JPS6216144A - Polyester laminates and their uses - 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 [Industrial Field of Application] The present invention provides a polyester laminate molded product having excellent melt moldability, excellent mechanical strength and gas barrier properties, and performance that can pass 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 empty containers are usually collected after use.
A method of circular reuse is adopted. however,
Glass containers are heavy, which increases shipping costs, and they also have drawbacks such as being easily damaged and inconvenient to handle.

In order to overcome the aforementioned disadvantages of glass containers, there is a growing shift from glass containers to various plastic containers. Various plastics are used as materials depending on the type of stored item and its intended use. Among these plastic materials, polyethylene terephthalate has excellent gas barrier properties and transparency, and is therefore used as a material for containers for seasonings, soft drinks, detergents, cosmetics, and the like. However, polyethylene terephthalate is still not sufficient for beer and carbonated beverage containers, which require the most stringent gas barrier properties, 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 melt moldability.

JP-A-59-64624 discloses polyalkylene isophthalates 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 comprising a layer made of a polyalkylene isophthalate or a copolymer thereof as described above and a layer made of a polyalkylene terephthalate such as poly(ethylene terephthalate) or a copolymer thereof, and a molded product made thereof, such as a bottle. Disclosed.

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

Although it is a material different from polyester, it is
No. 296 discloses that m-xylylene diamine or a mixture of m-xylylene diamine and p-xylylene diamine is used as a diamine component, and a dicarboxylic acid component of a mixture of a specific aromatic dicarboxylic acid and an aliphatic dicarboxylic acid is used as a diamine component. A polyamide with good transparency 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 No. 56-64866 discloses that the outermost layer and the innermost layer are made of polyester having ethylene phthalate as the main repeating unit, and the middle layer is made of m-xylylene diamine or m-xylylene diamine and p-kypa7lylene diamine. A multilayer container is disclosed, which is made of a polyamide containing a mixture of as a diamine component, and in which the thin wall portion is oriented in at least one direction.

The publication states that the container does not impair the excellent mechanical properties, transparency, chemical resistance, etc. of polyester (and has excellent oxygen barrier properties).

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 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 (c), +O-E -0-CI+2-CH-Cl
-12 Force -(g)CH Here, E is CH3 CHs i-C3Fi7. The gas barrier properties of the homopolyhydroxy ether represented by the following are disclosed. Most oxygen permeable 0.5cc-
ml/100 in/24hr/atm.

The one with the lowest water vapor mobility has an E of 5 g-mil/1 under CI (5 1,90% R, H,
00 in2/24hr.

Also, Journal of ApT)liend P
olymerScience, Volume 7, 2145-2
152 (1965) discloses the gas barrier properties of a fubohydroxy polyether represented by the following formula (wherein R1 and R2 are not the same). The highest H3 value of oxygen permeability is 5 g-ml/100 in/24 hr
/atm. The one with the lowest water vapor mobility is 4g-m+j under the conditions where R1 is Br and M3 Hr CH3 90% R, H? /100i
It is n2/24hr.

[Problem that the invention seeks to solve]

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

Another object of the present invention is to provide a polyester laminate molded product comprising a polyhydroxypolyester having excellent gas barrier properties, particularly barrier properties against oxygen and carbon dioxide.

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: 8. Polyalkylene terephthalate fat and polyhydroxy polyester (bl and (B) a polyalkylene terephthalate layer containing ethylene terephthalate as a main constituent unit, wherein R1 represents a p-phenylene group and R2 represents a divalent hydrocarbon group having 2 to 18 carbon atoms other than p~phenylene group, R3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and β is a positive number. , m and n are 0 or positive numbers, and l/(x+m+n) is 0.
3 to 1.0, m/(j2 +m+n)
is from 0 to 0.7, and n/(6+m+n) is from 0 to 0.5. ], and the intrinsic viscosity [η]
This is achieved by a polyester laminate molded article characterized in that it is a substantially linear polyhydroxypolyester having a glass transition temperature of 0.3 to 2 di/g and a glass transition temperature of 30 to 160°C.

The polyhydroxy polyester (bl) used in the polyester composition layer (2) of the present invention is novel and can be produced, for example, by the method below.

That is, (a) diglycidyl of at least one dicarboxylic acid represented by the general formula (Ill...(II [in the formula, R4 represents a divalent hydrocarbon group having 2 to 1 carbon atoms]); and (b) general formula [D (c) general formula HO-R-OH...1] [wherein R represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms] [In the formula, R1 represents a p-phenylene group] and at least one aromatic diol represented by the general formula (1) and R2 is p-
represents a divalent hydrocarbon group having 2 to 18 carbon atoms other than a phenylene group, R represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, l is a positive number, m and n are 0 or positive numbers], m and n of the polyhydroxy polyester are ゛0.5≦1'(C+na+n)≦1.00≦m/(6
+m+n)≦0.7 0≦n/(j?+m+n)≦0.5, and can be produced by reacting in an organic solvent.

When m = 0 and n = 0 in the above general formula (1), the polyhydroxy polyester M used in the present invention has the general formula (D [wherein R and l are the same as above] It is expressed as
When n = Q, it is represented by the general formula (VD...[Φ [in the formula, -R, R, l and m are all the same as above], and when m = O, It is represented by the general formula (to) [wherein R-R-l and n are the same as above], and further, when both 1.I!l and n are not 0, the general formula [I] (However, m\0
, n\0). When the polyhydroxy polyester is represented by the above general formula [■], its structure is a homopolyester, but when it is represented by the above general formula [D, general formula (to) or general formula (1')] The structure of the polyhydroxy polyester is and/or +or:H2ct+cq2o-R3-)
TE table b Each constituent component that sat'L is randomly arranged.

