JPS61296028A - Polyether ester, its manufacturing method and its uses - Google Patents

Abstract

PURPOSE:To obtain the titled polymer, having good moldability, transparency and gas barrier properties and useful for containers, by reacting a specific polyester diol with an aromatic diol and epihalohydrin in the presence of a base and phase-transfer catalyst in a mixed solvent of two phases. CONSTITUTION:(A) A polyester diol expressed by formula I (R<2> is 2-20C bifunctional aromatic hydrocarbon; R<3> is 2-20C bifunctional hydrocarbon; R<4> is 2-20C bifunctional hydrocarbon; p is 0 or a positive number) is reacted with (B) an aromatic diol expressed by formula II (R' is bifunctional aromatic hydrocarbon consisting essentially of p-phenylene) and (C) an epihalohydrin in the presence of a base and a phase-transfer catalyst in a mixed solvent of two phases consisting of water and an organic solvent to afford a linear polyether ester expressed by formula III [m and n are positive numbers; the value of m/(m+n) is 0.02-0.997].

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a polyether ester having excellent melt moldability, excellent mechanical strength, transparency, and gas barrier properties, and having performance suitable as a material for containers, a method for producing the same, and uses thereof. It is something. [Prior Art] Glass has been widely used as a material for containers for seasonings, oils, beer, alcoholic beverages such as Japanese sake, soft drinks such as carbonated drinks, cosmetics, detergents, and the like. However, although glass containers have excellent gas barrier properties, they are expensive to manufacture, so a method has been adopted in which empty containers are usually collected after use and recycled for reuse. However, glass containers are heavy, which increases shipping costs, and they also have drawbacks such as being easily damaged and inconvenient to handle. In order to overcome the aforementioned disadvantages of glass containers, there is a growing shift from glass containers to various plastic containers. Various plastics are used as materials depending on the type of stored item and its intended use. Among these plastic materials, polyethylene terephthalate has excellent gas barrier properties and transparency, and is therefore used as a material for containers for seasonings, soft drinks, detergents, cosmetics, and the like. However, polyethylene terephthalate is still not sufficient for beer and carbonated beverage containers, which require the most stringent gas barrier properties, and it is necessary to use thicker polyethylene terephthalate for use in these containers. The gas barrier properties had to be improved by increasing the amount of carbon. Currently, the demand for polyester containers is increasing, and in order to expand these uses, there is a strong demand for polyesters that have excellent gas barrier properties and excellent melt moldability. JP-A-59-64624 discloses polyisophthalates such as poly(ethylene isophthalate) and copolymers thereof and molded articles formed therefrom as packaging materials having good gas barrier properties against oxygen and carbon dioxide. 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 a polyisophthalate or a copolymer thereof as described above and a layer made of a polyterephthalate such as poly(ethylene terephthalate) or a copolymer thereof, and a molded product made thereof, such as a bottle. Disclosed. JP-A No. 59-39547 discloses that the innermost layer is made of polyester whose main repeating unit is ethylene terephthalate, and the outer layer is made of polynysdel whose main repeating unit is ethylene isophthalate. A gas permeable Y-container is disclosed in which the portions are oriented in at least one direction.
Publication No. 96 discloses that m-xylylene diamine has a mixture of m-xylylene diamine and p-xylylene diamine as the diamine component, and 2, a mixture of a specific aromatic dicarboxylic acid and an aliphatic dicarboxylic acid. A polyamide with good transparency is disclosed as a dicarboxylic acid component. Although the publication describes that the polyamide exhibits good impact strength and excellent processability, there is no mention of its gas barrier properties. Japanese Patent Publication No. 1983. Publication No. 64866 discloses that the outermost layer and the innermost layer are made of polyester having ethylene terephthalate as the main repeating unit, and the middle layer is made of m-xylylene diamine or a mixture of m-xylylene diamine and p-xylylene diamine as a diamine component. A multilayer container is disclosed, which is made of a polyamide having a thickness of approximately 100 nm and has thinner portions oriented in at least one direction. The publication states that the container has excellent oxygen barrier properties without impairing the excellent mechanical properties, transparency, chemical resistance, etc. of polyester. Furthermore, JP-A-58-183243 discloses a biaxially stretched blow-molded bottle body in which two inner and outer surface layers are made of polyethylene terephthalate and an intermediate layer is made of a mixed material of polyethylene terephthalate and xylylene group-containing polyamide. Disclosed. Furthermore, JP-A-56-100828 discloses that linear hydroquinone phenoxy polymers prepared from hydroquinone and epihalohydrin are characterized by low permeability to oxygen and carbon dioxide. Additionally, the Journal of Applied Polymer Science
LymerScience), Volume 7, 213
5-2144 (1963) discloses the gas barrier properties of homopolyhydroxyether represented by the following formula (c): H3 cH3i-C3[17]. Most oxygen permeable 0.5cc-
mil/11" Iflin /24hr/atm. The one with the lowest water vapor mobility is 5g-ml/1 under the conditions where E is CH3"P, 90% R,H,
00in2/24hr. Also, Journal of Applied Po
lymerScience, Volume 7, 2145-21
52 (1965), the gas barrier properties of cobohydroxy polyethers represented by G (wherein R1 and R2 are not the same) are disclosed. The value of C[(3) is 5g J/10[111n/24hr/at].
It is m. The one with the lowest water vapor mobility is R1 1/2-ct (3 g-ml/100 under conditions of 90% R, H).
