventional esterification method or etherification method. The polyhydroxy polyethers of the present invention include those having various terminals as described above.

The polyhydroxy polyether of the present invention is 30-150℃
It has a glass transition temperature of 40 to 12
It has a glass transition temperature of 0°C.

The polyhydroxypolyether of the present invention has a ratio of weight average molecular weight (MIll> to number average molecular weight (Mn) (Mlll)
/Ma1) is usually in the range of 1.5 to 10, for example.

The polyhydroxy polyether of the present invention can exhibit excellent performance as a gas barrier property imparting agent by blending with other thermoplastic resins. Examples of the thermoplastic resin include polyester, polyamide, polycarbonate, polyolefin, etc., but it is preferable to use polyester, particularly polyalkylene terephthalate having ethylene terephthalate as the main constituent unit, as the agent for imparting properties. In particular, a polyester composition composed of the polyhydroxy polyether and a polyalkylene terephthalate whose main constituent unit is ethylene terephthalate has excellent barrier properties against carbon dioxide gas and transparency, so it is suitable for use in containers for carbonated beverages such as beer and cola. It is suitable as a material for
It also has excellent oxygen barrier properties and transparency, making it suitable as a material for food packaging.

The polyalkylene terephthalate (A) constituting the above-mentioned polynisel composition according to the present invention is a polyester having ethylene terephthalate as a main constituent unit. The content of ethylene terephthalate structural units in the polyalkylene terephthalate is usually 50 mol% or more, preferably 70 mol% or more. The dicarboxylic acid component unit constituting the polyalkylene terephthalate is as follows:
In addition to the terephthalic acid component unit, it may contain a small amount of other aromatic dicarboxylic acid component units. Specific examples of the aromatic dicarboxylic acid component units other than the terephthalic acid component units include isophthalic acid, hepthalic acid, and naphthalene dicarboxylic acid. As the diol component units constituting the polyalkylene terephthalate, in addition to ethylene glycol component units, a small amount of Ike's 7-ol component units may be contained.

Specifically, other diol component units other than ethylene glycol component units include 1,3-propanediol, 1,
4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexane dimeta/-ol, 1,
4-bis(β-hydroxyethoxy)benzene, 1,3
-bis(β-hydroxyethoxy)benzene, 2,2-
Examples include diol component units having 3 to 15 carbon atoms such as bis(4-β-hydroxyethoxyphenyl)propane and bis(4-β-hydroxyethoxyphenyl)sulfone.

In addition, the polyalkylene terephthalate may contain a small amount of a polyfunctional compound, if necessary, in addition to the aromatic dicarboxylic acid component unit and the diol component unit. Specifically, the polyfunctional compound component units include trimellitic acid, trimesic acid, 3.3'
, aromatic polybasic acids such as 5.5'-tetracarboxydiphenyl, aliphatic polybasic acids such as butanetetracarboxylic acid, aromatic polybasic acids such as 70loglucin, 1,2,4.5-tetrahydroxybenzene, etc. Polyol, glycerin, trimethylolethane, trimethylolpropane,
Examples include aliphatic polyols such as pentaerythritol, and oxypolycarboxylic acids such as tartaric acid and malic acid.

The composition of the constituent components of the polyalkylene terephthalate is:
The content of terephthalic acid component units is usually 50 to 100.
The content of aromatic dicarboxylic acid component units other than terephthalic acid component units is usually in the range of 0 to 50 mol%, preferably 0 to 30 mol%. , the content of ethylene glycol component units is usually in the range of 50 to 100 mol%, preferably 70 to 100 mol%, and the content of diol component units other than ethylene glycol component units is usually 0 to 50 mol%, preferably is in the range of 0 to 30 mol %, and the content of polyfunctional compound component units is usually in the range of 0 to 2 mol %, preferably in the range of O to 0 mol %. In addition, the intrinsic viscosity of the polyalkylene tele-7 grade [ηJ (value measured at 25°C in a mixed solvent of 7E/-tetrachloroethane (weight ratio 1/1)) is usually 0.5 to 1.5 dl. /g, preferably in the range of 0.6 to 1°2 dl/g, the melting point is usually in the range of 210 to 265°C, preferably 220 to 260°C, and the plus transition temperature is usually 50 to 120°C, preferably The temperature is in the range of 60 to 100°C.