In the polyhydroxy polyester represented by the general formula (I) used in the present invention, l is a positive number, and m and n are both 0 or a positive number.The general formula CI''
The proportion of each component that makes up l is Jl? / (j7+
m+n) is in the range from 0.5 to 1.0, preferably from 0.4 to 1.0, particularly preferably from 0.5 to 1.0, and m/(g+m+n) is from 0 to 0.7, preferably 0 to 0.6, particularly preferably 0 to 0.6.
5, and n/(l+m+n) ranges from 0 to 0.5. When the value of Ill (j?+m+n) in the polyhydroxy polyester becomes smaller than 0.5, and the value of m/(l+m+n) becomes larger than 0.7, the gas barrier properties of the polyhydroxy polyester decrease. However, undesirable phenomena such as a decrease in the glass transition temperature or a decrease in the gas barrier properties and mechanical strength of the composition with polyalkylene terephthalate are observed.

The polyhydroxy polyester used in the present invention is substantially linear. Here, the term "substantially linear structure" means that it consists essentially of a chain structure having a straight chain or a branched chain, and does not mean that it is substantially a linear cross-linked structure (C network structure). do. This is confirmed by the fact that the polyhydroxy polyesters of the present invention are substantially completely dissolved in the solvent in which the intrinsic viscosity is measured.

R constituting the polyhydroxy polyester represented by the general formula (I) used in the present invention is a p-phenylene group theal. terR indicates a divalent hydrocarbon group having 2 to 18 carbon atoms other than p-phenylene group, and the divalent hydrocarbon group contains a halogen atom, an oxygen atom, or a sulfur atom in the molecule. You may do so. The divalent hydrocarbon group R
As ingredient +CH+ (-CH+ +ct(2+4.
+cH2 is also an alicyclic hydrocarbon group such as 22-23%.

Examples include alicyclic hydrocarbon groups such as.

These divalent hydrocarbon groups may be a mixed component of two or more types.

Further, R which can constitute the polyhydroxy polyester represented by the general formula [I] used in the present invention represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the divalent aromatic The hydrocarbon group may contain a halogen atom, an oxygen atom or a sulfur atom in the molecule. Specifically, the divalent aromatic hydrocarbon group R is:

Examples include CF (3). These divalent aromatic hydrocarbon groups may be a mixture of two or more types. Among these aromatic hydrocarbon groups, &i, p-F s-nylene group 1m-phenylene group, 2.6-naphthylene group,
p, p'-biphenylene group, 4. a'-oxydiphenylene! , 4.4'-thousodiphenylene group, 4.4-sulfodiphenylene group, 4.4'-methandiphenylene group, 2
．． 2-propane-bis-4-phenylene group and the like are preferred.

The polyhydroxypolyester used in the present invention varies depending on the proportion of raw material compounds used when producing it.
The terminal thereof can be an epoxy group or a phenol V-hydroxyl group. These terminal carboxyl groups, hydroxyl groups or epoxy groups can be converted into V-boxylic acid esters, such as acetic acid esters A/(-0000H3), by esterification methods known per se.

It can be converted into methyl ester (-a o o (! H3)-ethyl ester (-0000H20H3), etc.).

The polyhydroxy polyesters used in the present invention include those having various terminals as described above.

As mentioned above, the polyhydroxy polyester used in the present invention has an intrinsic viscosity of 0.5 to 261/g and a glass transition temperature of 50 to 160°C. Intrinsic viscosity is 267? If it exceeds /g, the melt moldability of the polyhydroxypolyester V composition will decrease, and furthermore, its stretchability will also decrease. Further, when the intrinsic viscosity is less than 0.5c311/l, the mechanical strength of the polyhydroxypolyester composition and its spread product decreases. The polyhydroxy polyester used in the present invention is preferably 0.4 to 1,
5 djl? /g, more preferably 0.4-1.2d/
It shows an intrinsic viscosity of /E.

On the other hand, if the glass transition temperature is lower than 30° C., it becomes difficult to perform drying economically.

The polyhydroxypolyester I used in the present invention is
Preferably 40-14Q℃, more preferably 40-1
It has a glass transition temperature of 20°C.

The polyhydroxy polyester used in the present invention has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (M
The value indicating the molecular weight distribution defined by w/Mn) is usually in the range of 1.5 to 10, for example.

The polyhydroxy polyester used in the present invention comprises a diglycidyl ester of at least one dicarboxylic acid represented by the above general formula [rll] and a diglycidyl ester of at least one dicarboxylic acid represented by the above general formula [rll];
It is formed by reacting at least one dicarboxylic acid represented by the formula G and/or at least one aromatic diol represented by the general formula G] in an organic solvent. The diglycidyl ester of dicarboxylic acid represented by the above general formula CM is a diglycidyl ester of dicarboxylic acid in which the hydrocarbon group R4 constituting it is a divalent hydrocarbon group having 2 to 18 carbon atoms. ,
Preferably, it is a diglycidyl ester of cicaV acid, in which R is a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and particularly preferably, R4 is a diglycidyl ester of carbonic acid having a carbon number of 6 to 18 carbon atoms, and is particularly preferably is a diglycidyl ester of cafrebonic acid, which is a divalent aromatic hydrocarbon group having 6 to 1 days.