in/24 hr. [Problem to be solved by the invention] The purpose of ψj is to provide a new polyether ester (
It's about doing Jt. Another object of the present invention is to provide a polyetherester having excellent gas barrier properties, particularly excellent barrier properties against oxygen and carbon dioxide. Still other objects of the present invention are 1. It is an object of the present invention to provide a polyetherester having a polyether ester having a melt-molding property of 1/4.A still further object of the present invention is to provide a drawn polyetherester as described above. Still another object of the present invention is to provide a polyester laminate molded product comprising a polyether ester layer as described above and a layer of polyalkylene terephthalate whose main constituent is ethylene terephthalate, and a stretched molded product thereof. Still another object of the present invention is to provide a method for producing polyetherester as described above. Still other objects and advantages of the present invention will become clear from the following description. [Means and Advantages] According to the present invention, the above-mentioned objects and advantages of the present invention are as follows: [In the formula, R1 represents a divalent aromatic hydrocarbon group containing a p-phenylene group as a main component; 7.1
represents a divalent hydrocarbon group having 2 to 20 carbon atoms, R4 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, p is 0 or a positive number, and m and n
is a positive number, provided that the value of m/(m+n) is in the range of 0.02 to 0.98. ] is a substantially linear polyether ester represented by -ζ, whose intrinsic viscosity [η] is in the range of 0.3 to 2 dl/g,
This is achieved using a polyetherester characterized by a glass transition temperature in the range of 30 to 160°C. Further, according to the present invention, the polyether ester of the present invention has the following formula: (a)-General formula [B] [wherein R is a divalent aromatic hydrocarbon group having 2 to 20 carbon atoms] 17, R3 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, R4 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and p is 0 or a positive number. ] Polyester diol represented by (1)) general formula (Ill) HO-R-OH-(1) [wherein R represents a divalent aromatic hydrocarbon group containing p-phenylene group as the main component] ] and (c) shrimp halohydrin in the presence of a base and a phase transfer catalyst in a two-liquid phase mixed solvent consisting of water and an organic solvent. In the above method G, the HoIJ ester diol used as one of the raw materials is represented by the following formula (II). In the above formula [11], R2 has the number of carbon atoms. 2
represents a divalent aromatic hydrocarbon group which may contain from 20 to 20 halogen atoms, oxygen atoms or sulfur atoms. Such aromatic hydrocarbon groups (J can be, for example, H3, etc.) Among such aromatic hydrocarbons, p-phenylene group, m-phenylene group, -phenylene group, 2,6-naphthylene group, etc. Also, in the above formula [11], R5 has a carbon atom number (2 to 2
It is a divalent hydrocarbon group which may contain zero oxygen or sulfur atoms. Such a divalent hydrocarbon group may or may not have an aromatic nucleus inside, but in the above formula (It), G can be replaced with an oxygen atom. It is preferable that the carbon atom to which it is directly bonded is a carbon atom belonging to a group or an alicyclic hydrocarbon group. Examples of such hydrocarbon groups include -(-CE(2-)2, +CI(2+3,(-c H2
→4. +CH2→5, -C[(2CH28CH2CH2
-1 -CH2CI(20Q-8o2Q-OCFT2CH2-
etc. can be given. Among such hydrocarbon groups,
1,2-dimethylene group, 1,4-tetramethylene group, 2
．． A 2-dimethylene 1,6-propylene group, a cyclohexane-1,4-dimethylene group, an oxydiethylene group, a benzene-1,3-bisoxyethylene group, or a benzene-1,4-bisoxyethylene group is preferred. Further, R in the above formula [for] is a hydrocarbon group having 2 to 20 carbon atoms and which may contain a divalent oxygen atom or a sulfur atom. Examples of such hydrocarbons include 〇. Among such hydrocarbon groups, p-phenylene group, m-phenylene group, 2°6-naphenyl group, etc. are preferred. In addition, in the above formula (1), p represents 0 or a positive number,
O~100. Particularly preferred is a number between θ and 50. Examples of the polyester diol of the above formula [Kawa] include the following compounds. -2- (p indicates a positive number), (p indicates a positive number), (IQ9) (i i 0) (+12) (p indicates a positive number), (p indicates a positive number) (p indicates a positive number), (+31) (p indicates a positive number), (p indicates a positive number), (p indicates a positive number), (1 , 11) (p indicates a positive number), the polyester diol represented by the above formula (It) is
An aromatic oxycarboxylic acid represented by the following formula 1] (wherein R represents a divalent aromatic hydrocarbon group having 2 to 20 carbon atoms), or an aromatic oxycarboxylic acid represented by the following formula [V] (wherein , the definition of R is the same as above, and R represents a -valent lower aliphatic hydrocarbon group.] and the ester derivative of aromatic oxycarboxylic acid represented by the following formula - [Here, R represents a divalent hydrocarbon group having 2 to 20 carbon atoms] as a raw material, or an aromatic oxycarboxylic acid represented by the above formula 1] or an ester I derivative of aromatic oxycarboxylic acid represented by the above formula (V), a dihydric alcohol represented by the above formula [machi], and the following formula ) or the following formula [■) (Here, the definition of R4 is the same as above, and R represents a -valent lower aliphatic hydrocarbon group. ) can be produced using an ester derivative of dicarboxylic acid as a raw material. "- In the polyester diol represented by the formula [■], p is equal to 0 when the aromatic oxycarboxylic acid represented by the above formula order or the ester of the aromatic oxycarboxylic acid represented by the above formula (V) This is the case where it is produced using a derivative and a dihydric alcohol represented by the following formula 〇〇 as raw materials, and when p is a positive number, it is an aromatic oxycarboxylic acid represented by the above formula [] or the above formula [ An ester derivative of an aromatic oxycarboxylic acid represented by VD, a dihydric alcohol represented by the above formula [in], and a dicarboxylic acid represented by the above formula 1 [] or a dicarboxylic acid not represented by the above formula [1] This is the case when the ester derivative of When producing a polynisderdiol with p equal to 0 in the above formula [G], when an aromatic oxycarboxylic acid represented by the L notation rlV) and a dihydric alcohol represented by the above formula [VD] are used as raw Fl For this purpose, a method of carrying out a Nisder-forming reaction between the two according to a conventional method can be adopted. In addition, when the ester derivative of aromatic A-oxycarboxylic acid represented by the notation [■] and the dihydric alcohol represented by the above formula (S'D) are used as raw materials, the catalyst can be prepared according to a conventional method. A method of carrying out transesterification in the presence of
I can. As the catalyst, any transesterification catalyst commonly used in the production of polyester can be used, and there are no particular limitations. When producing a polyester diol in which p is a positive number in the above formula (l'), an aromatic oxycarboxylic acid represented by When using cicatricial levonic acid represented by the formula as a raw material, it is possible to adopt a method in which they are simultaneously esterified in bulk according to a conventional method, or a method in which dihydric alcohol-7 is pre-treated according to a conventional method is adopted. and a dicarboxylic acid to produce an ester 1 represented by the following formula (where R3 and R4 are both defined as above, and n represents a positive number).
It is also possible to employ a method in which a compound is produced, and then the esterified product is subjected to an esterification reaction with an aromatic oxycarboxylic acid according to a conventional method. - An ester derivative of an aromatic oxycarboxylic acid represented by the above formula [■], a dihydric alcohol represented by the above formula [D], and an ester derivative of a dicarboxylic acid represented by the formula 1 (Vil+) are used as raw materials. In this case, it is possible to adopt a method in which the transesterification reaction is carried out simultaneously in the presence of a catalyst in a batch according to a conventional method, or a method in which a dihydric alcohol and an ester derivative of a dicarboxylic acid are mixed in advance in the presence of a catalyst according to a conventional method can be adopted. A transesterification reaction is carried out in the presence of a catalyst to produce a transesterification product represented by the above formula (2), and a transesterification reaction between the transesterification product and an estehaf derivative of an aromatic oxycarboxylic acid is carried out in the presence of a catalyst according to a conventional method. As these catalysts, any transesterification catalyst used in the production of polyesters can be used, and there are no particular limitations. ,
An esterified product represented by the formula α] is prepared in advance by carrying out an esterification reaction between the dihydric alcohol represented by the above formula (vl) and the cica I levonic acid represented by the order of 1 - 0. , further carrying out a transesterification reaction between the esterified product and an ester derivative of an aromatic oxycarboxylic acid represented by formula 1 [VD],
Alternatively, a transesterification product represented by the above formula is prepared in advance by carrying out a transesterification reaction between a dihydric alcohol represented by the above formula [~lI'''l and an ester derivative of a dicarboxylic acid represented by the above formula [■]. death,
Furthermore, a method of carrying out an esterification reaction between the transesterified product and the aromatic oxycarboxylic acid represented by the above symbol can also of course be adopted. In the polyester diol represented by the above formula [■], in the component unit represented by -R-, even if a single type of dihydric alcohol represented by the above formula C%'D is used in the production, one reaction time As a side reaction, a component unit which is reacted with a small amount of -R3-0-R- derived from an etherified compound produced by the reaction of the dihydric alcohols with each other may be contained. In addition, in the polyester diol represented by the above formula (11), the terminal group is a phenolic hydroxyl group derived from an aromatic oxycarboxylic acid or its ester derivative, but a small portion thereof is a polyether diol represented by the above formula (1). In the above method, it may be a hydroxyl group derived from a dihydric alcohol as a raw material, a levoxyl group derived from a dicarboxylic acid, or an ester group derived from an ester derivative of a dicarboxylic acid, as long as it does not reduce the molecular weight of the dihydric alcohol. Similarly, the aromatic diol used as one of the raw materials is represented by the above formula [11].In the above formula CiD, R is a divalent aromatic hydrocarbon whose main component is p-phenylene group. group, i.e. R is p
-phenylene group, or a mixed group of a p-phenylene group mainly consisting of a p-phenylene group and a divalent aromatic hydrocarbon group other than the p-phenylene group. The divalent aromatic hydrocarbon group other than the p-phenylene group may contain a halogen atom, an oxygen atom, or a sulfur atom, and the proportion thereof is 50 mol% D with respect to the p-phenylene group.