In the polyester composition of the present invention, the blending ratio of the polyhydroxypolyether (B) is 1oofflfiLflt of the polyfulkylene terephthalate (A)! The amount generally ranges from 1 to 100 parts by weight, preferably from 2 to 50 parts by weight, and particularly preferably from 3 to 30 parts by weight.

The polyester composition 1 of the present invention is added to the polyalkylene terephthalate (A) and the polyhydroxypolyether (B) as necessary with a conventionally known nucleating agent, inorganic filler, lubricant, slip agent, anti-slip agent, etc. blocking agent,
There is no problem even if JIi amounts of various additives such as stabilizers, antistatic agents, antifogging agents, and pigments are blended.

The above-mentioned polyester composition according to the present invention can also be used in an unstretched state as a raw material for molded articles of various shapes such as films, sheets, fibers, containers, and others by ordinary molding methods. Furthermore, when the polyester composition is formed into a film, sheet, or container in a stretched state, a molded article with even better properties can be obtained.First, a stretched molded article of the polyester composition will be described.

The stretched molded products of the polyester composition include -axis stretched molded products and two-axis stretched molded products, and the form thereof may be any one of a film, a sheet, and a fiber. Here, when the stretched polyester product is uniaxially stretched, the stretching ratio is usually 1.1 to 10 times, preferably 1.2 to 8 times, particularly preferably 1.
In the range of 5 to 7 times. Further, when the stretched product is biaxially stretched, the stretching ratio in the longitudinal axis direction is usually 1.1 to 8 times, preferably 1.2 to 7 times,
It is particularly preferably in the range of 1.5 to 6 times, and in the horizontal axis direction is usually in the range of 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5 to 6 times. The stretched product can also be heat set depending on its intended use.

Any conventionally known method can be employed as a method for producing a stretched molded article of the above-mentioned polyester composition. Generally, an evaporated product such as a film or sheet formed from the polyester composition or a composition further containing the additives as necessary, is used as it is.
Alternatively, the original molded product is first cooled and solidified to a temperature below the glass transition point, then reheated, and then heated to a temperature range between the glass transition point and the melting point, preferably between the glass transition point and 80°C higher than the glass transition point. Stretching treatment is performed.

In order to heat set the stretched product, an appropriate short-time heat treatment is performed at the stretching temperature or a higher temperature.

When the evaporated molded product is a film or a sheet as a method for producing a stretched molded product of the above-mentioned polyester composition,
A method of stretching an unstretched film or sheet in the uniaxial direction (-axial stretching), a method of stretching in the longitudinal direction and then further stretching in the transverse direction (biaxial stretching), a method of stretching in the longitudinal and transverse directions A method of stretching at the same time (biaxial stretching), a method of sequential stretching in any one direction after two-wheel 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 the space between the film or sheet-like material and a mold. Moreover, it is also possible to produce a stretched molded article of these polyester compositions in the form of a laminate with other resins. Such a manufacturing method includes a method in which a vapor-molded product such as a film or sheet of the polyester composition is formed with a vapor-molded product such as a film or sheet of another resin in a single layer or multiple layers, and then stretched. Examples include a method of adhering a film or sheet of another resin to a stretched molded product of the composition.

The stretched molded product of the polyester composition has mechanical strength,
Since it has excellent properties such as transparency and sparability, it can be used for various purposes such as films, sheets, tubular bodies, containers, and bottles.

The polyester stretched hollow molded preform is formed from the polyester composition layer, and is produced by a conventionally known method.