The constituent hydrocarbon group R has a halogen atom in the molecule.

It may contain an oxygen atom or a sulfur atom.

Specifically, the diglycidyl ester of the dicarboxylic acid includes diglycidyl terephthalate, diglycidyl isophthalate, diglycidyl phthalate, diglycidyl/L/
-2-Methyl terephthalate, diglycidyl-2-chloroterephthalate, diglycidyl-5-methylisophthalate, diglycidyl-2,6-naphthalene dicarboxylate, diglycidyl-1,5-naphthalene dicarboxylate, diglycine/l/- 1,4-naphthalene cicafurboxylate, diglycidyl-4,4-diphenyl ether dicarboxylate, diglycidyl-4,4-diphenyl ether dicarboxylate, diglycidyl-4+ 4-'/Fueni I Resulfonji Power! Examples include levoxylate, diglycidyl-4,4-diphenylmethane dicarboxylate, and diglycidyl-4,4-cyphenylpropanedica I levoxylate. The diglycidyl ester of Cica I levonic acid represented by the general formula [1].

In the process of production, it may contain a small amount of halogen atom that may be mixed in, and the following general formula (Vl!l'), which is produced by further addition reaction to the ebogishi group, In formula C, the definition of R4 is the same as above, and p is a positive number from 1 to 10). Polyhydroxypolyester (1'
) may be contained in a small amount within a range that does not reduce the molecular weight.

At least one dicarboxylic acid represented by the general formula ``is a hydrocarbon group R5 having 2 carbon atoms.
It is a dicarboxylic acid which is a divalent hydrocarbon group having 1 to 18 atoms, and the hydrocarbon group may contain a rogen atom, an oxygen atom or a sulfur atom. As the hydrocarbon group R5 constituting the dicarboxylic acid, the hydrocarbon groups exemplified as the hydrocarbon groups R1 and R2 in the general formula (II) can be exemplified in exactly the same manner. V phthalic acid, chloroisophthalic acid, methyl terephtha Iv'NI, phthalic acid, isophthalic acid, 5
-Methyl isophthalic acid, 5-chloroisophtha v 5!
.

2.6-naphthalene dicarboxylic acid, 1.5-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid I repon m, 2
゜7-naphthalene dicarboxylic acid, 4,4-diphenyl M dicarboxylic acid, 4,4-diphenyl ether M dicarboxylic acid a
, 4,4'-benzophenonedicarboxylic acid, 4. ii-
Sipheunires I lehon dicarvone m, 4 + 4-
Aromatic dicarboxylic acids such as dicarboxylic acid, 4.4-dipropanedicarboxylic acid, 4.4-triphenylmethanedicarboxylic acid, 4.4-tetraphenylmethanedicarboxylic acid, succinic acid, and M Examples include aliphatic dicarboxylic acids such as tarric acid, adipic acid, and pyruvic acid, and alicyclic dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,5-dicarboxylic acid.

At least one aromatic di-M represented by the above general formula G] is a di-M in which the aromatic hydrocarbon group R3 constituting it is an aromatic hydrocarbon group having 6 to 20 carbon atoms.
1, and the aromatic hydrocarbon group may contain a halogen atom, an oxygen atom, or a sulfur atom. Specific examples of the aromatic di-1 include hydroquinone, reso-V-syn, catechol, methylhydroquinone, 2,5-dimethylhydroquinone, 2,6-dimethylhydroquinone, 2,5.5.6 - Chitrame 1,000M hydroquinone, phenylhydroquinone, chloridehydroquinone, 2,
6-dichlorohydroquinone, 2-metholreso M-syn,
2,4゜6-drimethylresorcin, 2,6-naphthalenedio-7, 2,7-naphthalenedio-I, 1,5
-Naphthalenediol, 1,4-naphthalenedi, t-l,p,p-hyphenol, 4.4-oxydiphenol, 4゜4-ketodiphenol, 4.4-thiodiphenol
1-7! Near L/-1,1
-bis(4-hydroxyphenylv)ethane, 4.4-
Dipheno-M dipheniM methane, 4,4'-dihydroxy-5°5', 5,5-tetrametal bipheniM, bis(4-hydroxydi,5-dimethylphenyl)ether, bis(4-hydroxy-di, 5-dimethylphenyl), 5-dimethane, 2,2-bis(4-hydroxy-5,5
-dimethylphenyl)propane, 9.9-dimethylphenyl 5
, 6-hydroxyxanthene, etc. Among the aromatic diols, hydroquinone, resofrescin, 2,6-naphthalene 7', p*p-biphenol, 4,4'-oxydiphenol, 4,4-
Ketodiphenol, 4,4-sulfodipheno-I, bis(4-hydroxy-5,5-dimethyl phenyl)methane, 2,2-bis(4-hydroxy-3,5-dimethyl phenyl)
Phenyl)propane is preferred.