I, preferably in a proportion of up to 40 mol %. Examples of the divalent aromatic hydrocarbon group other than the p-phenylene group include the following. Therefore, compounds of the above formula [l[l] include, for example, hydroquinone or hydroquinone and other aromatic dihydroxy compounds such as reso I resinol, methylhydroquinone, chlorohydroquinone, 2,6-hydroxynaphthalene, p, p'- Biphenol v, 4.4-oxydiphenol, bisphenol A, dichlorobisphenol A, tetrachlorobisphenol A, tetrabromobisphenol A. Bisphenol F, bisphenol ACP, bisphenol L, bispheno-7L/V, 5,6-cyhydroxy-2.4,5,7,9,9,10.10-octamethy! Leanthracene, 4.4-dipheno-M sulfone, 4.4-diphenol ketone, 2.6-hydroxyanthraquinone mata is 5.6-dihydroxy-9,
Examples include mixtures with 9-dimethylxanthine and the like. Further, as the epihalohydrin similarly used as one of the raw materials in the above method, for example, epichlorohydrin or shrimp bromohydrin is preferable. The above manufacturing method is made of polyester as described above! It is carried out by reacting a rediol aromatic diol and an abihalohydrin in the presence of a base and a phase transfer catalyst in a two-component mixed solvent consisting of water and an organic solvent. Polyester di-7 [11] and aromatic diol (+
Ebihalohydrin is preferably used in a proportion of 0.95 to 1.05 mol per 1 mol of the total number of moles of +D. Preferred examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, tetraalkylammonium hydroxide, alkali metal alcoholade, etc.11]. As the tetraalkylammonium hydroxide, for example, tetramethylammonium hydroxide, tetramethylammonium hydroxide, etc. are preferably used. As the alkali metal alcoholade, for example, sodium, potassium or lithium salts of lower alcohols such as methanol, ethanol, 1so-propanol and tert-butanol are preferably used.As the zero phase transfer catalyst, for example, Quaternary ammonium halides such as methyltricaprylammonium chloride, benzyltriethylammonium chloride, and tetrabutylammonium bromide; rtn quaternary ammonium sulfates of methyltricaprylammonium sulfate; Quaternary ammonium acetate and the like are preferably used. Examples of organic solvents include methyl isobutyl getone, cyclohegisanone, 2-butanone, acetophenone, dichloromethane, γ-buzarolactone, sulfolane, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N
- Dimethylformamide etc. are used. The water is used in a proportion of, for example, 1 to 10 parts by weight per Nt part of the polymer produced, and the organic solvent is used in a proportion of, for example, 1 to 10 parts by weight per Nt part of the polymer to be produced. The reaction is carried out, for example, in the presence of a catalyst in a proportion of from 101 to 0.2 mol per 1 mol of polyester diol and aromatic diol in total, at a temperature of usually about 50 to 150°C, preferably about 70 to 150°C. The reaction is usually carried out with 1 to 1
It ends in 0 hours. After the reaction, the polymer is separated and obtained from the reaction system by a method known per se. Thus, according to the above method, the following formula (1) [wherein R1 represents a divalent aromatic hydrocarbon group having a p-phenylene group as a main component, and R represents the number of carbon atoms] is 2 or 2
0 divalent aromatic hydrocarbon group, R3 has 2 carbon atoms
represents a divalent hydrocarbon group having from 2 to 20 carbon atoms, -R4 represents a divalent hydrocarbon group having from 2 to 20 carbon atoms, p is 0 or a positive number, and m and n are positive numbers; be. However, the value of m/Cm+n) is in the range of 0.02 to 0.98. A substantially bilinear polyether ester represented by the following formula is obtained. ] In the two notations, the value of m + n is the value when the intrinsic viscosity [η] of the polyetherester is 0. It is a positive number between '5 and 2d1/takumi. Intrinsic viscosity is measured by the method defined later. A substantially linear structure is i′i′f
It means that it is substantially composed of a chain structure having a chain or branched chain, and it means that it is not substantially a gel-like crosslinked structure or a network structure. This is confirmed by the fact that the polyether ester of the invention is substantially completely dissolved in the solvent in which the intrinsic viscosity is measured. As described above, the polyether ester of the present invention is 01
It has an intrinsic viscosity of ~2 d/g, and has an intrinsic viscosity of ~16
It has a glass transition temperature of 0°C. Intrinsic viscosity is 2a
If it exceeds g/g, the melt moldability of the polyether ester will decrease, and furthermore, its stretchability will also decrease. Also, the intrinsic viscosity is 0. When it is smaller than Sdl/E, the mechanical strength of the polyether ester and its stretched product decreases. The polyether ester of the present invention preferably has a G of 0.4 to 1.5 dl/g (r
) Has an intrinsic viscosity of 2. On the other hand, if the glass transition temperature is lower than 50"C, it becomes difficult to dry economically. The polyetherester of the present invention preferably has a glass transition temperature of 40 to 1
It has a glass transition temperature of 30°C. The polyether ester of the present invention is composed only of the polyester component units because if the value of formula (1) % formula % m/(m+n) is less than 0.02, the proportion of polyester component units increases too much. Characteristics such as gas barrier properties are less likely to be exhibited compared to polyester. Also, when the value of m/(m+n) is larger than 0.98,
If the proportion of polyether component units increases too much, the compatibility and adhesion of polyethylene terephthalate to polyalkylene terephthalate, which are developed due to the presence of polyester component units, will become poor. The preferred range of the value of m/(m+n) is 0.05 to 0.9
7, a more preferable range is 0.05 to 0.95, and an even more preferable range is 0.1 to 0.95. The polyether ester of the present invention has a terminal structure mainly composed of aromatic oxycarboxylic acid component units derived from the polyester diol of formula (if), depending on the ratio of the raw material compounds used when producing it. The glycerin unit derived from the aromatic diol (-o-
cH2? HcH2o old, H can be used. In addition, a hydroxyl group derived from the dihydric alcohol of the formula (IV), which is a small amount of raw material produced in the process of producing the polyester diol of the formula (D), a levoxyl group derived from the dicarboxylic acid of the formula Cy, It may also be an ester group derived from the ester derivative of the dicarboxylic acid of the above formula (Vlfl).Furthermore, these terminal hydroxyl groups (-01(), sil groups) can be converted by a known esterification method or etherification method. The polyhydroxy polyethers of the present invention include those having ridged terminals as described above. The polyether ester I of the present invention may contain a small amount of halogen element derived from epihalohydrin, which is one of the raw materials.The polyether ester of the present invention has a weight average molecular weight (MW
) to the number average molecular weight (Mn) (W/100 n), which is usually in the range of 1.5 to 10. The polyether ester of the present invention can also be used in an unstretched state as a raw material for molded objects of various shapes such as films, sheets, fibers, containers, and others by ordinary molding methods. Furthermore, even if the stretched polyether ester is molded into a film, sheet, or container, molded products with excellent gas barrier properties can be obtained. Next, the stretched polyetherester product of the present invention will be explained. The polyether ester stretched products of the present invention include -axially stretched products and biaxially stretched products, and the form thereof may be any of a film, a sheet, and a fiber. here,
When the stretched product of polyhydroxy polyether is uniaxially stretched, the stretching ratio is usually 1.1 to 1.
