JPS6225043A - Polyester laminated molded shape and application thereof - Google Patents

Abstract

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

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a polyester laminate molded product that has excellent melt moldability, excellent mechanical strength and gas barrier properties, and has properties suitable as a material for containers, and a polyester laminate molded product thereof. It's about usage.

[Conventional technology]

Conventionally, glass has been widely used as a material for containers for seasonings, oils, beer, alcoholic beverages such as 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 is generally adopted in which empty containers are 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, in the case of containers for beer and carbonated drinks, which require the most stringent gas barrier properties, it is difficult to say that even bolier and tylene terephthalate are sufficient, and meat Gas barrier properties had to be improved by increasing the thickness. 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 polyalkylene isophthalates such as polyethylene isophthalate, copolymers thereof, and molded articles formed therefrom as packaging materials having good gas barrier properties against oxygen and carbon dioxide. ing.

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

Furthermore, JP-A No. 59-39547 discloses a container in which the innermost layer is made of polyester having ethylene terephthalate as the main repeating unit, the outer layer is made of polyester having ethylene isophthalate as the main repeating unit, and the thin wall portion of the container is at least partially A multilayer container with excellent gas permeation resistance that is oriented in the direction of the gas permeation is disclosed.

Although it is a material different from polyester, it is
Publication No. 296 discloses a polyamide with good transparency, which has m-xylylene diamine or a mixture of m-xylylene diamine and p-xylylene diamine as the diamine component, and a specific aliphatic dicarboxylic acid as the dicarboxylic acid component. is disclosed. Although the publication describes that the polyamide exhibits good impact strength and excellent processability, there is no mention of its gas barrier properties.

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

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

Furthermore, JP-A-56-100828 discloses that linear hydroquinone phenoxy polymers prepared from /S hydroquinone and epihalohydrin are characterized by low permeability to oxygen and carbon dioxide. .

Also, Journal of Applied Pol
ymer 5science.

Volume 7, 2135-2144 (1963),
The following formula (1) (A), ÷-0-E-0-CH12CH-
Cl3+x-1/'JH Here, E is H5 CH31-03H7 Is the gas barrier property of the homopolyhydroxy ether represented by this formula disclosed? ), the most oxygen permeable 0.5cc
-min/1001n/24hr/atm.

The one with the lowest water vapor mobility is E under the conditions of c[(3 raw, 91'l1% R,
1/1001n2/24hr.

Also, Journal of Applied Po
lymerScience, Volume 7, 2145-21
52 (1965) discloses the gas barrier properties of a copohydroxy polyether represented by the following formula (B) (wherein R1 and R2 are not the same). The highest CH,5 value of oxygen permeability is 5 g-ml/100 in/24 hr
/atm. The one with the lowest water vapor mobility is 4g-J/1001n/ under the condition that R1 is CH3 90% R,H.
It is 24 hours.

[Problems that the invention attempts to solve]

An object of the present invention is to provide a polyester laminate molded product containing a novel polyhydroxy polyether ester as a constituent component.

Another object of the present invention is to provide a polyester laminate molded product containing a polyhydroxypolyether ester as a constituent component, which has excellent gas barrier properties, particularly barrier properties against oxygen and carbon dioxide gas.

Still another object of the present invention is to provide a polyester laminate molded product which not only has excellent gas barrier properties but also has excellent melt moldability and stretchability.

Still another object of the present invention is to provide a stretched product of the above molded body of the present invention, a preform for a multilayer hollow molded body, and a multilayer hollow molded body thereof.

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 objects and advantages of the present invention are achieved as follows: A polyester laminate molded product comprising: a polyester composition layer consisting of an ether ester (BL); and (B) a polyalkylene terephthalate layer containing ethylene terephthalate as a main constituent unit, wherein the polyhydroxy polyether ester (b) , -OH (wherein R1 represents a p-phenylene group, R2 represents a divalent hydrocarbon group having 2 to 18 carbon atoms, and R3 represents a divalent hydrocarbon group having 6 to 18 carbon atoms other than the p-phenylene group) represents a divalent aromatic hydrocarbon group, β and m are positive numbers, n is 0 or a positive number, and 1/(1+m+n
) is 0.3 to 1.0, m/(6+m+n) is 0.01 to 0.5, and n/(jl!+m+n)
is between 0 and 0.7. However, when R2 is a p-phenylene group, m/(A+m+n) is less than 0.5, and when R'' is two or more divalent hydrocarbon groups containing a p-phenylene group, m/ (A +m+n) is 0
．． 5 or the proportion of p-phenylene groups to all divalent hydrocarbon groups constituting R2 is less than 0.6. ], the intrinsic viscosity [η] is in the range of 0.3 to 2 dl/g, and the glass transition temperature is in the range of 30 to 160°C. This is achieved by a polyester laminate molded product with special characteristics.

The polyhydroxy polyether ester (bl) used in the polyester composition layer (g) of the present invention is novel and can be produced, for example, by the method described below.

(a) diglycidyl ether of at least one diol represented by the general formula (If') [wherein R4 represents a divalent hydrocarbon group having 2 to 1B carbon atoms]; and (b) the general formula 1) [In the formula, R2 represents a divalent hydrocarbon group having 2 to 18 carbon atoms. ] and further optionally (C) General formula G] HO-R5-OH...-(IV') [wherein R5 is 2 having 6 to 20 carbon atoms] represents a valent aromatic hydrocarbon group. ] At least one aromatic di-ol represented by the general formula CI) (-0-OHOH-
0-R3→ ...(1) [wherein R is η-] represents a unicine group, R represents a divalent hydrocarbon group having 2 to 18 carbon atoms, and R3 represents p- Represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms other than a phenylene group,
4 and m are positive numbers, and n is 0 or a positive number.

However, when R is p-phenylene group, m/(!
m+n) is less than 0.5, and when R is two or more divalent hydrocarbon groups containing 1)-7,Z nylene group, m/(j?+m+n) is less than 5. The proportion of p-phenylene groups to all the divalent hydrocarbon groups present or constituting R is less than 0.6. ] of the polyhydroxy polyetherester represented by 0.5≦(1/(#+m+n)≦1.00≦m/(l
+m+n)≦0.5 0≦n/(J?+m+n)≦0.7 It can be produced by reacting in an organic solvent so as to satisfy the following.

When n = O in the above formula [■], the polyhydroxy polyether ester used in the present invention is represented by the general formula [■] ... [■), and furthermore, 4, l and n are When neither of them is 0, it is represented by the general formula [I] (where n\0). Whether the polyhydroxy polyether ester is represented by the general formula [v] or the general formula (1'), the structure of the polyhydroxy polyether ester is 0CR20HC!
H2-0-R→, "H entered + OOH (:! HC! 6 structures represented by H-0-R3+ 2+ 2 H 51 minutes: Arranged in Nodam.