In the above method, the diglydyl ester of the dicarboxylic acid and the dicarboxylic acid and/or the aromatic di-1 are combined to form a polyhydroxypolyether having the general formula [I] niote, (1/(β0 m+n) ratio of 0.5 to 1.O1, preferably 0.4 to 1.0;
Particularly preferably in the range of 0.5 to 1.0, m/(
jl? +m+n) ranges from 0 to 0.7, preferably from 0 to 0.6, particularly preferably from 0 to 0.5, and the ratio n/(,g-1-m+n) ranges from 0 to 0.
．． The charging ratio of each raw material is adjusted and supplied so that it falls within the range of 5. In the reaction system, the total number of moles of the dicarboxylic acid and the aromatic diol per mole of the diglycidyl ester of the dicarboxylic acid is usually 0.95 to 1.
05, preferably from 0.97 to 1.05, particularly preferably from 0.98 to 1.02,
The diglycidyl ester of the dicarboxylic acid, the dicarboxylic acid and/or the aromatic diol are provided.

In the method for producing the polyhydroxy polyester, the reaction between the diglycidyl ester of dicarboxylic acid and the dicarboxylic acid and/or aromatic diol is carried out in the presence of an organic solvent. The organic solvent is preferably one that is soluble in the diglycidyl ester of aromatic dicarboxylic acid, dicarboxylic acid and/or aromatic diol that is the raw material, and the polyhydroxy ester that is the resulting polymer, such as methyl in butyl ketone, Cyclohexanone, 2-butanone, acetophenone, γ-butyrolactone, sulfolane, dimethyl sulfoxide, 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 30-200°C, preferably at about 100-200°C.
It is carried out at a temperature of so''c.

Although the reaction proceeds in the above temperature range without a catalyst, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-inbutylamine, tri-n-hexylamine, and tricyclohexylamine are used.

tertiary amines such as dimethylbenzylreamine, tetramethylammonium hydroxide such as tetramethylammonium hydroxide, tetraethylreammonium hydroxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide; oxide, sodium ethylate, sodium ethylate, sodium isopropionate,
Alcolades of alkali metals such as sodium r-butylene, potassium methylate, potassium ethylate,
Alternatively, it is preferable to carry out the reaction in the presence of an appropriate small amount of a basic compound such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, etc., since one reaction is promoted.

After the repulsion, 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 [wherein R
represents a p-phenylene group, R represents a divalent hydrocarbon group having 2 to 18 carbon atoms other than the p-phenylene group, and R represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. represents a group, l is a positive number, m and n are O or positive numbers, IJ/(/+m+n) is 0.5'f:
1.0, m/(j'+m+n) is 0 to 0.7, and n/(1-+-m+n) is 0 to 0.
．． It is 5. ) is obtained which is a substantially linear polyhydroxy polyester. In the above method, by reacting the raw material with diglycol ester of terephthalic acid and terephthalic acid (Vm) in step 17, a polyhydroxypolyester represented by the general formula [V] can be obtained. In addition, when dicarboxylic acid diglycidi 7 reeste IV todicarboxylic acid is reacted as a raw material in a proportion such that terephthalic acid component units in all dicarboxylic acid component units are 50 mol% or more, polyhydroxypolyester represented by the general formula I can get the result. When a diglycidyl ester of terephthalic acid and an aromatic diol are reacted as raw materials, or a diglycidyl ester of terephthalic acid, terephthalic acid, and an aromatic diol are reacted, a polyhydroxypolyester represented by the general formula (2) is obtained. Furthermore, diglycol ester of dicarboxylic acid, dicarboxylic acid, and diol are reacted as raw materials in a proportion such that the terephthalic component units in all dicarboxylic acid component units are 80% or more. (However, m\
0, n\0) is obtained.

The polyhydroxy polyester 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 cough polyalkylene terephthalate may contain small amounts 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, neopendel glycol, cyclohexanediol, cyclohexane dimetatool, 1゜4-bis(β -hydroxyethoxy)benzene, 183-bis(β-hydroxyethoxy)benzene, 2゜2-bis(4-β-hydroxyethoxyphenyl)propane, bis(4-β-hydroxyethoxyphenyl)sulfone, etc. 3 to 1
The diol component unit of No. 5 can be exemplified.

In addition, the polyalkylene terephthalate may contain a small amount of a polyfunctional compound, if necessary, in addition to the aromatic dicarboxylic acid component unit and the diol component unit. Specifically, the polyfunctional compound component units include trimellitic acid, trimesic acid, 3,3°,
5. Aromatic polybasic acids such as 5'-tetracarboxydiphenyl, aliphatic polybasic acids such as butanetetracarboxylic acid, aromatic polyols such as phloroglucin, 1,2,4.5-tetrahydroxybenzene, 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 in the range of 0 to 50 mol%, preferably 0 to 30 mol%. , the content of ethylene glycol component units is usually in the range of 50 to 100 mol%, preferably 70 to 100 mol%, and the content of diol component units other than ethylene glycol component units is usually 0 to 50 mol%, preferably The content of polyfunctional compound component units is usually in the range of 0 to 30 mol % and in the range of O to 2 mol %, preferably O to 1 mol %. Further, the limiting viscosity [η] of the polyalkylene terephthalate [value measured at 25°C in a mixed solvent of phenol-tetrachloroethane (weight ratio 1/l)] is usually 0.5 to 1.5 dl/g, preferably is in the range of 0.6 to 1.2j/g, and the melting point is usually 210 to 2
The glass transition temperature is usually 50 to 120°C, preferably 60 to 100°C.