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

Moreover, the polyester stretched hollow molded body is a stretched hollow molded body formed from the polyester composition, and is produced by stretch blow molding the preform for the stretched hollow molded body. The stretched hollow molded product may be a uniaxially stretched molded product or a biaxially stretched product,
In general, biaxially oriented materials are preferred because they have excellent mechanical strength and sparring properties. As for the stretching ratio of the stretched hollow molded article, the stretching ratio described for the stretched molded article of the polyester composition is applied as is.

The polyester stretch hollow molded body is produced by stretch blow molding the preform for the polyester hollow molded body. The method is to stretch the preform at the above temperature in the longitudinal axis direction and then blow mold it to stretch it in the tsumugi direction (biaxial stretch blow molding).
For example,

Polyester stretched hollow molded articles have excellent mechanical strength, transparency, and smear properties, and can therefore be used for a variety of purposes. In particular, biaxially stretched multi-layer blow-formed containers have excellent properties, making them excellent containers for seasonings, oils, alcoholic beverages such as beer and sake, soft drinks such as cola, cider, and juice, cosmetics, and detergents. However, especially when used as a container for beer or carbonated drinks, it becomes possible to reduce the wall thickness of the container and extend the shelf life.

[Example 1] Next, the present invention will be specifically explained by referring to Examples. In addition, in Examples and Comparative Examples, parts mean parts by weight, and performance evaluation was performed according to the following method.

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

The intrinsic viscosity [η1] of polyhydroxy polyether was measured in 0-chlorophenol at 25°C.

The content of nonionic organic halogen in polyhydroxy polyether is determined by Saito, Yoyo, Analytical Chemistry, Vol. 31, E-37.
First, the total chlorine content was determined by the combustion flask method (Schaniger method), and then the content of inorganic halogen (71) - ionic halogen) was determined by the silver nitrate titration method, according to the method described in Shin (1982). Seeking,
It was decided based on the difference between the two.

That is, approximately 50 milligrams of a sample of polyhydroxypolyether was accurately weighed, completely decomposed in a flask by the combustion method, and the decomposition gas was introduced into 10 ml of water to make an absorbent liquid.
4 were made. Then, the absorption liquid was subjected to a 200Oi type ion chromatography column (column: As-4 type ion chromatography column manufactured by the same company, eluent: 2.8 mmol sodium bicarbonate and 2.25 mmol carbonate) + 7 um mixed. It was measured using an aqueous solution, a detector; an electrical conductivity detector).

In addition, the content of inorganic halogen (71) - ionic halogen) was determined by accurately weighing 10 g of a sample of polyhydroxypolyether, adding 100 mA of cyclohexanone and dissolving it under stirring under heating, and after cooling to room temperature, 2 ml of distilled water and 1 ml of acetic acid. was added to prepare a measurement solution.

Then, titration was performed with N1500 isopropyl alcoholic silver nitrate solution using an automatic titrator model E-536 manufactured by Metrohm (buret capacity: 10 ml, electrode: composite silver electrode). A blank test was conducted without using a sample of polyhydroxypolyether, and calculations were made based on the difference from the case using a sample.

The transparency of the polyester composition was determined using an NDH-20 haze meter manufactured by Nippon Denshoku Kogyo Co., Ltd.
Measured according to K-6714.

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

Regarding the properties of sheets or stretched films of polyhydroxypolyether compositions, the oxygen gas permeability coefficient is determined by Oxytran (OX1) manufactured by MOCON.
'RAM) device, and the carbon dioxide permeability coefficient was determined using PERMATRA manufactured by MOCON.
N) Measured at 25° C. using a C-IV wave device.