In the polyhydroxy polyether ester represented by the general formula CI') used in the present invention, l and m are both positive numbers, and n is 0 or a positive number. The proportion of each component unit constituting the general formula CI) is! 1
/ (j?+m+n) is in the range of 0.3 to 1.0, preferably 0.4 to 1.0, particularly preferably 0.5 to 1.0, and m/(j?4-n+m) is 0
．． 01 to 0.5, preferably 0.02 to 0.5
, particularly preferably in the range of 0.05 to 0.5, and n/(l+m+n) is 0 to 0.7, preferably 0.
The range is from 0 to 0.6, particularly preferably from 0 to 0.5. However, if R2 is p-phenylene group, m/(j?+m+n)4i less than 0.5,
In the case of two or more types of divalent hydrocarbon groups containing an R+-phenylene group, m/(Jl?10m+n) is 0.
5 or the proportion of p-phenylene groups to all divalent hydrocarbon groups constituting R2 is less than 0.6.

In the polyhydroxy polyether ester, 11/
The value of (A'+m+n) is 0. If the value of n/(j?+m+n) is greater than 0.7, the gas barrier properties of the polyhydroxy polyether ester may decrease, the glass transition temperature may decrease, or the polyalkylene :/Unfavorable phenomena such as a decrease in co-molding properties and adhesion with terephthalate, and a decrease in gas barrier properties and mechanical strength of the composition with polyalkylene terephthalate are observed.

The polyhydroxy polyether esters used in this invention are substantially linear. The term "substantially linear structure" as used herein means that it consists essentially of a linear or branched chain structure, and it means that it does not substantially have a gel-like crosslinked structure (network structure).

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

RIL constituting the polyhydroxy polyether ester represented by the general formula (I) used in the present invention is a p-phenylene group. In addition, R has 2 to 1 carbon atoms.
8, and the divalent hydrocarbon group has a halogen atom, an oxygen atom, or a sulfur atom in the molecule.
may contain. Specifically, the divalent hydrocarbon group R2 is ζ, +CH2+2, +CH2÷5, +CH2
→4, -C-c H2→5, aliphatic hydrocarbon groups such as OO. These divalent hydrocarbon groups may be a mixed component of two or more.

Furthermore, R3, which can constitute the polyhydroxypolynylene ester 2 represented by the general formula (Il) used in the present invention, has 6 carbon atoms other than the p-phenylene:/ group.
7″I: indicates a divalent aromatic hydrocarbon group of 20, and the divalent aromatic hydrocarbon group may contain a rogen atom, an oxygen atom, or a sulfur atom in the molecule. Specifically, the divalent aromatic hydrocarbon group R is:

etc. can be given. These divalent aromatic hydrocarbon groups may be a mixture of two or more groups.Among these aromatic hydrocarbon groups, :/ group, chain, p'-biphenylene:/ group, 4.4'-oxydiphenylene di/group, 4.4'
-1,1,4'-Sulfodiphenylene group, 4,4'-Meta:Fujiphenylene group, 2,2'
-Propa:/-bis-4-phenyle:/ group and the like are preferred.

The polyhydroxy ether ester used in the present invention may have an epoxy group Ii phenolic hydroxyl group at its terminal depending on the ratio of raw material compounds used in producing it. These terminal carboxyl groups, hydroxyl groups or epoxy groups can be converted into carboxyl/acid esters, such as acetic acid ester (-ococH5), methyl ester (
-COOOH3), ethyl ester (-CoOCH2
0H3) etc. To the polyhydroxy polyether ester used in the present invention! '1 Includes those having various terminals as described above.

As mentioned above, the polyhydroxy polyether ester used in the present invention has an intrinsic viscosity of 0.5 to 2 dβ/only, and a glass transition temperature of 50 to 160'C. When the intrinsic viscosity is greater than 2 d#/g, the melt moldability of the polyhydroxy polyether ester composition decreases, and furthermore, its spreadability also decreases. Further, when the intrinsic viscosity is less than 0.5 dl/g, the mechanical strength of the polyhydroxy polyether ester composition and its stretched product decreases. The polyhydroxy polyether ester used in the present invention preferably exhibits an intrinsic viscosity of 0.4 to 1,564 #/g, more preferably 0.4 to 1.26 #/g. On the other hand, if the glass transition temperature is lower than 30'C, it becomes difficult to perform drying economically.

The polyhydroxy polyetherester used in the present invention preferably has a glass transition temperature of 40 to 140°C, more preferably 40 to 120"C.

The polyhydroxy polyether ester used in the present invention usually has a molecular weight distribution defined by the ratio of weight average molecular weight (Mw) to number average molecular weight (un) (Mw/Mr+), for example, from 1.5 to 10. Exists within the range.

The polyhydroxy polyether ester used in the present invention is a diglycidyl ether of at least one diol represented by the general formula (n) and the general formula Cl1
It is formed by reacting at least one dicarboxylic acid/acid represented by 1') and, if necessary, an aromatic diol represented by the above general formula in an organic solvent. The diglycidyl ether of a diol represented by the general formula (1) is a diglycidyl ether of a diol in which the hydrocarbon group R4 forming the diol is a divalent hydrocarbon group having 2 to 18 carbon atoms. is preferably a diglycidyl ether of a diol in which R4 is a 1,18 divalent aromatic hydrocarbon group having 6 or less carbon atoms, and particularly preferably R4 is a diglycidyl ether of a diol having 6 or less carbon atoms. The constituent hydrocarbon group R, which is a diglycidyl ether of diol which is a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, contains a halogen atom, an oxygen atom, or a sulfur atom in the molecule. It's okay. Specifically, the diglycidyl ether of the diol includes hydroquinone diglycidyl ether, Resolche/diglycidyl ether, and Catefu! Regiglycidyl ether, mesenruhydroquinoni/Siglycidyl ether! Reether, 2,5-dime4
1L/Hydroquino:/diglycidyl ether, 2.6
-dimethylhydroquinodi/diglycidyl ether, 2
, 5.5゜6-titrahydroquino:/diglycidyl ether, phenylhydroquinodiglycidyl ether, chlorohydroquino/diglycidyl ether,
2-Methyl resorcindi/diglycidyl ether tV, 2,
416-Dorimethylresorci:/diglycidyl ether, 2.6-naphthalene:/diol diglycidyl ether, 2.7-naphthalene:/diol diglycidyl ether, 1.4-naphthalene/diol diglycidyl ether! ether, 1,5-naphthalene/diol diglycidyl ether, p*T''-biphenol diglycidyl ether, 4,4-oxydiphenol diglycidyl ether,
4゜4-thousand odiphenol diglycidyl ether, 4゜4-sulfodiphenol diglycidyl ether, bisphenol-F-diglycidyl ether, bispheno-&
-A-diglycidyl ether, bisphenol-p-
';) y-dimethyl ether, 4,4-dimethyl-bis(2,6-dimethylphenol) diglycidyl ether, 3,6-dihydroxy-9,9-dimethyl lexani/teninodiglycidyl Aete! Shi, Ethyreni/Glyfur diglycidyl ether, Diethyre: Nogelicol diglycidyl ether, Torie Chishi:/Gerifu! cyclohexani/- An example is 1,4-dimethanol digericidyl ether.