In the polyester composition, the blending ratio of polyhydroxypolyester (b) is usually 2 to 500 parts by weight per 100 parts by weight of the polyalkylene terephthalate (al).
Parts by weight are preferably in the range from 3 to 300 parts by weight, particularly preferably from 5 to 100 parts by weight.

In addition to the polyalkylene terephthalate (al) and the polyhydroxy polyester (bl), the polyester composition may contain conventionally known nucleating agents, inorganic fillers, lubricants, slip agents, anti-blocking agents, and stabilizers, as required. , an antistatic agent, an antifogging agent, a pigment, and other various additives may be blended in appropriate amounts.

Next, the polyester laminate molded article of the present invention composed of the polyester composition layer (c) and polyalkylene terephthalate (r@[F]) whose main constituent unit is ethylene terephthalate will be described. Specifically, the laminate molded product is a two-layer laminate molded product composed of two layers, the polyester composition layer and the polyalkylene terephthalate layer, the polyester composition layer is the middle layer, and both outer layers are the polyester composition layer and the polyalkylene terephthalate layer. A three-layer laminate molded product having an alkylene terephthalate layer, a three-layer laminate having the polyalkylene terephthalate layer as an intermediate layer and both side layers as the polyester composition layer.

a layered molded product, a multilayer laminate molded product having a four-layer structure or more in which layers of the polyester composition and layers of the polyalkylene terephthalate are alternately laminated, both outermost layers of which are composed of the polyalkylene terephthalate layer; A multilayer laminate molded product having a four-layer structure or more in which layers of the polyester composition and layers of the polyalkylene terephthalate are alternately laminated, the outermost layers of which are both layers of the polyester composition, and the polyester composition layer. Examples include a multilayer laminate molded product having a four-layer structure or more in which the polyalkylene terephthalate layers are alternately laminated, and the outermost layer is composed of the polyester composition layer and the polyalkylene terephthalate layer. can. The laminated molded product 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, and the like. The laminate can be manufactured by a conventionally known method.

The thickness of the polyester composition layer and the polyalkylene terephthalate layer constituting the laminate molded product are appropriately determined depending on the use of the laminate molded product, and are not particularly limited. When the laminate molded product is the two-layer laminate molded product, the thickness of the polyester composition layer is usually 1.
The thickness of the polyalkylene terephthalate layer ranges from 8 to 600μ, preferably from 10 to 500μ.

When the laminate 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 layers of the polyalkylene terephthalate layer is usually in the range of 4 to 300μ,
Preferably it is in the range of 5 to 250μ. 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 both outer layers of the polyester composition is usually I to 100μ, preferably 1
The range is from 50μ to 50μ. 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 as described above.

The polyalkylene terephthalate (al) constituting the polyester composition layer does not necessarily have to be the same as the polyalkylene terephthalate (al). Appropriate amounts of various additives such as inorganic fillers, lubricants, antiblocking agents, stabilizers, antistatic agents, antifogging agents, and pigments may be blended.

The polyester laminate molded article 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 general formula of a polyester composition and a polyalkylene terephthalate layer (B) having ethylene terephthalate as a main constituent unit, will be described. The polyester stretch laminate molded product of the present invention is a polyester laminate molded product that is composed of the polyester composition layer and the polyalkylene terephthalate N, and has the above-mentioned laminate structure, and at least one of the polyalkylene terephthalate layers is stretched. This is a polyester stretch laminate molded product in a stretched state.

Preferably, the polyester is a polyester laminate molded product consisting of the general formula of the polyester composition and the polyalkylene terephthalate layer 03) and having the above-mentioned laminate structure, and at least all of the polyalkylene terephthalate layers are in a stretched state. A stretch laminate molded product, particularly preferably a polyester laminate molded product having the above-mentioned laminate structure, comprising the polyester composition formula and the polyalkylene terephthalate layer (1), and the polyester composition layer and the polyalkylene terephthalate layer. All layers of the layer are in a stretched state. The stretched layer may be in a −axially stretched state or in a biaxially 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.
．． The stretching ratio 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 two-wheel stretched layer, the stretching ratio is in the longitudinal direction. Usually 1.1 to 8 times, preferably 1 in the axial direction
．． It is in the range of 2 to 7 times, particularly preferably 1.5 to 6 times, and in the horizontal axis direction is usually 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5 to 6 times. is within the range of 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 used for manufacturing the same.

Generally, the polyester composition and the polyalkylene terephthalate are melted in separate extruders, and the original laminate molded product, such as a multilayer laminate film or laminate sheet, is molded from a multilayer T-die by a melt coextrusion method while being heated. Alternatively, a method may be employed in which the material is cooled and solidified to a temperature below the double-layer glass transition point, further reheated, 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. It may be uniaxially stretched, it may be biaxially stretched, or it may be similarly stretched after lamination. Among these stretching methods, if the first coextrusion method is used to form an original laminate molded product and then a stretching treatment is applied, the process is simple and the polyester stretched laminate molded product has excellent interlayer adhesion. This is particularly preferred because it provides the following.