Example 1 Hydroquino 22202 parts, Hydroquinone diglycinol ether (epoxy containing ffi:a, 98 eq/k
g, terminal hydroxyl group content: 20eq/10'g
), 2800 parts of cyclohexanone, and 13 g of a 20% aqueous solution of tetraethyl 7 ammonium hydroxide were charged into a reaction tank equipped with a stirring device, a reflux device, a distillation tube, and a discharge valve at the bottom. Both the reflux device and the distillation tube are installed in the reaction tank via valves, and by opening and closing each valve, reflux or evaporated components can be distilled out of the system. In addition, the distillation pipe is connected to a vacuum device consisting of a vacuum pump and a pressure reduction regulator, and the structure is such that evaporated matter can be distilled off under reduced pressure.For zero polymerization, the valve to the distillation pipe is closed; Open the valve to the reflux device to enable reflux, first purge the system with nitrogen, then heat at about 130°C for about 2 hours, then heat to about 150°C.
The temperature was raised to 0.degree. C., and the reaction was allowed to proceed under stirring under a nitrogen atmosphere at normal pressure for about 3 hours. Then, after opening the valve to the distillation pipe and closing the valve to the reflux device, the reaction system was heated to 170°C.
The temperature was raised to about 1 hour to 170℃, and then about 1
Maintained under stirring for an hour. During this time, cyclohexanone was distilled off through the distillation tube, increasing the viscosity in the system. Then,
The temperature inside the reaction system was raised to about 240°C over about 1 hour, and the vacuum pump was activated to gradually lower the pressure inside the system from normal pressure to about 2 m1aH, and then about 240°C.
The temperature was maintained at 40° C. and about 2 taIIHg for about 1 hour. This opening,
A small amount of remaining cyclohexanone and unreacted hydroquinone was distilled off.

After the polymerization reaction as described above, the system was returned to normal pressure with nitrogen and the temperature was lowered to approximately 150°C. Then, the discharge valve at the bottom of the reaction tank was opened, and the formed polymer was taken out in the form of strands and passed through water. After cooling, it was cut into pellets using a cutter.

Furthermore, the obtained pellet was dried at about 40° C. under reduced pressure.

The polymer thus obtained has an intrinsic viscosity [η] of 0.
28 dl/g, the glass transition temperature is 57°C,
In addition, the content of nonionic organic chlorine is 0.022ml1%
It was hydroquinone polyhydroxy polyether.

Example 2 Using the reaction vessel shown in Example 1, a polymerization reaction between hydroquinone and hydroquinone diglycidyl ether was carried out in the same manner as in Example 1, except that the amount of hydroquinone diglycidyl ether was changed to 3697 g1S.

After the polymerization was completed, the system was returned to normal pressure with nitrogen and the temperature was lowered to 130° C., and then the discharge valve at the bottom of the reaction tank was opened and the produced polymer was taken out.

The discharged polymer was in the form of strands. However, after being cooled in water, it was easily broken, so although it was possible to make it into pellets with a cutter, it was collected in a coarse powder form using a crusher. Further, it was dried under reduced pressure in the same manner as in Example 1.

The polymer thus obtained has an intrinsic viscosity of 0.
16 dl/g, the glass transition temperature is 55°C,
The content of nonionic organic chlorine is 0.020% by weight.
It was hydroquinone polyhydroxy polyether.

Example 3 Using the reaction tank shown in Example 1, the same procedure as in Example 1 was carried out except that the amount of hydroquinone diglycidyl ether was changed to 3,697 parts, at about 130° C. for about 2 hours, and then at about 150° C.
The initial polymerization reaction was carried out for up to about 3 hours at . After completing such an initial polymerization reaction, 425 parts of p-cumylphenol was added, and the reaction was further carried out at about 150°C for about 1 hour.

After that, the valve was opened and closed again in the same manner as in Example 1, and then the temperature was raised to about 170°C over about 1 hour, held for about 1 hour, and further raised to about 240°C and heated at about 2+e.
After the pressure was reduced to mHg over about 1 hour, the pressure was maintained for about 1 hour for a post-polymerization reaction. Further, after the polymerization reaction, post-treatment was performed in the same manner as in Example 1 to obtain a pellet-shaped polymer.