The range is 0 times, preferably 1.2 to 8 times, particularly preferably 1.5 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,
Particularly preferably, it is in the range of 1.5 to 6 times, and in the horizontal axis direction, it 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 drawn product of the polycother ester of the present invention may contain various known inorganic fillers, lubricants, slip agents, antipro-sigming agents, stabilizers, antistatic agents, pigments, etc., as necessary. There is no problem even if an appropriate amount of additives are blended. Any conventionally known method can be adopted as a method for producing the stretched polyether ester of the present invention. In general, an original molded product such as a film-like product or a sheet-like product formed from the polyester composition, or the polyether ester, or a composition containing the additives, if necessary. Stretched as it is or after cooling and solidifying to a temperature below -B glass transition point and then reheating, at a temperature above the glass transition point, preferably at the glass transition point or 80°C higher than the glass transition point. Process. The method for producing a stretched polyetherester molded product of the present invention and (7), for example, when the original molded product is a film-like product or a sheet-like product (:1, an unstretched film-like product or The horn method (-
axial stretching), 2k stretching in the longitudinal direction and 2k ((-axial stretching), (i) method of simultaneously stretching in the axial and horizontal directions (-axial stretching) ), biaxially stretched (without repeating sequential stretching in one direction) J method, method in which biaxially stretched and then further stretched in both directions, film-like material (sheet B-like material) An example is the vacuum forming method in which stretch molding is performed by reducing the pressure in the space between the mold and the mold.Also, these stretch molded polyether esters are It is also possible to produce it in a laminated form.Moreover, as a manufacturing method, an original molded product such as a polyether ester film or a sheet material is combined with another resin film or A method in which an original molded product such as a sheet-like material is stretched after forming an intermediate layer or a multi-layered material, or a film-like material of another resin or a sheet-like material of another resin is adhered to the polyetherester material. A laminate comprising a polyether ester layer of the present invention and a polyalkylene terephthalate layer having ethylene terephthalate 1 as a main constituent unit will be described below. A two-layer laminate consisting of two layers, the polyether ester layer and a polyalkylene terephthalate layer, and a three-layer laminate comprising the polyether ester layer as an intermediate layer and both outer layers as the polyalkylene terephthalate layer. , a third F in which the polyalkylene terephthalate layer is the intermediate layer and both side layers are the polyether ester layers.
fffJ layer, a multilayer laminate having a four-layer structure or more in which the polyether ester layer and the polyalkylene terephthalate layer are alternately laminated, in which both outer layers are composed of the polyalkylene terephthalate layer; A laminate having a four-layer structure or more in which polyether ester layers and the polyalkylene terephthalate layers are alternately laminated (a multilayer laminate whose layers are composed of the polyether ester layers, the polyether ester layers) A laminate having a 1 to 4 layer structure in which ester layers and the polyalkylene terephthalate layers are alternately laminated (the outermost layer is the polyether ester layer and the polyalkylene terephthalate layer and the polyalkylene terephthalate layer and the polyalkylene terephthalate layer). An example of this is a multilayer laminate, etc. The fi11rft body can be applied not only to sheet-like objects, plate-like objects, and tubular objects, but also to various hollow bodies, containers, structures of various shapes, etc. The laminates T and J can be manufactured by a conventionally known method. Thickness of the polyetherester layer and the polyurethane terephthalate layer constituting the laminate: 1 Use of the laminate It is determined appropriately depending on the situation and is not particularly limited. When the laminate is the single-layer carcass, the thickness of the polyether Nisdel layer is 4 to 350 μm when energized.
, preferably from 6 to 6. 200 II, and the polyalkyl

[The thickness of one layer of mentelephthalate is 8 to 600μ, preferably 1
It is in the range of 500μ. When the laminate is the former of the three-layer laminate, the thickness of the intermediate layer consisting of the polyetherester layer is usually 4 to 35 mm.
0μ, preferably in the range of 6 to 2001+, and both outer 1ul1 made of the polyalkylene terephthalate layer
The thickness of each layer usually ranges from 4 to 300 microns, preferably from 5 to 250 microns. In addition, when the laminate is the latter of the former three-layer laminate, the thickness of the intermediate layer made of the polyalkylene terephthalate 1-ff is i.
18 to 600μ, preferably 10 to 500μ
The thickness of the polyetherester layer on both sides is usually in the range of 4 to 100 μm, preferably 6 to 50 μm. The laminate has a four-layer structure or more.
Even in the case of a multilayer laminate, the thickness of the middle layer and the outermost layer made of the polyetherester layer and the thickness of the middle layer and the outermost layer made of the polyalkylene terephthalate layer are the same as above. You can choose. The polyalkylene terephthalate constituting the polyester composition of the present invention is a polyester containing ethylene terephthalate as a main constituent unit. The content of ethylene terephthalate structural units in the polyalkylene terephthalate is usually 50 mol% or more, preferably 70 mol% or more. The dicarboxylic acid component units constituting the polyalkylene terephthalate may contain a small amount of other aromatic dicarboxylic acid component units in addition to the terephthalic acid component units. Specific examples of aromatic dicarboxylic acid component units other than terephthalic acid component units include isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid. The diol component units constituting the polyalkylene terephthalate may contain small amounts of other diol component units in addition to ethylene glycol component units. Specifically, other diol component units other than ethylene glycol component units include L3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexane dimetatool, 1°4-his(β -hydroxyethoxy)benzene, 1゜3-his(β-hydroxyethoxy)benzene, 2゜2-his(4-β-hydroxyethoxyphenyl)propane, bis(4-β-hydroxyethoxyphenyl)sulfone, etc. The number of carbon atoms in is 3 to 1
The diol component unit of No. 5 can be exemplified. In addition to the aromatic dicarboxylic acid component units and the diol component units, the polyalkylene terephthalate may optionally contain a small amount of a polyfunctional compound. Specifically, the polyfunctional compound component units include trimellitic acid, trimesic acid, 3.3',
Aromatic polybasic acids such as 5,5ゝ-tetracarboxydiphenyl, aliphatic polybasic acids such as butanetetracarphonic acid, aromatic polyols such as phloroglucin, 1,2,4,5-tetrahydroxybenzene, etc. , glycerin,
Aliphatic polyols such as trimethylolethane, trimethylolpropane, and pentaerythritol, tartaric acid,
Examples include oxypolycarboxylic acids such as 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 0 to 50 mol%, preferably O to 30 mol%. , the content of ethylene glycol component units is usually 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 O to 30
The range of mol % and the content of polyfunctional compound component units are usually in the range of O to 2 mol %, preferably in the range of 0 to 1 mol %. In addition, the intrinsic viscosity [η] of the polyalkylene terephthalate (measured at 25τ in a mixed solvent of phenol and 1 lachloroethane (weight ratio 1/1)) is usually 0.5 to 1.5 dl/g, preferably 0. 6 to 1.2 dl/g, the melting point is usually 210 to 265°C, preferably 220 to 260°C, and the glass transition temperature is 50 to 120°C.