The diglycidyl ether of the aromatic diol of formula (Il) above may contain a halogen/ element that may be mixed in during its production process, and may further undergo an addition reaction with the epoxy group. The following general formula [ψ] is generated when It may contain a low polymer represented by the following general formula [m] in which one of the terminals is present as a glycerin:/ unit [wherein, the definition of R1 is the same as above]. ] may be contained in a small amount within a range that does not reduce the molecular weight of the polyhydroxypolyether ester CI).

At least one dicarboxylic acid represented by the general formula [1] is a dicarboxylic acid in which the hydrocarbon group R5 constituting it is a divalent hydrocarbon group having 2 to 18 carbon atoms, and the hydrocarbon The radicals may contain halogen, oxygen or sulfur atoms. Hydrocarbon groups R5 constituting the dicarboxylic acid include hydrocarbon groups R1 and R2 in the general formula (1') and 1. Hydrocarbon groups can be exemplified in exactly the same manner. Specifically, the cica7levonino acids include terephthalic acid, chlorotin phthalic acid, methyl terephthalic acid, phthalic acid, isophthalic acid, 5-〆-(-ruin phthalic acid, 5-chloroisophthalic acid, 2.6-Natsuta Den'2/Cica l reponide/acid, 1,5-naphthalini/Cica l repon2) acid, 1.4-naphthalinide/Cical reponino acid, 2.7-naphtalin/dicarboni/ Acid, 4.4'-Diphenylene/Cica! Levoni'Ml, 4.4'-diphenyl ether recarbo:/acid, 4.4-beni/zopheno:/cical rejo:/
%, 4.4'-diphenyls v honjiki report:/acid,
4.4- Jipheni! Remeta di/Cica M bonic acid-4,4'
-Diphenylbrovani/Cica l Revo:/Acid, 4.4
'-) rifhenylmec:/dicarboxylic acid, 4.4'-diphenyllevonic acid, 4.4'-triphenylmeth:/dicar7levoni/? ), 4.4'-
Tetraphenylmeth:/dicarpo:/l! ? Aromatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, aliphatic dicarboxylic acids such as pyruvic acid, cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,5-
Examples include alicyclic cicafrebonic acids such as dicarboxylic acids.

At least one aromatic diol represented by the above general formula J] is a diol in which the aromatic hydrocarbon group R3 constituting it is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the aromatic The hydrocarbon group may contain a halogen atom, an oxygen atom or a sulfur atom. Specifically, the aromatic diols include hydroquinone, resorcinol, catechol, dihydroquinone, 2,5-dimethylhydroquinone, 2,6-dimethylhydroquinone,
2,3,5゜6-ketramethylhydroquinone, phenylhydroquinone, chlorhydroquinone, 2,6-
Cyclolhytroquinone, 2-methylresorcinol, 2°d,6-)dimethylresorcinol, 2.6-naphthalenediol, 2,7-naphthalenediol, 1.5-naphthalenediol, 1.4-naphthalenediol, 1 )j
p-biphenol, 4. - monooxydiphenol, 4.
4-ketodipheno-I, 4,4-thiodipheno-k,
d, 4-sulfodiphenol, bis(A-hydroxyphenyl)methane, 2.2-bis(4-hydroxyphenyl)propane, 1-phenylene 1.1-his(4-hydroxyphenyl)ethane, 41. /-Diphenol dipheni! Remethane, 4,4-dihydroxy-5,”+
, 5,5-tetramethoxyl, bis(4-hydroac-5,5-cyclohydrocylate) ether.

Bis(4-hydroxy-5,5-dimethylphenyl)methane, 2,2-bis(A-hydroxy-5,5-dimethylphenyl)propane, 9,9-dimethyl-5,6-dihydroxyquinthene, etc. can be exemplified. Among these aromatic diols, hydroquinone, resorcinol,
2.6-naphthalene, p.

p-biphenol tV, 4,4'-oxydiphenol,
4.4-ketodiphenol, 4,4'-sulfodife/
-/bis(4-hydroxyphenyl)methane, 2.
2-bis(-monohydroxyphenyl)propane, bis(4-hydroxy-5,5-dimethylphenyl)methane, and 2,2-bis(A-hydroxy-5,5-dimethylphenyl)propane are preferred.

In the method for producing the polyhydroxypolyetherester V, the diglycidyl ether of Dio-I, the dicarboxylic acid, and optionally the aromatic diol are combined with a general compound representing the polyhydroxypolyetherester to be produced. In formula (I), l/(#+m+
The ratio of n) is preferably from 0.3 to 1.0, preferably from 0.5 to 1.0, and particularly preferably from 0.5 to 1.0, and the ratio of m/(fi+m+n) is from 0.01 to 0. ．．
5. Preferably the range is from 0.02 to 0.5, particularly preferably from 0.05 jr to 0.5, and n/(/
'4-m+n) is between 0 and 0.7, preferably 0.
The ratio of each raw material is adjusted and supplied so that the ratio ranges from 0 to 0.6, particularly preferably from 0 to 0.5. In the reaction system, the total number of moles of the dicarboxylic acid and the aromatic diol per mole of the diglycidyl ether of the diol is usually 0.95 to 1.05, preferably 0.97 to 1.05, particularly Preferably 0.9
The diglycidyl ether of the diol and, if necessary, the aromatic diol are supplied so that the dicarboxylic acid is in the range of 8 to 1.02.

In the method for producing the polyhydroxypolyether ester M, the reaction between the diglycidyl ether of the diol, the dicarboxylic acid, and the optionally used aromatic di-I is carried out in the presence of an organic solvent. Examples of the organic solvent include diglycidyl ether of diol and dicarboxylic acid, which are raw materials.

Those that are soluble in the aromatic diol used as necessary and the polyhydroxy polyether ester that is the resulting polymer are preferred, such as methyl isobutyl ketone and cyclohexanone.

2-butanone, aceFphenone, γ-1,000 rolactone,
Sulfolane, dimethyllus V phoxite, N-methyl-2-
Pyrrolidone, N,N-dimethylformamide, etc. are used. The amount of organic solvent used is, for example, 1 to 10 parts by weight per 1 part by weight of the polymer to be produced.

The reaction is usually carried out at about 80 to 200°C, preferably about 100 to 200°C.
It is carried out at a temperature of 180°C.