In addition, when producing the polyester stretch laminate molded product,
When the evaporated molded product is a film or sheet, the stretching treatment can be performed by stretching the evaporated molded product in a uniaxial direction (-axial stretching), or by stretching the evaporated molded product 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 in which the material is stretched in both directions, and a so-called vacuum forming method in which the material is stretch-formed by reducing the pressure in the space between the vapor-molded product and the mold. The temperature during the stretching treatment is in the range of the glass transition point or melting point of the resin constituting the vapor-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 primam for multilayer hollow molded bodies having the above-mentioned laminated structure. Examples of the preform having a laminate structure include the two-layer laminate molded product preform exemplified in the laminate molded product of the present invention described above, the similar three-layer laminate molded product preform, and the similar multi-layer laminate molded product preform with four or more layers. Renovation can be similarly exemplified. Among these preforms for multilayer hollow molded bodies, there are preforms having a laminated structure consisting of two layers, the polyester composition layer and the polyalkylene terephthalate layer, and the polyester composition as an intermediate layer and both valve sides. When a stretched multilayer hollow molded body is formed from a preform having a laminated structure consisting of three layers of the polyalkylene terephthalate layer, the stretched multilayer hollow molded body has excellent properties such as excellent mechanical strength, transparency, and gas barrier properties. This is preferred because a multilayer hollow molded body can be obtained.

If necessary, conventionally known nucleating agents, inorganic fillers, lubricants, slip agents, and anti-blocking agents may be used in both the polyester composition and the polyalkylene thirefrate constituting the preform for a multilayer hollow molded body of the present invention. , stabilizers, antistatic agents, antifogging agents, pigments, and other various additives may be blended in appropriate amounts.

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

For example, the preform for a polyester multilayer medium-projection molded article of the present invention can be obtained by molding the tubular article having the laminated structure.

The polyester stretched 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 Ff, 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 hollow body is the two-layer hollow molded body, it is a stretched two-layer hollow molded body in which the polyester composition layer is the outer layer and the polyalkylene ethylene reflex crate N is the inner layer. Alternatively, 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 (1) f multilayer hollow molded product may be a uniaxially stretched molded product or a biaxially stretched molded product, but in general, a biaxially stretched molded product has better mechanical strength and gas barrier properties. −
It is suitable because it has excellent properties. 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 polyester 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 the polyhydroxy polyester was determined by measuring it in 0-chlorophenol at 25°C.

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

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 PHRMATRA-N C-IV device manufactured by MOCON.

Reference Example I N ~ In a reaction tank loaded with 7500 parts of methylpyrrolidone,
Diglycidyl terephthalate (Journal ofC
chemical and engineering D
ate, Volume 11, 448-449 (1966)
281 parts of epoxide (epoxide content: 7.1 epoxide equivalents/km), 166 parts of terephthalic acid, and 2 parts of N,N-dimethylbenzylamine were charged, and the temperature of the system was lowered while stirring. When the temperature was raised to about 140°C, an increase in the viscosity of the system was observed after about 30 minutes, so N-methylpyrrolidone 10 was added to continue stirring.
The reaction was carried out for about 3 hours while adding 0.00 parts. After the reaction was completed, the reaction mixture was poured into a large amount of water to precipitate the polyhydroxy polyester produced, and then the polyhydroxy polyester was washed with water and methanol, collected, and dried under vacuum at 40°C. did. The yield of the polyhydroxy polyester thus obtained was 393 parts.

In addition, the intrinsic viscosity of this polyhydroxy polyester is 0
．． 64 dl/g, the glass transition temperature is 54°C,
Ivy. The composition of this polyhydroxy polyester is a structure in which terephthalic acid component units and 2-hydroxy-1,3-propanediol component units are alternately dehydrated and condensed to form ester bonds (j2:m:n=50:50: O).

Reference Examples 2 to 3 Polyhydroxypolyesters were obtained in the same manner as in Reference Example 1, except that terephthalic acid and hydroquinone or hydroquinone were used in the amounts shown in Table 1 instead of terephthalic acid.

The yield, intrinsic viscosity, glass transition temperature, and ratio of terephthalic acid component units to hydroquinone component units of these polyhydroxypolyesters were as shown in Table 1.

Reference Examples 4 to 5 In Reference Example 2, the catalyst shown in Table 2 was used as shown in Table 2 instead of N,N-dimethylbenzylamine, and the solvent shown in Table 2 was used instead of N-methylpyrrolidone. Polyhydroxypolyesters 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 terephthalic acid component units to hydroquinone component units of these polyhydroxy polyesters were as shown in Table 2.

Reference Example 6 In Reference Example 3, 196.4 parts of diglycidyl terephthalate and diglycidyl isophthalate-1 (Journal of Che
mical and engineering data
a% 0, epoxide content 7, manufactured according to the method described in Vol. 11, 448-449 (1966)
．． A polyhydroxypolyester was produced in the same manner except that a mixture with 84.9 parts of 1-functional poxide equivalent/kg was used. The yield of the obtained polyhydroxypolyester was 325 parts, the intrinsic viscosity was 0.76 dl/g, and the glass transition temperature was 56°C. Also, the ratio (molar ratio) of terephthalic acid component units, isophthalic acid component units, and hydroquinone component units of this polyhydroxypolyester.
is 35:15:50 (1:m:n=50:O:50
)Met.

Reference Examples 7 to 10 In Reference Example 2, dicarboxylic acids shown in Table 3 were used as shown in Table 3 instead of terephthalic acid, and aromatic diols shown in Table 3 were used instead of hydroquinone as shown in Table 3. A polyhydroxy polyester was produced in the same manner except that The yield, intrinsic viscosity, glass transition temperature, and composition of the obtained polyhydroxypolyester were as shown in Table 3.