1 preferably in the range of 60 to 100°C. The laminate has excellent properties such as melt moldability, stretchability, mechanical strength, transparency, and gas barrier properties, and can be used for various purposes. A stretched laminate comprising a polyether ester layer of the present invention and a polyalkylene terephthalate layer having ethylene terephthalate i as a main constituent unit will be described. The stretched laminate of the present invention is formed by stretching the above. The stretched laminate includes -axially stretched products and biaxially stretched products, and its form may be any shape such as a film, sheet, or plate. As for the stretching ratio of the stretched laminate, the ratio proposed for the stretched product of the polyetherester can be applied as is, and it is also possible to heat set the stretched product. The stretched laminate of the present invention can be obtained by stretching an original molded product made of the laminate described above in the same manner as the polyetherester. Since the stretched laminate of the present invention has excellent properties such as mechanical strength, transparency, and gas barrier properties, it can be used for various purposes. The preform for a multilayer hollow molded body of the present invention is for a multilayer hollow molded body having a laminated structure composed of the polyether ester layer and 1 to 1 layers of polyalkylene terephthalate mainly composed of 11 to 10 ethylene terephthalates. This is a preform for a multilayer hollow molded body having the laminate structure described above. Examples of the preform having a laminate structure include the two-layer laminate preform exemplified in the laminate of the present invention described above, a similar three-layer Y integral preform, and a similar multilayer laminate preform of four or more layers. can be similarly illustrated. Among these preforms for multilayer hollow molded bodies, there is a preform having a laminated structure consisting of two layers, the polyether ester layer and the polyalkylene terephthalate layer, and the polyether ester layer is used as an intermediate layer and both the polyether ester layer and the polyalkylene terephthalate layer. When a stretched multilayer laminate hollow molded body is formed from a preform having a laminate structure in which the outer layer is composed of three layers of polyalkylene terephthalate 1, it has excellent mechanical strength, transparency, and gas barrier properties. This is preferable because a stretched multilayer hollow molded article having excellent properties such as elasticity can be obtained. Inorganic fillers and lubricants, which are blended into conventional polyesters as necessary, in both the polyether ester and the polyalkylene thirephthalate I that constitute Prefor J2 for multilayer hollow molded bodies of the present invention, Appropriate amounts of various slip agents, anti-blocking agents, stabilizers, antistatic agents, antifogging agents, pigments, etc. may be blended. The preform for a multilayer hollow molded body of the present invention is produced by a conventionally known method. For example, the preform for a multilayer hollow molded body of the present invention can be obtained by molding the tube 1 having the laminated structure. The stretched multilayer hollow molded body of the present invention is a stretched multilayer hollow molded body composed of the polyether ester layer and the polyalkylene terephthalate layer, and is produced by stretch blow molding the preform for the multilayer hollow molded body. Ru. The stretched multilayer hollow molded body may be a stretched two-layer hollow molded body composed of the polyether ester layer and the polyalkylene terephthalate layer, or may be a stretched two-layer hollow molded body composed of the polyether ester layer and the polyalkylene terephthalate layer. It may be a stretched three-layer hollow molded product composed of three layers laminated alternately, or it may be a stretched three-layer hollow molded product composed of three layers laminated alternately. - It may be a stretched multilayer hollow molded body composed of multiple layers. The stretched multilayer hollow molded product may be a uniaxially stretched product or a biaxially stretched product, but generally a biaxially stretched product has excellent mechanical strength and gas barrier properties. suitable. As for the stretching ratio of the stretched multilayer hollow molded body, the stretching ratio described for the stretched product of the polyetherester is applied as is. The stretched multilayer hollow molded body of the present invention is produced by stretch blow molding the preform for the multilayer hollow molded body. Examples of this method include a method (biaxial stretch blow molding) in which a preform at the above temperature is stretched in the vertical axis direction and then further blow molded to stretch it in the horizontal axis direction. The stretched multilayer hollow molded article of the present invention has excellent mechanical strength, heat resistance, gas barrier properties, and transparency, and can therefore be used for various purposes. In particular, the biaxially stretched multilayer blow-molded container of the present invention has excellent gas barrier properties, so it can be used for seasonings, oil, beer, alcoholic beverages such as Japanese sake, cola, etc.
It is excellent as a container for soft drinks such as cider and juice, cosmetics, detergents, etc., but especially when used as a container for beer or carbonated drinks, the wall thickness of the container can be made thinner, and the shelf life can be extended. It becomes possible. Next, when the stretched polyether ester of the present invention is a stretched film, these can be specifically used for gas barrier packaging materials, metallized films, etc. . [Example] Next, the present invention will be specifically explained by referring to an example. Note that in Examples and Comparative Examples, parts mean parts by weight, and performance evaluation was performed according to the following method. The composition of the polyether ester was determined by measuring nuclear magnetic resonance spectroscopy. The intrinsic viscosity [η] of the polyether ester was measured in o-chlorophenol at 25°C. The glass transition temperature of the polyether ester was determined by measuring at a heating rate of 10° C./min using a differential scanning calorimetry needle. Regarding the gas barrier properties of polyether ester or its laminate sheets, stretched films, or stretched bottles, the oxygen gas permeability coefficient is determined by MOCON.
The carbon dioxide gas permeability coefficient was measured at 25° C. using an OXTRAN device manufactured by MOCON Co., Ltd., and a PERMATl?AN C-IV packing device manufactured by MOCON Co., Ltd., respectively. Example 1 Bis(2-hydroxyethyl) terephthalate [Terephthalic acid and ethylene glycol (molar ratio, 1:10) were prepared at 240°C with stirring under pressure of 5 kg/- nitrogen gas in the presence of a small amount of triethylamine. After carrying out the nistylation reaction while distilling off the water produced, the reaction product was cooled, then poured into a large amount of water to precipitate it, washed with water and methanol, collected by filtration, and dried. Manufactured by. ] and] p-hydroxybenzoic acid molar ratio 1:2) were charged into a reaction tank, and the esterification reaction was carried out for 5 hours while stirring and distilling off the water produced at 240°C, and then the reactants were cooled and pulverized. terephthalic acid, ethylene glycol and p-
A polyester diol (p=1) containing hydroxybenzoic acid as a constituent was produced. Next, one portion of hydroquinone was added into a reaction tank charged with 700 parts of cyclohexane and 550 parts of distilled water at room temperature while stirring.
98.2 parts, 98.9 parts of the above polyester diol,
After adding 48 parts of trimethylbenzylammonium chloride, 185.1 parts of epichlorohydrin, and 179.2 parts of a 50% aqueous sodium hydroxide solution in this order, the temperature was raised to 90°C for 6 hours to carry out a polymerization reaction with stirring. The viscosity of the system increased over time. After the reaction was completed, the reaction system was cooled, 60 parts of acetic acid was added to neutralize the reaction system, and when it was allowed to stand still, an aqueous layer was separated as a lower layer and an oil layer containing the polyether ester produced by the reaction was separated as an upper layer. . After removing the aqueous layer and adjusting the viscosity of the oil layer using cyclohexanone, the operation of pouring water, stirring, standing still, and removing the separated aqueous layer was repeated twice, and then poured into a large amount of methanol. Water was poured to precipitate polyether ester. Further, the polyether ester was collected by filtration, washed with water and methanol, and then dried at 50° C. under reduced pressure. The amount of polyetherester thus obtained was 368 parts. Furthermore, the intrinsic viscosity of this polyether ester is 0.70.
dl/g, the glass transition temperature is 64°C, the ratio of hydroquinone component units to polyester diol component units is 90:10 (molar ratio), and m/(m+n)
(The directivity was 0.9. Furthermore, a press sheet with a thickness of about 100μ was prepared from this polyether ester, and its gas barrier properties were measured. As a result, the carbon dioxide sludge permeation coefficient was 1.1 sl · mm.