The reaction proceeds without a catalyst in the above temperature range, but it is possible to use a reaction mixture such as triethylamine, tri-n-propylamine, tri-n-1,000 amine, triisobutylamine, tri-n-hexylamine, tri-n-hexylamine, dimethylbenzylamine, etc. Tertiary amine, tetra-n-butylene ammonium hydroxide.

Tetraalkylammonium hydroxide, such as trimechloride ammonium hydroxide,
alcolate of alkali metals such as sodium mechloride, sodium ethylate, sodium isopropionate, sodium n-butylate, potassium ethylate, potassium ethylate or sodium hydroxide;
It is preferable to carry out the reaction in the presence of a suitable small amount of a basic compound such as potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, etc., since this will accelerate the reaction. After reaction.

The produced polymer is separated and obtained from the reaction system by a method known per se.

In this way, according to the above method, the general formula %formula %(
1) [In the formula, R4Jp-phenylene group, R represents a divalent hydrocarbon group having 2 to 1B carbon atoms, and R3 represents p
- represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms other than a phenylene group, 1 and m are positive numbers, n is 0 or a positive number, and! /(e+m+n) is 0
．． 3 to 1.0, m/(p+m+n) is O, f
)IQ is 0.5, and n/(10m+n) is 0.7. However, when R2 is a p-phenylene group, m/(ff+m+n) is less than 0.5, and when R2 is a divalent hydrocarbon group of 2@ or more containing a p-phenylene group, m / (β10+n) is 0.5
or the proportion of p-phenylene groups to all divalent hydrocarbon groups constituting R2 is less than 0.6.

] A substantially linear polyhydroxy polyether ester is obtained. In the above method, in the case of reacting hydroquinone diglycidyl ether 7 as a raw material with approximately equimolar dicarboxylic acid, or reacting dicarboxylic acid and Noh
When hydroquinont is reacted, a polyhydroxypolyether ester represented by the general formula (n) is obtained.In addition, as a raw material, the reaction of di-I di-glycidyl ether! or when dicarboxylic acid and aromatic diol are reacted in such a manner that the total number of moles is approximately equal to digericidyl reate I of diol, both hydroquinone component units and other diol component units are exists and the hydroquinone component unit is 50
If the reaction is carried out at a ratio of mol% or more, the general formula [I) (
However, a polyhydroxy polyether ester represented by n\0) is obtained.

The polyhydroxy polyether ester obtained by the above method is subjected to the above-mentioned molecular end treatment, if necessary.

The polyalkylene terephthalate (a) constituting the polyester composition layer 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 1,3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexane dimetatool, 1゜4-bis(β Carbon atoms such as -hydroxyethoxy)benzene, 1゜3-bis(β-hydroxyethoxy)benzene, 2゜2-bis(4-β-hydroxyethoxyphenyl)propane, bis(4-β-hydroxyethoxyphenyl)sulfone, etc. number 3 or 1
The diol component unit of No. 5 can be exemplified.

Further, in addition to 1, the aromatic dicarboxylic acid component unit and the diol component unit, the polyalkylene terephthalate may contain a small amount of a polyfunctional compound as required. Specifically, the polyfunctional compound component units include trimellitic acid, trimesic acid, 3.3'
, aromatic polybasic acids such as 5,5'-tetracarboxydiphenyl, aliphatic polybasic acids such as butanetetracarboxylic acid, aromatic polyols such as phloroglucin, 1,2,4,5-tetrahydroxybenzene, etc. Examples include aliphatic polyols such as , glycerin, trimethylolethane, trimethylolpropane, and 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%. The content of polyfunctional compound component units is preferably 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 0 to 1 mol%. Further, the intrinsic viscosity [η] of the polyalkylene terephthalate [value measured at 25°C in a phenol-tetrachloroethane mixed solvent (weight ratio 1/1)] is usually 0.5 to 1. FMf/g, preferably 0.6 to 1.2d! /g, the melting point is usually in the range of 210 to 265°C, preferably 220 to 260°C, and the glass transition temperature is usually in the range of 50 to 120'C1, preferably 60 to 100°C.

In the polyester composition, the blending ratio of the polyhydroxy polyether ester (bl) is usually 2 to 500 parts by weight, preferably 3 to 300 parts by weight, per 100 parts by weight of the polyalkylene terephthalate (al).
Particularly preferred is a range of 5 to 100 parts by weight.

In addition to the polyalkylene terephthalate fa) and the polyhydroxy polyether ester (b), the polyester composition may optionally contain a conventionally known nucleating agent,
Appropriate amounts of various additives such as inorganic fillers, lubricants, slip agents, antiblocking agents, stabilizers, antistatic agents, antifogging agents, and pigments may be blended.

Next, a polyalkylene terephthalate layer containing ethylene terephthalate as the main constituent unit (
The polyester laminate molded article of the present invention comprising B) will be explained. Specifically, the laminate molded product is a two-layer laminate molded product composed of two layers, the polyester composition layer and the polyalkylene terephthalate layer, the polyester composition layer is the middle layer, and the outer layer is the polyester composition layer. A three-layer laminate molded product having an alkylene terephthalate layer, a three-layer laminate molded product having the polyalkylene terephthalate layer as an intermediate layer and the polyester composition layer on both sides, and alternating the polyester composition layer and the polyalkylene terephthalate layer. A multilayer laminate molded product having a four-layer structure or more, in which both liquid outer layers are composed of the polyalkylene terephthalate layer, and a four-layered product in which the polyester composition layer and the polyalkylene terephthalate layer are alternately laminated. A multilayer laminate molded product having a structure or more, in which both liquid outer layers are composed of the polyester composition layer, a laminate molded product having a four-layer structure or more in which the polyester composition layer and the polyalkylene terephthalate layer are alternately laminated. Examples include multilayer laminate molded bodies in which the outermost layer is composed of the polyester composition layer and the polyalkylene terephthalate layer. The laminated molded product is a sheet,
It can be used not only for plate-shaped objects and tubular objects, but also for various hollow bodies, containers, and structures of various shapes. The laminate can be manufactured by a conventionally known method.

The thickness of the polyester composition layer and the polyalkylene terephthalate layer CB) constituting the laminate molded product is determined as appropriate depending on the use of the laminate molded product,
Not particularly limited. When the laminate molded product is the two-layer laminate molded product, the thickness of the polyester composition layer is usually in the range of 1 to 350μ, preferably 2 to 200μ, and the thickness of the polyalkylene terephthalate layer is 8
It ranges from 10 to 600μ, preferably from 10 to 500μ.