Reference Example 11 Instead of diglycidyl terephthalate in Reference Example 1, diglycidyl terephthalate (epoxide content: 5.7 epoxide equivalents/kg, chlorine content: 1 .2%) was used, and the amount of N-methylpyrrolidone used before starting the reaction was reduced to 60 parts.
A polyhydroxypolyester was produced in the same manner as in Reference Example 1, except that the amount of N-methylpyrrolidone added during the reaction was 1200 parts. The yield of the obtained polyhydroxy polyester was 460 parts. In addition, the extreme viscosity of this polyhydroxy polyester is 0.71 dl/g, and the glass transition temperature is 55°.
It was C. The composition of this polyhydroxypolyester is terephthalic acid component units and 2-hydroxyl 1,3
- A structure in which propanediol component units are alternately dehydrated and condensed to form an ester bond (l:m:n=50:501
) and contained 0.8% chlorine.

Reference example 12 Digcidyl terephthalate in Reference Example 11.

A polyhydroxy polyester was produced in the same manner as in Reference Example 3 except that 350.9 parts were used. The yield of the obtained polyhydroxy polyester was 419 parts. Also,
The intrinsic viscosity of the polyhydroxy polyester is 0.80
dl/g, and the glass transition temperature was 59°C. In addition, the ratio (molar ratio) of terephthalic acid component units and hydroquinone component units in polyhydroxypolyester is 56:4.
4 (6:m2n=50:0:50), and 0.
It contained 9% chlorine.

Reference Examples 13 to 15 Polyhydroxy polyesters were produced in the same manner as in Reference Example 11, 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 polyhydroxypolyester were as shown in Table 4.

Reference Examples 16 to 19 Polyhydroxypolyesters were produced in the same manner as in Reference Example 12, except that the aromatic diols shown 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 polyhydroxypolyester were as shown in Table 5.

Example 1 Polyethylene terephthalate (trade name, Mitsui 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 10
A mixture of 0 parts by weight and 40 parts by weight of the polyhydroxy polyester 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. The pellets of the composition were then press-molded at about 260°C to a thickness of about 1.
A 00μ press sheet was produced. Further, the press sheet of the polyethylene terephthalate and the press sheet of the composition of polyethylene terephthalate and polyhydroxy polyester are superimposed and press-molded at about 260°C to form a two-layer, two-layer laminate with a thickness of about 150μ. was created. The obtained laminated sheet has good adhesion between the polyethylene terephthalate layer and the composition layer, and its carbon dioxide gas permeability coefficient is 18 m1-m*/g・day
・ATM% and oxygen gas permeability coefficient is 3.217
・+u/rd-day ・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 25 ml-*m/g・day-a
tm, and the oxygen gas permeability coefficient is 4.51・Tsuru/g-
day・It was ATM.

Examples 2 to 11 In the same manner as in 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 polyester listed in Table 1 was used.
A two-layer, two-layer laminate sheet having a thickness of approximately 150 μm was produced. All of the obtained laminated sheets had good adhesion between the polyethylene terephthalate layer and the composition layer, and the carbon dioxide permeability coefficients of these laminated sheets were shown in Table 6.
It was as described.

Example 12 Polyethylene terephthalate isophthalate was used instead of the polyethylene terephthalate used in Example 5 [ratio of terephthalic acid component units to isophthalic acid component units (molar ratio) 90/10, intrinsic viscosity [η] 0.85
A/g) was prepared in the same manner as in Example 5 except that a polyethylene terephthalate/isophthalate layer and a composition layer of polyhydroxypolyester and polyethylene terephthalate/isophthalate had a thickness of about 150 mm.
A laminated sheet of two types and two layers of μ was prepared. The adhesion between the polyethylene terephthalate/isophthalate layer and the composition layer of this laminate sheet was good. In addition, the carbon dioxide permeability coefficient of this laminated sheet is 151 Z-mm/bo day
-It was an ATM.

Example 13 The polyethylene terephthalate in Example 1 was melted using an extruder at a molding temperature of about 270°C, and separately prepared in Example 1.
A mixture of 100 parts by weight of polyethylene terephthalate and 40 parts by weight of polyhydroxypolyester produced in the same manner as in Reference Example 12 was melted at about 260°C using another extruder to form a three-layer coating. The upper and lower layers are made of polyethylene terephthalate, and the middle layer is made of a composition, and the polyethylene terephthalate layers are fed into a hanger type T-die, extruded into a sheet, and further cooled with rolls, so that each polyethylene terephthalate layer is approximately 75 μm thick. In addition, a two-type, three-layer laminate sheet having a composition layer of about 75 μm was prepared. The obtained laminated sheet had good adhesion between the polyethylene terephthalate layer and the composition layer, and the carbon dioxide permeability coefficient was 19 mf-am.
/ g day - atm.

Example 14 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. Further, the carbon dioxide permeability coefficient of this biaxially stretched film was 9.5 m/·mm/m·day·atm.

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 15m/-mm/
It was r+(・day −aLm.

Examples 15 to 22 Biaxially stretched films having the stretching ratios shown in Table 7 were prepared in the same manner as in Example 14, except that the laminate sheets shown in Table 7 were used instead of the laminate sheets in Example 14.

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.