/rd ・day -atm, and the oxygen gas permeability coefficient is 0.25if'-im/%-day -a
It was tm. Example 2.3 A polyether ester was obtained in the same manner as in Example 1, except that the amounts of Hi-1 paroginone, the same polyester diol and cyclohexanone as in Example 1, and the reaction times were as shown in Table 1. . The yield, intrinsic viscosity, glass transition temperature, high l: ratio of quinone component to medium ethylene glycol component, and carbon dioxide gas permeability coefficient and oxygen gas permeability coefficient of the press sheet of these polyether esters are shown in Table 1. That's right. JP-A-6L-29GO28 (19) Table 1 (Continued) Comparative Example 1 Polyethylene terephthalate (Product name: Mitsui PET
A press sheet having a thickness of approximately 100 μm was produced in the same manner as in Example 1 using J 125). The carbon dioxide permeability coefficient of this press sea is 25 m1.
mm/rrr・day −atm, and the oxygen gas permeability coefficient is 4.5mf・in/n(・day
・It was an ATM. Comparative Example 2 A polymerization reaction was carried out in the same manner as in Example 1 except that 220.2 parts of hydroquinone and 185.1 parts of epichlorohydrin were used as raw materials, and further 600 parts of cyclohexanone and 510 parts of distilled water were used. Post-treatment was performed in the same manner as in Example 1 to obtain 320 parts of polyhydroxypolyether. The intrinsic viscosity of this polyhydroxy polyether is 0.85d17g, its composition is consistent with that of a structure formed by alternating dehydration condensation of hydroquinone and 2-hydroxy-L3-propanediol, and its glass transition temperature is 56. It was ℃. The carbon dioxide gas permeability coefficient of a press sheet made from this polyhydroxybolyethyl in the same manner as in Example 1 was 1.8 m1Hmm/n (
-day・aim available, and oxygen gas permeability coefficient is 0.3
It was 5mf-mm/-day-atm. Example 4 Under the same conditions as Example 1, a polymerization reaction of 198.2 parts of hydroquinone, 98.9 parts of the polyester diol (p-1) of Example 1, and 15.1 parts of Ebichlor 1-E was carried out at 90°C. After that, 300 parts of 200 g of cyclopentane was added in portions to the cyclo-coat, and the reaction was continued at 90° C. for 5 hours while suppressing the increase in viscosity. Example 1 after completion of reaction
Post-treatment was carried out in the same manner as above to obtain 384 parts of polyether ester. The intrinsic viscosity of the polyetherester is 1
．． 2111/g, the glass transition temperature is 67°C, the ratio of hydroquinone component units to polyester diol component units is 90:10 (mozuki 71:shi), and m/g.
(rntenn) was 0.9. Further, the carbon dioxide permeability coefficient of a press sheet made from this polyetherester in the same manner as in Example 1 was 1.0 mZ tntn/r
It was d-day-atm. Example 5 Methyl isobutyl ketone 70 instead of cyclohexane
The polymerization reaction and post-treatment were carried out in the same manner as in Example 1, except that 0 part was used, to obtain 368 parts of polyether ester. The intrinsic viscosity of the polyether ester is 0.59 dl/
g, the glass transition temperature is 64°C, and the ratio of hydroquinone component units to polyester diol component units is 90.
:10 (molar ratio), and m/(m+n) was 0.9. Further, the carbon dioxide gas permeability coefficient of a press sheet made of this polyether ester prepared in the same manner as in Example 1 was 1.2 ml·IIIIl/day-atm. Example 6 The polymerization reaction and post-treatment were carried out in the same manner as in Example 1, except that 700 parts of acetophenone was used instead of cyclohexane and 48 parts of tetra-n-butylammonium chloride was used instead of trimethylbenzylammonium chloride. A polyether ester was obtained. The polyether ester has an intrinsic viscosity of 0.52d17g, a glass transition temperature of 65°C, and a ratio of hydroquinone component units to polyester diol component units of 90:
10 (molar ratio), and m/(m1n) was 0.9. Furthermore, Example 1 from this polyether ester
The carbon dioxide gas permeability coefficient of the press sheet prepared in the same manner as 1.2 mZ-nun/ rrr ・day ・at
It was m. Example 7 Instead of bis(2-hydroxyethyl) terephthalate in Example 1, methanol was produced by mixing dimethyl terephthalate and ethylene glycol (molar ratio 1:3) with zinc acetate as a catalyst and stirring at 200°C for 7 hours. After carrying out an ester conversion reaction while removing, the reaction product was cooled, poured into a large amount of water to precipitate, washed with water and methanol, recovered by filtration, and dried to produce bis(2-hydroxyethyl). ) A polyester diol was produced in the same manner as in Example 1 using terephthalate (p=1). Furthermore, in the same manner as in Example 1 except that 98.9 parts of the polyester diol was used,
Polymerization reaction with hydroquinone and epichlorohydrin and post-treatment yielded 365 parts of polyether ester. The intrinsic viscosity of the polyetherester is 0.
11a/g, the glass transition temperature is 66°C, the ratio of hydroquinone component units to polyester diol component units is 90:10 (molar ratio), and m/(m+n
) was 0.9. Furthermore, the carbon dioxide gas permeability coefficient of a press sheet made from this polyetherester in the same manner as in Example 1 was 1.1 mZ-Il1m/cd-day
-It was an ATM. Example 8 Ethylene glycol was used instead of bis(2-hydroxyethyl) terephthalate in Example 1, and ethylene glycol and p-hydroxybenzoic acid (molar ratio, 1
: Example 1 except that the esterification reaction with 2) was carried out at 230°C under a pressure of 3 kg/ctA with nitrogen gas.
In the same manner as above, a polyester diol containing ethylene glycol and p-hydroxybenzoic acid as constituent components was produced. Furthermore, a polymerization reaction with hydroquinone and epichlorohydrin and post-treatment were carried out in the same manner as in Example 1 except that 60.5 parts of the polyester diol was used.