When the mN molded product is the former of the three-layer laminate molded product, the thickness of the intermediate layer consisting of the polyester composition layer is usually 1 to 350μ, preferably 2 to 200μ.
The thickness of each of the outer circular layers of the polyalkylene terephthalate layer is usually in the range of 4 to 300 microns, preferably in the range of 5 to 250 microns. Further, when the laminate molded product is the latter of the three-layer laminate molded products, the thickness of the intermediate layer consisting of the polyalkylene terephthalate layer is usually in the range of 8 to 600μ, preferably 10 to 500μ. The thickness of the outer layer of the polyester composition is usually in the range of 1 to 100 microns, preferably 1 to 50 microns. Even when the laminate molded product is a multilayer laminate molded product having a four-layer structure or more, the thickness of the intermediate layer and the outermost layer made of the polyester composition layer, and the thickness of the intermediate layer and the outermost layer made of the polyalkylene terephthalate layer. The thickness of the layer can be chosen as before.

The resin constituting the polyalkylene terephthalate layer of the polyester laminate molded product is a polyalkylene terephthalate whose main constituent unit is ethylene terephthalate,
Specifically, polyalkylene terephthalate similar to the polyalkylene terephthalate (a) having ethylene terephthalate as a main structural unit, which is a constituent resin of the polyester composition of the present invention, can be exemplified. The polyalkylene terephthalate constituting the polyalkylene terephthalate layer of the polyester laminate molded product is not necessarily the same as the polyalkylene terephthalate (a) constituting the polyester composition layer. The polyalkylene terephthalate constituting the polyalkylene terephthalate layer may contain nucleating agents, inorganic fillers, lubricants, anti-blocking agents, stabilizers, antistatic agents, antifogging agents, There is no problem even if appropriate amounts of various additives such as pigments are blended.

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

Next, the polyester stretch laminate molded product of the present invention, which is composed of a polyester composition layer and a polyalkylene terephthalate layer (B) having ethylene terephthalate as a main constituent unit, will be explained. A polyester laminate molded product comprising the polyester composition layer and the polyalkylene terephthalate layer and having the above-described laminate structure, and in which at least IN of the polyalkylene terephthalate layer is in a stretched state. be.

Preferably, the polyester laminate molded product is composed of the polyester composition layer (1) (A) and the polyalkylene terephthalate layer, and has the above-mentioned laminate structure, and at least all of the polyalkylene terephthalate layers are stretched. It is a polyester stretch laminate molded product in a state in which the polyester composition layer and the polyalkylene terephthalate layer CB) are formed, and the polyester laminate molded product has the above-mentioned laminate structure, and the polyester composition layer and all layers of the polyalkylene terephthalate layer are in a stretched state. The stretched layer may be in a -axis stretched state or in a two-wheel stretched state.

Further, the form of the polyester stretched laminate molded product may be any shape such as a film or a sheet.

When the resin layer constituting the polyester stretched laminate is uniaxially stretched, the stretching ratio is usually 1.
．． It is in the range of 1 to 10 times, preferably 1.2 to 8 times, particularly preferably 1.5 to 7 times, and when the constituent resin layer is a biaxially stretched layer, the stretching ratio is Usually 1.1 to 8 times, preferably 1
．． 2 to 7 times, and (preferably 1.5 to 6 times), and in the horizontal axis direction, usually 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5 to 6 times. The range is 6 times.Furthermore, the stretched laminate molded product can be heat set depending on its intended use.

When the polyester stretch laminate molded product is a film or a sheet, any conventionally known method can be employed as the manufacturing method.

Generally, the polyester composition and the polyalkylene terephthalate are melted in separate extruders, and a multilayer laminated film or a laminated sheet, etc., is formed by melt coextrusion from a multilayer T-die and is left in a heated state. Alternatively, a method may be adopted in which the material is once cooled and solidified to a temperature below the glass transition point, further heated again, and then subjected to a stretching treatment. Other methods include extrusion lamination or sandwich lamination of the polyester composition onto a film or sheet previously formed from the polyalkylene terephthalate; It may be uniaxially stretched or biaxially stretched before lamination, or the same stretching treatment may be performed after lamination. There is also a method of extrusion laminating the polyalkylene terephthalate on a film or sheet preformed from the polyester composition or a method of sandwich laminating, in which case the film or sheet made of the polyester composition is uniaxially stretched before lamination. There is no problem even if the film is stretched, biaxially stretched, or similarly stretched after lamination. Among these stretching methods,
It is particularly preferable to adopt the method of forming a layered laminate molded product by the first coextrusion method and then subjecting it to stretching treatment, since the process is simple and a polyester stretched laminate molded product with excellent interlayer adhesion can be obtained.

In addition, when producing the polyester stretch laminate molded product,
When the layer molded product is a film or sheet, the stretching treatment may be performed by stretching the layer molded product in a uniaxial direction (-axial stretching), or by stretching it in the longitudinal direction and then further in the transverse direction. A method of stretching (biaxial stretching), a method of stretching simultaneously in the vertical and horizontal directions (biaxial stretching), a method of repeating sequential stretching in any one direction after biaxial stretching, and a method of stretching sequentially in any one direction after biaxial stretching. Further examples include a method of stretching 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 layer molded product and a mold. The temperature during the stretching treatment is in the range of the glass transition point or melting point of the resin constituting the layer molded product, preferably 80° C. higher than the glass transition point or glass transition point. In order to heat set the polyester stretched laminate molded product, an appropriate short-time heat treatment is performed at the stretching temperature or a higher temperature.

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

The polyester stretched hollow molded preform of the present invention is a multilayer hollow body preform having a laminated structure composed of the polyester composition layer and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate, and further This is a preform for a multilayer hollow molded body having the above-mentioned laminate structure. Examples of the preform having a laminate structure include the two-layer laminate preform exemplified in the laminate molded product of the present invention described above, a similar three-layer laminate preform, and a similar multilayer laminate molded product having four or more layers. Renovation can be similarly exemplified. Among these preforms for multilayer hollow molded bodies, a preform having a laminated structure composed of two layers, the polyester composition layer and the polyalkylene terephthalate layer,
When a stretched multilayer hollow molded article is formed from a preform having a laminate structure consisting of the polyester composition as an intermediate layer and the polyalkylene terephthalate layer as the outer layer, it has excellent mechanical strength and transparency. This method is preferable since it is possible to obtain a stretched multilayer hollow molded article having excellent properties such as gas barrier properties.

Both the polyester composition and the polyalkylene terephthalate constituting the preform for a multilayer hollow molded body of the present invention may be added with conventionally known nucleating agents, inorganic fillers, lubricants, slip agents, anti-blocking agents, and stabilizing agents. Appropriate amounts of various additives such as antistatic agents, antistatic agents, antifogging agents, and pigments may be blended.

The polyester multilayer hollow molded preform of the present invention is produced by a conventionally known method.

For example, the polyester multilayer hollow molded preform of the present invention can be obtained by molding the tubular article having the laminated structure.