Example 23 Using a two-layer injection molding machine, the polyethylene terephthalate in Example I was melted by one injection molding machine at a molding temperature of about 270°C, and the mixture of polyethylene terephthalate and polyhydroxy polyester in Example 13 was separately melted. Molding temperature is approximately 270℃ using another injection molding machine.
The inner layer is made of polyethylene terephthalate (about 1.6 mm thick), and the outer layer is made of a composition of polyethylene terephthalate and polyhydroxypolyester. (
A two-layer preform with a thickness of approximately 1.6 mm was produced. Then, using a biaxial stretch blow molding machine (manufactured by Coho Plast Co., Ltd., LBOI), two wheels were stretched to 2.5 times the length and about 4 times the width, resulting in an inner volume of about 17! A multilayer container was fabricated.

The average thickness of the polyethylene terephthalate layer of this multilayer container is approximately 150μ, and the average thickness of the composition layer is approximately 150°C.
It was confirmed that the film was stretched uniformly. Also, the carbon dioxide permeability of this multilayer container is 2.1iZ/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 23 to obtain an inner volume of about 1.1 mm. A stretched polyethylene terephthalate bottle was molded.

The carbon dioxide permeability of this stretched bottle is 4. OiZ/day
・It was a bottle-ATM.

〔Effect of the invention〕

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

Claims (4)

[Claims] (1) (A) A polyester composition layer consisting of polyalkylene terephthalate (a) whose main constituent unit is ethylene terephthalate and polyhydroxypolyester (b), (B) a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate, A polyester laminate molded product composed of polyhydroxypolyester (b) having the general formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, R^1 is p- Represents a phenylene group, R^2 is p
- Represents a divalent hydrocarbon group having 2 to 18 carbon atoms other than a phenylene group, and R^3 is a divalent hydrocarbon group having 6 to 2 carbon atoms.
0 divalent aromatic hydrocarbon group, l is a positive number, m and n are 0 or positive numbers, l/(l+m+
n) is 0.3 to 1.0, m/(l+m+n)
is from 0 to 0.7, and n/(l+m+n) is from 0 to 0.5. ] and the intrinsic viscosity [η]
A polyester laminate molded article, characterized in that it is a substantially linear polyhydroxy polyester having a glass transition temperature of 0.3 to 2 dl/g and a glass transition temperature of 30 to 120°C. (2) (A) A polyester composition layer consisting of polyalkylene terephthalate (a) whose main constitutional unit is ethylene terephthalate and polyhydroxypolyester (b), and (B) a polyalkylene terephthalate layer whose main constitutional unit is ethylene terephthalate. , and the polyhydroxypolyester (b) has the general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] [In the formula, R^1 is p-phenylene group, R^2 is p
- Represents a divalent hydrocarbon group having 2 to 18 carbon atoms other than a phenylene group, and R^3 is a divalent hydrocarbon group having 6 to 2 carbon atoms.
0 divalent aromatic hydrocarbon group, l is a positive number, m and n are 0 or positive numbers, l/(l+m+
n) is 0.3 to 1.0, m/(l+m+n)
is from 0 to 0.7, and n/(l+m+n) is from 0 to 0.5. ] and the intrinsic viscosity [η]
1. A polyester stretch laminate molded article, which is a substantially linear polyhydroxy polyester having a glass transition temperature of 0.3 to 2 dl/g and a glass transition temperature of 30 to 120°C. (3) (A) A polyester composition layer consisting of polyalkylene terephthalate (a) whose main constituent unit is ethylene terephthalate and polyhydroxypolyester (b), and (B) a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate. , a polyester multilayer hollow molded preform consisting of the polyhydroxypolyester (b) has the general formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] [In the formula, R ^1 represents p-phenylene group, R^2 represents p-phenylene group, and R^2 represents p-phenylene group.
- Represents a divalent hydrocarbon group having 2 to 18 carbon atoms other than a phenylene group, and R^3 is a divalent hydrocarbon group having 6 to 2 carbon atoms.
0 divalent aromatic hydrocarbon group, l is a positive number, m and n are 0 or positive numbers, l/(l+m+
n) is 0.3 to 1.0, m/(l+m+n)
is from 0 to 0.7, and n/(l+m+n) is from 0 to 0.5. ] and the intrinsic viscosity [η]
1. A preform for a polyester multilayer blow molded article, characterized in that it is a substantially linear polyhydroxy polyester having a glass transition temperature in a range of 0.3 to 2 dl/g and a glass transition temperature in a range of 30 to 120°C. (4) (A) A polyester composition layer consisting of polyalkylene terephthalate (a) whose main constituent unit is ethylene terephthalate and polyhydroxypolyester (b), and (B) a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate. , and the polyhydroxypolyester (b) has the general formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼...[I] [In the formula, R^1 is p-phenylene group, R^2 is p
- Represents a divalent hydrocarbon group having 2 to 18 carbon atoms other than a phenylene group, and R^3 is a divalent hydrocarbon group having 6 to 2 carbon atoms.
0 divalent aromatic hydrocarbon group, l is a positive number, m and n are 0 or positive numbers, l/(l+m+
n) is 0.3 to 1.0, m/(l+m+n)
is from 0 to 0.7, and n/(l+m+n) is from 0 to 0.5. ] and the intrinsic viscosity [η]
A polyester stretched multilayer hollow molded article, which is a substantially linear polyhydroxy polyester having a glass transition temperature of 0.3 to 2 dl/g and a glass transition temperature of 30 to 120°C.