337 parts of polyetherester were obtained. The intrinsic viscosity of the polyether ester is 0.81 dZ/g, the glass transition temperature is 63°C, the ratio of hydroquinone component units to polyester diol component units is 90:10 (molar ratio), and m/(m+n) is It was 0.9. Further, the carbon dioxide gas permeability coefficient of a press sheet produced from this polyetherester in the same manner as in Example 1 was 0.90 mP·mm/rd·day -atm. Example 9 Terephthalic acid and ethylene glycol (molar ratio, 2:3)
The esterification reaction with biochemical triethylamine was carried out under a pressure of 5 kg/cl nitrogen gas (S, 5 kz
/cJ of nitrogen gas while stirring.24(1')
The reaction was carried out for 5 hours while removing the water produced, and the reaction system was further cooled to a temperature below about 200°C to remove VF. Add and raise the temperature again to 3 kg/cn
The esterification reaction was carried out while removing the water produced by pressurizing with 1 of nitrogen gas, and bis(2-
Hydroxyethyl) terephthalate oligomer and p-
Polyester diol containing H-roxybenzoic acid, and the polyester diol+37.3gl+
t:Y Same as in Example 1 except that 416 parts of polyniskel 4 was obtained by carrying out a polymerization reaction with hydroquinone and echylylhydrin and post-treatment. The polyester pole 1<rN viscosity t, j: 0.16d
l/g 1. The 'J'y transition temperature is ((8℃), and the ratio between the medium quinone component and the polyester diol component unit is 90:10 (molar ratio), m/(m↑
-n) IJ: 0.9. Further, the carbon dioxide gas permeability coefficient of Press Sea I, which was prepared from this polyether ester in the same manner as in Example 1, was 1. ]ml・mn/g
-day・arm. Example 10 In Example 9, phthalic acid, cochlear gellicol, and phi1. 'C + Kushibenzoic acid 5 each:
A polyester containing bis(β-hydroxyethyl) terephthalate and p-hydroxybenzoic acid having an average degree of polymerization of 5 was obtained by carrying out the esterification reaction in the same manner except that the ratio was 6:2 (mole 1). A diol (where p is 5 on average) was produced.Furthermore, a polymerization reaction with hydroquinone and epichlorohydrin and post-treatment were carried out in the same manner as in Example 1 except that 252.6 parts of the polyester diol was used. 517 parts of polyether ester was obtained.The polyether ester had an ultimate viscosity of 0.66 dl/g, a glass transition temperature of 73°C, and a ratio of hydroquinone component units to polyester diol component units of 90:10. (molar ratio), and m/(m+n) was 0.9. Also, the carbon dioxide permeability coefficient of a press sheet made from this polyetherester in the same manner as in Example 1 was 2.3 m/m
m/m-day・atm. Examples 11 to 17 In Example 1, 1,3-his(2-hydroxyethyl)benzene, his(4β-hydroxyethyl), quidiphenyl)sulpone, bis(2-hydroxyethyl)sulfone, and bis(2-hydroxyethyl)benzene were used instead of bis(2-hydroquinethyl)terephthalate. -hydroxyethyl) succinate, bis(2-hydroxytetramethylene) terephthalate, bis(2,β-hydroxyethoxyethyl) terephthalate, bis(2-hydroxyethyl) isophthalate or 2,6-bis(2-hydroxyethyl) natuthalate were used in the same ratio (molar ratio) as in Example 1, and each polyester diol was produced in the same manner. Furthermore, a polymerization reaction with hydroquinone and epichlorohydrin and post-treatment were carried out in the same manner as in Example except that each polyester diol was used as shown in Table 2 to obtain a polyether ester. The yield of the polyneedle ester, the viscosity of the rod C, the glass transition temperature, the ratio of the medium high 10 quinone component to the polyester diol component unit, and the carbon dioxide gas permeability coefficient of the press sheet prepared in the same manner as in Example 1 are as follows. Each was as described in Table 2. 18 Open) 1; JGI-296028 (24) Example 18 In Example 1, m instead of p-hydroxybenzoic acid
Polyester diols (p=1) were prepared except that -hydroxybenzoic acid was used in the same proportions. Furthermore, in the same manner as Reference Example 1 except that 98.9 parts of the polyester diol was used,
Polymerization reaction with hydroquinone and epichlorohydrin and post-treatment yielded 356 parts of polyether ester. The intrinsic viscosity of the polyetherester is 0.
12 dl/g, the glass transition temperature is 62°C, the ratio of hydroquinone component units to polyester diol component units is 90:10 (molar ratio), and m/(m+n) is 0.
．． It was 9. Furthermore, the carbon dioxide gas permeability coefficient of a press sheet produced from this polyetherester in the same manner as in Example 1 was 1.1if-mm;/rd ・day ・
It was an ATM. Examples 19-21 Polyether esters were obtained in the same manner as in Example 1, except that a mixture of hydroquinone and aromatic diol as shown in Table 3 was used instead of hydroquinone. Yield, intrinsic viscosity of their polyether esters,
The glass transition temperature, the ratio of the hydroquinone component unit to the polyester diol component unit, and the carbon dioxide permeability coefficient of the press sheet prepared in the same manner as in Example I were as shown in Table 3. Examples 22-26 Examples 1, 3, 9. Press sheets with a thickness of about 200 microns were made using the polyether esters in II and 20, respectively. Furthermore, these press sheets were simultaneously stretched three times in the vertical and horizontal directions at a temperature range of about 60 to 95°C using a biaxial stretching device, so that the average thickness of each polyether ester was approximately A 22μ biaxially stretched film was produced. Table 4 shows the carbon dioxide permeability coefficients of these biaxially stretched films. Table 4 Comparative Example 3 The press sheet of polyethylene terephthalate in Comparative Example 1 was biaxially stretched in the same manner as in Example 22 to produce a biaxially stretched film having a thickness of about 22 μm. The carbon dioxide gas permeability coefficient of the biaxially stretched film J2 is 15mf-am
/m・day-atm. Example 27 The polyether ester produced in the same manner as in Example 9 was
from about 150°C to about 180°C using an extruder equipped with a die.
Extrusion molding was performed at °C to produce an extruded sheet with a thickness of about 200 μm. Furthermore, this extruded sheet was simultaneously stretched approximately 3 times in the longitudinal axis (parallel to the extrusion flow) and transverse axis (perpendicular to the extrusion flow) directions at a temperature of approximately 65 to 85°C using a biaxial stretching device. A biaxially stretched film having a thickness of about 22 μm was prepared. The carbon dioxide gas permeability coefficient of this biaxially stretched film is 1.0iZ・mm/rd-day
It was -aim. Example 28 The press sheet in Example 24 and a press sheet of polyethylene terephthalate (product name, three-piece PRT, +015) with a thickness of about 200 μm were stacked and further press-molded to form a multi-layer press with a thickness of about 35011 mm. A sheet was produced. The adhesion between the polyether ester layer of this multi-layer press sheet and one layer of polyethylene terephthalate was good. Furthermore, this multi-layer press sheet was prepared in Example 24.
A two-wheel stretched film having an average thickness of 40 μm was produced by simultaneous biaxial stretching under the same conditions as above. The thickness of the polyether ester layer of this biaxially stretched film was 18 μm, and the thickness of the polyethylene terephthalate layer was about 22 μm. Furthermore, the adhesion between the polyether ester IW and the polyethylene prephthalate layer of this biaxially stretched film was also good. Furthermore, the carbon dioxide permeability coefficient of this biaxially stretched film is 2.
It was 1*l·mm/rrr·day-atm. Example 29 First, polyethylene terephthalate 1 (trade name, three-piece PI!T J 015) was injection molded, and then the polyether ester in Example 27 was injection molded again to form a polyethylene terephthalate layer and polyether. The thickness of each layer is approximately 1.
A preform having a diameter of 6 mm was produced. Next, this preform is heated to 80°C to 100°C using a far-infrared heating device.
°Cj, and then molded into about 2
．． The bottle was stretched 5 times and about 4.3 times in width to form a stretched bottle having a polyethylene terephthalate layer of about 150 microns and a polyether ester layer of about 150 tt at the minimum thickness, and an internal volume of about 11. Next, we measured the oxygen gas permeability of this stretched bottle and found that it was 0.13 m1・day −
bottle-aim, and the carbon dioxide gas permeability was 0.55 ml-day/bottle-atm. Comparative Example 4 Same polyethylene terephthalate 1 as used in Example 29
- (Product name, three-piece P[!T J 015 "I) was injection molded to the same thickness as the preform of Example 29 (approximately 3.