The stretched polyester multilayer hollow molded body of the present invention is a stretched multilayer hollow molded body composed of the polyester composition layer and the polyalkylene terephthalate layer, and is produced by stretch blow molding the preform for the multilayer hollow molded body. be done. The polyester stretched multilayer hollow molded body may be a stretched two-layer hollow molded body composed of the polyester composition layer and the polyalkylene terephthalate layer, or the polyester composition layer and the polyalkylene terephthalate layer may be It may be a stretched three-layer hollow molded product composed of three layers laminated alternately, or a stretched three-layer hollow molded body composed of four or more layers in which the polyester composition layer and the polyalkylene terephthalate layer are alternately laminated. It may also be a multilayer hollow molded body. When the stretched multilayer hollow body is the two-layer hollow molded body, it may be a stretched two-layer hollow molded body in which the polyester composition layer is the outer layer and the polyalkylene terephthalate layer is the inner layer. However, it may be a stretched two-layer molded article in which the polyester composition layer is the inner layer and the polyalkylene terephthalate layer is the outer layer.

Further, when the stretched multilayer hollow molded body is the three-layer hollow molded body, the stretched three-layer blow molded body has the polyester composition layer as an intermediate layer and the polyalkylene terephthalate layer as an inner layer and an outer layer. The polyester composition layer may be an inner layer and an outer layer, and the polyalkylene terephthalate layer may be an intermediate layer. When the stretched multilayer hollow molded body is a stretched multilayer hollow molded body composed of four or more layers, the polyester composition layer may be the inner layer, and the polyalkylene terephthalate layer may be the inner layer. It may be. Among the polyester stretched multilayer hollow molded bodies of the present invention, it is preferable that the inner layer is a stretched multilayer hollow molded body whose inner layer is a polyalkylene terephthalate layer, and in particular, the polyester composition layer is an intermediate layer and the polyalkylene terephthalate layer is a stretched multilayer hollow molded body. Preferably, the three-layer stretched hollow molded body is an inner layer and an outer layer. The stretched multilayer hollow molded product may be a uniaxially stretched molded product or a biaxially stretched molded product, but generally a biaxially stretched molded product has excellent mechanical strength and gas barrier properties. It is suitable because it has As for the stretching ratio of the stretched multilayer hollow molded product, the stretching ratio described for the stretched laminate molded product made of the polyester composition and the polyalkylene terephthalate is applied as is.

The polyester stretched multilayer hollow molded article of the present invention is produced by stretch blow molding the preform for the polyester multilayered hollow molded article. Examples of this method include a method in which a preform at the above temperature is stretched in the longitudinal direction and then further blow-molded to stretch it in the transverse direction (biaxial stretch blow molding).

The polyester stretched multilayer hollow molded article of the present invention has excellent mechanical strength, heat resistance properties, and gas barrier properties, and therefore can 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 containers for seasonings, oils, alcoholic beverages such as beer and Japanese sake, soft drinks such as cola, cider, and juice, cosmetics, detergents, etc. 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〕

Next, the present invention will be specifically explained using examples. Note that the polyhydroxy polyether ester used in the Examples was manufactured by the method shown in Reference Examples.

Furthermore, in the Reference Examples, Examples, and Comparative Examples, performance evaluation was performed according to the following method.

The intrinsic viscosity of polyhydroxy polyether ester is 0
- Determined by measuring in chlorophenol at 25°C.

The glass transition temperature of the polyhydroxypolyether ester was determined using a differential scanning calorimeter at a heating rate of 10°C/min.

Regarding the gas barrier properties of polyester laminate molded products, polyester stretched laminate molded products, or polyester stretched multilayer hollow molded products, the oxygen gas permeability coefficient is
The carbon dioxide permeability coefficient was measured at 25° C. using an OXTRAN device manufactured by CON and a PERMATRAN C-TV device manufactured by MOCON.

Reference Example I In a reaction tank loaded with 500 parts of N-methylpyrrolidone,
Hydroquinone diglycidyl ether (U.S. Pat. No. 24)
67171g publication, manufactured according to the method described in Example 1, epoxide content 8.3 epoxide/1
/kg), 166.2 parts of terephthalic acid and 2.0 parts of N,N-dimethylbenzylamine were charged.
When the temperature of the system was raised to about 130°C while stirring, an increase in the viscosity of the system was observed after about 30 minutes, so while stirring continued, 800 parts of N-methylpyrrolidone was added and A time reaction was performed. After the reaction is complete, the reaction mixture is poured into a large amount of water to precipitate the polyhydroxy polyether ester, which is then washed with water and methanol and recovered at 40"C. The yield of the polyhydroxy polyether ester thus obtained was 371 parts.The intrinsic viscosity of this polyhydroxy polyether ester was 0.68 dl/g, and the glass transition The temperature is 57°C
Met. In addition, the composition of this polyhydroxy polyether ester has a ratio (molar ratio) of hydroquinone component units and terephthalic acid component units of 53:47, and both hydroquinone component units and terephthalic acid component units are 2-hydroxy-1°. A structure in which the 3-propanediol component unit is bonded via an ether bond, an ester bond, or a bond (j!: m: n=50:5
0: Consistent with O).

Reference Examples 2-3 Reference Example 1 except that terephthalic acid and hydroquinone were used as shown in Table 1 instead of terephthalic acid.
A polyhydroxy polyether ester was obtained in the same manner as above. The yield, intrinsic viscosity, glass transition temperature, and ratio of hadroquinone component units to terephthalic acid component units of these polyhydroxypolyether esters were as shown in Table 1.

Reference Examples 4 to 5 In Reference Example 2, the catalyst shown in Table 2 was used instead of N,N-dimethylbenzylamine as shown in Table 2, and the solvent shown in Table 2 was used instead of N-methylpyrrolidone as shown in Table 2. Polyhydroxypolyether esters were produced in the same manner except that they were used as described and the reaction times were as shown in Table 2. The yield, intrinsic viscosity, and ratio of hydroquinone component units and terephthalic acid component units of these polyhydroxy polyether esters are shown in Table 2.
It was as described.

Reference Example 6 In Reference Example 2, hydroquinone diglycidyl ether 1 was used instead of hydroquinone diglycidyl ether.
57.3 parts and redulsin diglycidyl ether (manufactured according to the method described in US Pat. No. 2,467.171, Example 3, epoxide content 8.0 i/kg of epoxide) 74 A polyhydroxy polyether ester was produced in the same manner except that a mixture of .7 parts and 7 parts was used. The yield of the obtained polyhydroxy polyether ester was 333 parts, the intrinsic viscosity was 0.72 dl/g,
Further, the glass transition temperature was 55°C. In addition, the ratio (molar ratio) of hydroquinone component units, resorcin component units, and terephthalic acid component units in this polyhydroxypolyether ester was 60:16:24 (e:m:
n=50:25:50).