The polymer thus obtained has an intrinsic viscosity [η] of 0.
26 dl/g, the glass transition temperature is 57°C,
The hydroquinone polyhydroxy polyether had a nonionic organic chlorine content of 0.021% by weight.

Example 4 Using the reaction tank shown in Example 1, polymerization and post-treatment were carried out in the same manner as in Example 1, except that a mixture of 1762 parts of hydroquinone and 745 parts of p111'-biphenol was used instead of hydroquinone. A pellet-like polymer was obtained.

The polymer thus obtained has an intrinsic viscosity [η] of 0,
26tj! /g, the glass transition temperature is 70°C, the content of nonionic organic chlorine is 0.020% by weight, and the molar ratio of hydroquinone and p,p'-vinylene is 89: 11 hydroquinone'-p+p'-biphenol copolyhydroxypolyether.

Examples 5-7 10&? at 150°C Polyethylene terephthalate (manufactured by Mitsui PET Resin Co., Ltd., Mitsui PET J
135) Mix the amounts listed in Table 1 of the polyhydroxypolyether of Example 1 with 100 parts of the polyhydroxy polyether of Example 1, and extrude the mixture at a molding temperature of 250 to 2
Melt extrusion was carried out at 90°C, and after cooling, the mixture was cut using a cutter to produce a pellet of a composition of polyethylene terephthalate and polyhydroxypolyether. ``Furthermore, press molding was performed using these pellets to produce a press sheet having a thickness of approximately 100 μm. Next, the press sheets of these compositions were simultaneously stretched 3 times in the vertical axis direction and the horizontal axis direction using a biaxial stretching device to produce a biaxially stretched film.

All of the obtained biaxially stretched films had a thickness of about 11 μm, and were uniformly stretched with little thickness unevenness. Further, the press sheet, biaxially stretched film, transparency, and carbon dioxide gas permeability coefficient of the obtained composition were as shown in Table 1, respectively.

Comparative Example 1 The polyethylene terephthalate used in Example 5 was press-molded to create a press sheet having a thickness of about 100 μm. The haze level (HAZE) of the press sheet was measured and found to be 1.5%, and the carbon dioxide permeability coefficient was 2.
The press sheet was then biaxially stretched in the same manner as in Example 5 to produce a biaxially stretched film having a thickness of about 11 μm. The haze (HAZE) of the biaxially stretched film is 0.3
%, and the carbon dioxide permeability coefficient is 1511A-Theory II
/l112・day-atIll.

Examples 8-11 10 each of the polyhydroxy polyethers of Examples 2-4
of polyethylene terephthalate 10 used in Example 5.
0g1S and kneaded each mixture using an extruder in the same manner as in Example 5 to produce pellets of the composition. Furthermore, a press sheet having a thickness of about 100 μm was produced in the same manner as in Example 5 using each pellet. The results of measuring the transparency and carbon dioxide permeability of these press sheets are shown in Table 2.

Furthermore, biaxially stretched films each having a thickness of about 11 μm were produced in the same manner as in Example 5 using these press sheets. The transparency and carbon dioxide permeability of these biaxially stretched films were as shown in Table 2.

[Effect of the invention] The polyhydroxy polyether of the present invention has excellent transparency and
Excellent compatibility.

Furthermore, the sparring properties imparting agent of the present invention made of the polyhydroxypolyether described above can be formed into a film or the like as a composition with other polymers such as polyethylene terephthalate, and exhibits excellent sparring properties.

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Claims (2)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・[I] [In the formula, R^1 is a divalent aromatic hydrocarbon group whose main component is p-phenylene group and n is a positive number. A substantially linear polyhydroxypolyether represented by
3 dl/g, and the content of nonionic organic halogen is in the range of 0.2% by weight or less. (2) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・[I] [In the formula, R^1 is a divalent aromatic hydrocarbon group whose main component is p-phenylene group and n is a positive number. A substantially linear polyhydroxypolyether represented by
3 dl/g and a nonionic organic halogen content of 0.2% by weight or less.