A preform consisting only of a polyethylene terephthalate layer with a thickness of 2 mm) was prepared. This preform was then stretch-blown in the same manner as in Example 23 to produce a stretched bottle having a minimum wall thickness of approximately 300μ and an internal volume of approximately 1β. Furthermore, as a result of measuring the oxygen gas permeability and carbon dioxide gas permeability of this stretched bottle, 1. ]OmZ・d
ay・bottle-aill and 4.0 m
It was 1-day, bottle, and ATM. Example 30 Polyethylene terephthalate (trade name, Sankata PET J
125) was melted using one extruder, and separately, the polyether ester in Example 27 was melted using another extruder, and each of the polyether esters was fed to a three-layer pa/but die, and polyethylene terephthalate was melted using one extruder. Hydophthalate (thickness approx. 1.2/], 2/1.2mm
) was extruded and cooled with water to obtain a three-layered vibrator with an outer diameter of 24.8 mmφ and a thickness of 3.6 mm. Next, cut off this vibrator and heat and melt one end.
The bottom part was processed by heating, and the other end was similarly heated and melted to process the plug part, thereby obtaining a preform having a total length of 16.5 cm and a weight of 50 g. Next, a biaxial stretch blow molding machine [LB manufactured by CORPOPLAST] was used.
OI), biaxially stretched 2.5 times in length and 4 times in width,
Multi-layer container with inner lamination of 1.5β (polyethylene terephthalate/polyethylene terephthalate - about 120/about 1
20/about 120μ) was obtained. Next, the oxygen gas permeability of this multilayer container was measured and was found to be 0.22 ml/day.
・It is a bottle-atm, and the carbon dioxide permeability measurement result is 0.64 m1/day-bot.
It was tle/atm. Subsequently, the multilayer container was filled with water at 0° C., but the multilayer container did not break. Further, delamination of each layer was not observed. [Effects of the Invention] The polyether ester of the present invention has excellent melt moldability, stretch moldability, transparency, and gas barrier properties, and both the polyester laminate molded product and the preform for polyester multilayer hollow molded products of the present invention have excellent melt moldability, stretch moldability, transparency, and gas barrier properties. It has excellent stretch formability, transparency, and gas barrier properties, and both the polyester stretch laminate molded product and the polyester stretched multilayer hollow molded product of the present invention have excellent transparency and gas barrier properties. Applicant Mitsui Petrochemical Industries Co., Ltd. Agent Yamaguchi Written amendment to Japanese procedures (voluntary) July 1985 No.

Claims (7)

[Claims] (1) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R' represents a divalent aromatic hydrocarbon group whose main component is p-phenylene group, and R^ 2 represents a divalent aromatic hydrocarbon group having 2 to 20 carbon atoms, R^3 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and R^
4 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, p is 0 or a positive number, and m and n are positive numbers, provided that the value of m/(m+n) is 0 It ranges from .02 to .98. ] is a substantially linear polyetherester having an intrinsic viscosity [η
] is in the range of 0.3 to 2 dl/g, and the glass transition temperature is 30
A polyether ester characterized by a temperature ranging from 160°C to 160°C. (2) (a) General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [II] [In the formula, R^2 represents a divalent aromatic hydrocarbon group having 2 to 20 carbon atoms. , R^3 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, R^4 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and p is 0 or a positive number. It is. ] (b) General formula [III] HO-R^1-OH...[III] [In the formula, R^1 is a divalent diol whose main component is p-phenylene group An aromatic hydrocarbon group] and (c) epihalohydrin are reacted in a two-liquid phase mixed solvent consisting of water and an organic solvent in the presence of a base and a phase transfer catalyst. The following general formula [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I] [In the formula, the definitions of R^1, R^2, R^3, R^4 and p are Same as above, and m and n are positive numbers, provided that the value of m/(m+n) is between 0.02 and 0.98
within the range of ], has an intrinsic viscosity [η] in the range of 0.3 to 2 dl/g, and has a glass transition temperature in the range of 30 to 160°C. (3) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I] [In the formula, R^1 is a divalent aromatic hydrocarbon whose main component is p-phenylene group R^2 represents a divalent aromatic hydrocarbon group having 2 to 20 carbon atoms, R^3 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and R
^4 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, p is 0 or a positive number, and m and n are positive numbers, provided that the value of m/(m+n) is It is in the range of 0.02 to 0.98. ] A substantially linear drawn polyetherester having an intrinsic viscosity [η] in the range of 0.3 to 2 dl/g and a glass transition temperature in the range of 30 to 160°C. (4) A laminate molded product composed of a polyalkylene terephthalate layer (A) and a polyetherester layer (B) whose main constituent unit is ethylene terephthalate,
The polyether ester has the general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I] [In the formula, R^1 is a divalent aroma whose main component is p-phenylene R^2 represents a divalent aromatic hydrocarbon group having 2 to 20 carbon atoms, and R^3 represents a divalent hydrocarbon group having 2 to 20 carbon atoms. ,R
^4 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, p is 0 or a positive number, and m and n are positive numbers, provided that the value of m/(m+n) is It is in the range of 0.02 to 0.98. ] and is characterized by being a substantially linear polyetherester having an intrinsic viscosity [η] in the range of 0.3 to 2 dl/g and a glass transition temperature in the range of 30 to 160°C. Polyester laminate molded product. (5) A polyester stretch laminate molded product composed of a polyalkylene terephthalate layer (A) and a polyether ester layer (B) whose main constituent unit is ethylene terephthalate, wherein the polyether ester has the general formula [
I 〕 ▲ There are mathematical formulas, chemical formulas, tables, etc. represents a divalent aromatic hydrocarbon group having 2 to 20 carbon atoms, R^3 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, R^
4 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, p is 0 or a positive number, and m and n are positive numbers, provided that the value of m/(m+n) is 0 It ranges from .02 to .98. ] and is characterized by being a substantially linear polyetherester having an intrinsic viscosity [η] in the range of 0.3 to 2 dl/g and a glass transition temperature in the range of 30 to 160°C. Polyester laminate molded product. (6) A preform for a polyester multilayer blow molded article having a laminated structure composed of a polyalkylene terephthalate layer (A) and a polyether ester layer (B) whose main constituent unit is ethylene terephthalate, wherein the polyether ester General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼・・・・・・[I] [In the formula, R^1 represents a divalent aromatic hydrocarbon group whose main component is p-phenylene group. , R^2 represents a divalent aromatic hydrocarbon group having 2 to 20 carbon atoms, R^3 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and R
^4 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, p is 0 or a positive number, and m and n are positive numbers, provided that the value of m/(m+n) is 0 It ranges from .02 to .98. ] and is characterized by being a substantially linear polyetherester having an intrinsic viscosity [η] in the range of 0.3 to 2 dl/g and a glass transition temperature in the range of 30 to 160°C. A preform for polyester multilayer hollow molded bodies. (7) A polyester multilayer hollow molded article having a laminated structure composed of a polyalkylene terephthalate layer (A) and a polyether ester layer (B) whose main constituent unit is ethylene terephthalate, wherein the polyether ester has the general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R^1 represents a divalent aromatic hydrocarbon group whose main component is p-phenylene group, and R^2 is a carbon atom. represents a divalent aromatic hydrocarbon group having 2 to 20 carbon atoms, R^3 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and R
^4 represents a divalent hydrocarbon group having 2 to 20 carbon atoms, p is 0 or a positive number, and m and n are positive numbers, provided that the value of m/(m+n) is 0 It ranges from .02 to .98. ] and is characterized by being a substantially linear polyetherester having an intrinsic viscosity [η] in the range of 0.3 to 2 dl/g and a glass transition temperature in the range of 30 to 160°C. Polyester multilayer hollow molded body.