Reference Examples 7 to 9 In Reference Example 2, dicarboxylic acids listed in Table 3 were used as listed in Table 3 instead of terephthalic acid, and aromatic diols listed in Table 31 were used instead of hydroquinone as listed in Table 3. Polyhydroxy polyether ester was produced in the same manner except that it was used in The yield, intrinsic viscosity, glass transition temperature, and composition of the obtained polyhydroxy polyether ester were as shown in Table 3.

Reference Examples 10 to 12 Polyhydroxy polyether esters were produced in the same manner as in Reference Example 1, except that the dicarboxylic acids shown in Table 4 were used as shown in Table 4 instead of terephthalic acid. The yield, intrinsic viscosity, glass transition temperature, and composition of the obtained polyhydroxy polyether ester were as shown in Table 4.

Reference Examples 13 to 16 1 Polyhydroxy polyether esters were produced in the same manner as in Example 2, except that the aromatic diols listed in Table 5 were used as shown in Table 5 instead of hydroquinone. The yield, intrinsic viscosity, glass transition temperature, and composition of the obtained polyhydroxypolyether ester were as shown in Table 5.

Example 1 Polyethylene terephthalate (trade name, Sankata PETJ125) dried at 150°C for 10 hours was press-molded at about 260°C to produce a press sheet with a thickness of about 100μ. Separately, the above polyethylene terephthalate 100
A mixture of 40 parts by weight of the polyhydroxypolyetherester of Reference Example 1, which had been vacuum-dried at 40°C for 18 hours, was melt-extruded at about 260°C using another extruder to obtain a composition. Pellets are produced, and the pellets of the composition are press-molded at about 260°C to a thickness of about 1.
A 00μ press sheet was produced. Furthermore, the press sheet of the above polyethylene terephthalate and the press sheet of the composition of the above polyethylene terephthalate and polyhydroxy polyether ester are superimposed on each other at about 260°C.
Press molding was carried out to produce a two-layer, two-layer laminate sheet with a thickness of approximately 150 μm.

The obtained laminated sheet has good adhesion between the polyethylene terephthalate layer and the composition layer, and has a carbon dioxide gas permeability coefficient of 17 mf/rd-day-atm and an oxygen gas permeability coefficient of 3.0 mf/rd-day-atm. /Lee day
-It was an ATM.

Comparative Example 1 A single-layer press sheet having a thickness of about 150 μm was produced in the same manner as in Example 1 using the polyethylene terephthalate in Example 1. The carbon dioxide permeability coefficient of this press sheet is 251!・Dragon/d・day -atm %
Also, the oxygen gas permeability coefficient is 4.5mf-xwb/rd
・It was day-atm.

Examples 2 to 10 Same as Example 1 except that in Example 1, a press sheet of polyethylene terephthalate listed in Table 6 or a press sheet of a composition of polyethylene terephthalate and polyhydroxy polyether ester listed in Table 6 was used. A two-layer, two-layer laminate sheet having a thickness of approximately 150 μm was prepared.

All of the obtained laminated sheets had good adhesion between the polyethylene terephthalate layer and the composition layer, and the carbon dioxide gas permeability coefficients of these laminated sheets were as shown in Table 6.

Example 11 Polyethylene terephthalate isophthalate was used instead of the polyethylene terephthalate used in Example 3 [ratio of terephthalic acid component units to isophthalic acid component units (molar ratio) 90/10, intrinsic viscosity [η] 0.85
J/g) was carried out in the same manner as in Example 3, except for using a polyethylene terephthalate/isophthalate layer and a composition layer of polyhydroxypolyether ester and polyethylene terephthalate/isophthalate, each having a thickness of about 150 μm. A laminated sheet of layers was prepared. The adhesion between the polyethylene terephthalate/isophthalate layer and the composition layer of this laminate sheet was good.

Also, the carbon dioxide permeability coefficient of this laminated sheet is 14mf・a
rm/rd・day−atm.

Example 12 Polyhydroxypolyether was produced by melting the polyethylene terephthalate in Example 1 at a molding temperature of about 270°C using an extruder, and separately producing 100 parts by weight of the polyethylene terephthalate in Example 1 in the same manner as in Reference Example 2. A mixture of 40 parts by weight of ester was melted at about 260°C using another extruder, and then put into a three-layer coat hanger type T-die, with the upper and lower layers made of polyethylene terephthalate, and the middle layer made of the composition. By extruding it into a sheet and cooling it with a roll, a laminated sheet of two types and three layers, each having a polyethylene terephthalate layer with a thickness of about 75 μm and a composition layer with a thickness of about 75 μm, was produced. The obtained laminated sheet has good glabellar adhesion between polyethylene terephthalate i and polyhydroxy polyether ester layer, and its carbon dioxide permeability coefficient is 18mf・w/rd・day
-It was an ATM.

Example 13 Using a biaxial stretching device, the laminated sheet consisting of the polyethylene terephthalate layer and the composition layer in Example 1 was simultaneously stretched 3 times in the vertical axis direction and the horizontal axis direction to produce a biaxially stretched film. did. The obtained biaxially stretched film had a thickness of about 17 μm and was uniformly biaxially stretched. Furthermore, this biaxially stretched film had good glabellar adhesion between the polyethylene terephthalate layer and the composition layer. Furthermore, the carbon dioxide gas permeability coefficient of this biaxially stretched film is 9.0ml -mm/ rrr-day -atm
Met.

Comparative Example 2 The press sheet of polyethylene terephthalate in Comparative Example 1 was simultaneously stretched 3 times in the vertical axis direction and the horizontal axis direction in the same manner as in Example 10 to produce a biaxially stretched film. Each of these biaxially stretched films has a thickness of approximately 17 μm.
, and its carbon dioxide permeability coefficient is 15m1 ・tm /
It was m day - atm.

Examples 14 to 20 Biaxially stretched films having the stretching ratios shown in Table 7 were prepared in the same manner as in Example 13, except that the laminated sheets listed in Table 7 were used instead of the laminated sheets in Example 13.

The obtained biaxially stretched films all had the thicknesses shown in Table 7 and were uniformly stretched. In addition, all of these biaxially stretched films had good glabella adhesion between the polyethylene terephthalate layer and the composition layer. Furthermore, the carbon dioxide gas permeability coefficients of these biaxially stretched films were as shown in Table 7.

Using a layer injection molding machine in Example 2, the polyethylene terephthalate in Example 1 was molded at a molding temperature of about 2
The mixture of polyethylene terephthalate and polyhydroxypolyether ester prepared in Example 12 was melted at 70°C and molded at a temperature of about 2°C using another injection molding machine.
Two layers were injection molded into a single preform mold that was melted at 70'C and cooled, with the inner layer consisting of polyethylene terephthalate (approximately 1.6 mm thick) and the outer layer consisting of polyethylene terephthalate and polyhydroxypolyether. A two-layer preform consisting of a composition with ester (approximately 1.6 mm thick) was prepared. Then, using a biaxial stretch blow molding machine (manufactured by Kohoplast, LBOI), it was biaxially stretched 2.5 times in length and about 4 times in width to produce a multilayer container with an internal volume of about 1 p. The average thickness of the polyethylene terephthalate layer of this multilayer container was about 150 metres, and the average thickness of the composition layer was about 150° C., and it was confirmed that the polyethylene terephthalate layer was stretched uniformly.

Further, the carbon dioxide gas permeability of this multilayer container was 1.7 mZ/day-bottle-atm.

Comparative Example 3 A preform with a thickness of 3.2 mm was produced by injection molding the polyethylene terephthalate in Example 1 at a molding temperature of about 270'C, and then blow stretch molded in the same manner as in Example 21 to obtain an inner volume of about A stretched bottle of polyethylene terephthalate weighing 1 g was molded.

The carbon dioxide permeability of this stretched bottle is 4.0ml/day
・It was a bottle-ATM.

〔Effect of the invention〕

The polyester laminate molded product, polyester stretch laminate molded product, preform for a polyester multilayer hollow molded product, and polyester stretched multilayer hollow molded product of the present invention are all excellent in melt moldability, stretch moldability, and gas barrier properties.

Claims (4)

[Claims] (1) (A) A polyester composition layer consisting of polyalkylene terephthalate (a) whose main constitutional unit is ethylene terephthalate and polyhydroxypolyether ester (b), (B) polyalkylene terephthalate whose main constitutional unit is ethylene terephthalate A polyester laminate molded article comprising a layer, wherein the polyhydroxy polyetherester (B) has the general formula [I
] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, R^1 represents a p-phenylene group, and R^2 represents a divalent hydrocarbon group having 2 to 18 carbon atoms. and R
^3 has 6 to 1 carbon atoms other than p-phenylene group
8 divalent aromatic hydrocarbon group, l and m are positive numbers, n is 0 or a positive number, l/(l+m+
n) is 0.3 to 1.0, m/(l+m+n)
is 0.01 to 0.5, and n/(l+m+n) is 0 to 0.7, provided that when R^2 is a p-phenylene group, m/(l+m+n) is less than 0.5. When R^2 is two or more divalent hydrocarbon groups including p-phenylene group, m/(l+m+n) is 0.
5 or the ratio of p-phenylene groups to all divalent hydrocarbon groups constituting R^2 is less than 0.6. ], the intrinsic viscosity [η] is in the range of 0.3 to 2 dl/g, and the glass transition temperature is in the range of 30 to 160°C. A polyester laminate molded product featuring: (2) (A) A polyester composition layer consisting of polyalkylene terephthalate (a) whose main constitutional unit is ethylene terephthalate and polyhydroxypolyether ester (b), and (B) polyalkylene whose main constitutional unit is ethylene terephthalate. A polyester stretch laminate molded article comprising a terephthalate layer, wherein the polyhydroxypolyetherester (b) has the general formula [
I 〕 ▲Mathematical formulas, chemical formulas, tables, etc.▼...[I] [In the formula, R^1 represents a p-phenylene group, and R^2 represents a divalent hydrocarbon having 2 to 18 carbon atoms. Indicates a group, R
^3 has 6 to 1 carbon atoms other than p-phenylene group
8 divalent aromatic hydrocarbon group, l and m are positive numbers, n is 0 or a positive number, l/(l+m+
n) is 0.3 to 1.0, m/(l+m+n)
is 0.01 to 0.5, and n/(l+m+n) is 0 to 0.7, provided that when R^2 is a p-phenylene group, m/(l+m+n) is less than 0.5. When R^2 is two or more divalent hydrocarbon groups including p-phenylene group, m/(l+m+n) is 0.
5 or the ratio of p-phenylene groups to all divalent hydrocarbon groups constituting R^2 is less than 0.6. ], the intrinsic viscosity [η] is in the range of 0.3 to 2 dl/g, and the glass transition temperature is in the range of 30 to 160°C. A polyester stretch laminate molded product characterized by: (3) (A) A polyester composition layer consisting of polyalkylene terephthalate (a) whose main constitutional unit is ethylene terephthalate and polyhydroxypolyetherester (b), and (B) polyalkylene whose main constitutional unit is ethylene terephthalate. A polyester multilayer hollow molded preform consisting of a terephthalate layer, in which the polyhydroxypolyetherester (b) has a general formula [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] [In the formula, R^1 represents a p-phenylene group, R^2 represents a divalent hydrocarbon group having 2 to 18 carbon atoms, and R
^3 has 6 to 1 carbon atoms other than p-phenylene group
8 divalent aromatic hydrocarbon group, l and m are positive numbers, n is 0 or a positive number, l/(l+m+
n) is 0.3 to 1.0, m/(l+m+n)
is 0.01 to 0.5, and n/(l+m+n) is 0 to 0.7, provided that when R^2 is a p-phenylene group, m/(l+m+n) is less than 0.5. When R^2 is two or more divalent hydrocarbon groups including p-phenylene group, m/(l+m+n) is 0.
5 or the ratio of p-phenylene groups to all divalent hydrocarbon groups constituting R^2 is less than 0.6. ], the intrinsic viscosity [η] is in the range of 0.3 to 2 dl/g, and the glass transition temperature is in the range of 30 to 160°C. A preform for polyester multilayer hollow molded bodies characterized by: (4) (A) A polyester composition layer consisting of polyalkylene terephthalate (a) whose main constitutional unit is ethylene terephthalate and polyhydroxypolyether ester (b), and (B) polyalkylene whose main constitutional unit is ethylene terephthalate. A polyester multilayer hollow molded body consisting of a terephthalate layer,
The polyhydroxypolyether ester (b) has the general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, R^1 represents a p-phenylene group, and R^2 is Represents a divalent hydrocarbon group having 2 to 18 carbon atoms, R
^3 has 6 to 1 carbon atoms other than p-phenylene group
8 divalent aromatic hydrocarbon group, l and m are positive numbers, n is 0 or a positive number, l/(l+m+
n) is 0.3 to 1.0, m/(l+m+n)
is from 0.01 to 0.5, and n/(l+m+n) is from 0 to 0.7. However, when R^2 is a p-phenylene group, m/(l+m+n) is less than 0.5, and R^2 is two or more divalent hydrocarbon groups containing a p-phenylene group. In this case, m/(l+m+n) is 0.
5 or the ratio of p-phenylene groups to all divalent hydrocarbon groups constituting R^2 is less than 0.6. ], the intrinsic viscosity [η] is in the range of 0.3 to 2 dl/g, and the glass transition temperature is in the range of 30 to 160°C. A polyester stretched multilayer hollow molded product characterized by: