JPS61277443A - 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 relates to a polyester composition having excellent melt moldability, excellent mechanical strength and gas barrier properties, and suitable performance as a material for containers, and uses thereof. It is related to.

[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 was 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, poly'-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 the wall thickness must be increased in order to use polyethylene terephthalate for these containers. As a result, gas barrier properties had to be improved. Currently, the demand for polyester containers is increasing, and in order to expand these uses, there is a strong demand for polyesters that have excellent gas barrier properties and excellent melt moldability.

JP-A-59-64624 discloses polyisophthalates such as poly(ethylene isophthalate) and copolymers thereof and molded articles formed therefrom as packaging materials having good gas barrier properties against oxygen and carbon dioxide. is disclosed.

Japanese Unexamined Patent Publication No. 59-670 filed by the same applicant as the above application
Publication No. 49 discloses a multilayer packaging material consisting of a layer made of polyisophthalate or a copolymer thereof as described above and a layer made of polyterephthalate such as poly(ethylene terephthalate) or a copolymer thereof, and a molded article made therefrom.
For example, a bottle is disclosed. Also, JP-A-59-3
No. 9547, the innermost layer is made of polyester having ethylene terephthalate as the main repeating unit, the outer layer is made of polyester having ethylene phthalate as the main repeating unit, and the thin wall portion of the container is blended in at least one direction. A multilayer container with excellent gas permeability resistance 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-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-xylylene diamine. Consisting of polyamide with a mixture as a diamine component,
Moreover, a multilayer container is disclosed in which the thin wall portion is oriented in at least one direction ζζ. 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 hydroquinone and epihalohydrin are characterized by low permeability to oxygen and carbon dioxide.

Also, Journal of 5pplied Po
lymerf3c 1ence Volume 7 2135-214
4 (1963) discloses the gas barrier properties of a homopolyhydroxy ether represented by the following formula (A). Most oxygen permeable 0.5Cc-
mil/l 00 in”/24 hr/24 h
r/atm. The lowest water vapor mobility is that of E, which has a value of 100°F and 190%R,H.

39-ml 1/100 in”/24
It is hr.

Also, Journal of Applied Po
lymerScience Volume 7, 2145-2152
(1963) This is the following formula (B) -14,-beno(,:l-1,Ul-1(,:l-1,
(J-R, -ichihiba;li, [1-IL:11.(J...
...(b) (However, R1 and R2 are not the same) The gas barrier property of the copolyhydroxy polyether is disclosed.The highest value of oxygen permeability is 5.
9-Ilj/ 10 Q in”/ 24 hr/ai
It is m. The one with the lowest water vapor mobility has R1 of 10
411-M/100 under the conditions of 0〒, 90% R, Ho
in”/24 hr.

[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 polyether as a constituent component.

Another object of the present invention is to provide a polyester laminate molded product containing polyamide 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 drawn product of the above-mentioned molded product of the present invention, a preform for a multilayer hollow molded product, and a multilayer hollow molded product thereof.

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

[Means and effects for solving the problems] According to the present invention, the above objects and advantages of the present invention are as follows: (A) polyalkylene terephthalate (a) containing ethylene terephthalate as a main constituent unit and polyamide; (b) a polyester composition layer consisting of a polyester composition layer; (B) a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit; 35 to 50 moles of dicarboxylic acid component units containing saturated dicarboxylic acid component units; 0 to 35 to 50 moles of diamine component units having 2 to 12 carbon atoms; and optionally (c) 0 to 50 moles of aminocarboxylic acid component units having 5 to 12 carbon atoms. 30 mol%, and (d) has an intrinsic viscosity [η] of 0.2 to 3.0 dl/, 9
and (e) a polyester laminate molded article characterized in that it is a substantially linear polyamide having a glass transition temperature in the range of 40 to 180°C.

The polyamide (B) used in the present invention is novel, and includes (a)' a dicarboxylic acid containing an oxy-saturated dicarboxylic acid having 3 to 6 carbon atoms, (b) a diamine having 2 to 12 carbon atoms, and (c)' Produced by a method characterized by polycondensing a raw material mixture consisting of an aminocarboxylic acid having 5 to 12 carbon atoms, a salt or a lower condensate formed therefrom, in the presence of an organic solvent. Ru.

In the present invention, the oxy-saturated dicarboxylic acid having 3 to 6 carbon atoms as part or all of the dicarboxylic acid (a)' used as one of the raw materials includes, for example, tartronic acid,
Examples include methyltartronic acid, malic acid, methylmalic acid, tartaric acid, methyltartaric acid, dioxyglutaric acid, and dioxyadipic acid. Among these, malic acid and tartaric acid are preferred, and malic acid is also preferably used. The proportion of the oxy-saturated dicarboxylic acid component having 3 to 6 carbon atoms in the dicarboxylic acid component (a)' is usually 2 to 100%, preferably 5 to 100%, particularly preferably 10 to 100%.
It is in the mole-〇 range. Dicarboxylic acid components other than the oxysaturated dicarboxylic acid components having 3 to 6 carbon atoms include:
For example, aliphatic, alicyclic or aromatic dicarboxylic acids having a carbon atom number in the range of 5 to 18 are used.

Such dicarboxylic acids include, for example, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, etc.
Examples include alicyclic dicarboxylic acids such as dicarboxylic acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid.

The other raw material, diamine having 2 to 12 carbon atoms (b
)' is preferably an aliphatic diamine or a diamine containing an aromatic ring. Such diamines include:
For example, ethylene diamine, propylene diamine, 1.
4-diaminobutane, 1°6-diamithexane, 1.
8-diaminooctane, 1.10-diaminodecane, 1
．． Aliphatic diamines such as 12-diaminododecane;
Para-xylylene diamine, orthoxylylene diamine,
Mention may be made of diamines containing an aromatic ring such as metaxylylene diamine. These diamine components can be used alone or in combination of 28 or more. Among these diamines, 1,4-diaminobutane, 1,6-diamithexane, 1,10-diaminodecane, metaxylylene diamine, and the like are preferably used.

Another raw material used as an optional component in the above method is an aminocarboxylic acid (c)' having 5 to 12 carbon atoms. Such an aminocarboxylic acid component has 6 to 6 carbon atoms.
10 is preferably used. It should be understood that the above aminocarboxylic acid component (c)' also includes lactams that form aminocarboxylic acid component units in the polyamide molecule.

Examples of the aminocarboxylic acid component include δ-aminoacrylic acid, ε-aminocaproic acid, ω-amizukaglylic acid,
Examples include ω-amine capric acid.

In the above method, a raw material mixture consisting of a dicarboxylic acid (a)' containing an oxy-saturated dicarboxylic acid, a diamine (b)', and optionally an aminocarboxylic acid &(c)' is condensed in the presence of an organic solvent. This will be implemented by In this case, the raw material mixture can be used in the form of a salt or a lower condensate by a method known per se. That is, the dicarboxylic acid component (a)' can be used as a free acid, as an alkyl ester, or as a salt with a diamine, and in the diamine component (a)' can be used as a free base or as a salt with a dicarboxylic acid. The aminocarboxylic acid component (c)' can also be used as an aminocarboxylic acid, a lactam, an alkyl ester, or an amide or salt with a diamine or dicarboxylic acid.

These raw materials (a)', (b)' and (c)' can be supplied to the reaction system at once or in portions.

The polycondensation reaction can also be carried out by known melt polycondensation, but it is preferably carried out in the presence of a solvent.

As such a solvent, one that dissolves the polyamide to be produced is preferably used. Examples of such solvents include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, O-talesol, m-cresol, p-cresol, chlorobenzene, dichlorobenzene, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N
Examples include organic solvents such as -dimethylformamide, N-methylaceamide, and hexamethylene phosphoramide. The proportion of the solvent to be used is not particularly limited, but it is preferably used in a proportion of 1 to 10 parts by weight per part by weight of the polymer to be produced. The solvent can be used all at once at the beginning of the polycondensation reaction, or can be divided and used during the reaction.

The reaction temperature for polycondensation is usually 90 to 200°C, preferably 100 to 180°C. The time for the polycondensation reaction is not particularly limited, but it is generally preferable to complete the polycondensation reaction within a range of 30 minutes to 10 hours.

After the polycondensation reaction, recovery of the polyamide produced in the reaction system is as follows:
For example, the reaction can be carried out by a conventionally known method, such as injecting the reaction solution into a solvent with low solubility for the polyamide to precipitate and recover the polyamide.

Thus, according to the above method, as mentioned above, (a)
35 to 50 molty dicarboxylic acid component units containing oxy-saturated dicarboxylic acid component units having 3 to 6 carbon atoms, 35 to 50 molty diamine component units having 2 to 12 carbon atoms, and optionally (c) 5 to 12 carbon atoms. A substantially linear polyamide composed of 0 to 30 molar aminocarboxylic acid component units, and (d) having an intrinsic viscosity [v] of 0.2 to 3. A polyamide is obtained having a glass transition temperature in the range of Qdl/9 and (e) a glass transition temperature in the range of 40 to 180°C. The term "substantially linear structure" means that it consists essentially of a linear or branched chain structure, and it means that it is not substantially a gel-like crosslinked structure (network structure). This means that the polyamide of the present invention contains sulfuric acid,
It is confirmed by substantially complete dissolution in trifluoroacetic acid, dimethylacetamide/Litecum chloride mixed solvent, N-methylpyrrolidone/lithium chloride mixed solvent, etc.

In addition, the above-mentioned molti has units (a), (b) and (c)
The standard is the sum of

The above polyamide can be a binary polyamide consisting of a dicarboxylic acid component unit (a) and a diamine component unit (b), and may also include these units (a), (b) and an aminocarboxylic acid component unit ( It can also be a ternary co-condensed polyamide consisting of c). In either case, the polyamide forms a polymer molecular chain by condensing adjacent carboxyl groups and amino groups of each component unit to form an amide bond. Any of the above-mentioned component units may be placed at the molecular end of the polyamide, and the carboxyl group present at the molecular end may be amidated with another lower amine,
It may also be amidated with other lower amides. Similarly, the amino group present at the end of the molecule may be amidated with another lower carboxylic acid.

The above polyamide has an intrinsic viscosity [η] of 0.2 to 3.0 as measured at 25°C in a mixed solvent of N,N-dimethylacetamide and lithium chloride (weight ratio 100:5). Qdl/
, 9, and even 0.
Preferably it has a value in the range 3 to 25 dJ/g. Intrinsic viscosity [W) is 3. When Qd is larger than 17g,
The melt moldability of the polyamide decreases, and furthermore, its stretchability also decreases. Also, the intrinsic viscosity is 0
．． When it is less than 3 dt/g, the mechanical strength of the polyamide and its stretched product decreases due to ζ moss. Further, the glass transition temperature of the polyamide needs to be in the range of 40 to 180°C, and more preferably in the range of 50 to 140°C.
Preferably, the temperature is in the range of °C.

Furthermore, if the glass transition temperature is lower than 40° C., the polyamide cannot be easily and economically dried.

Polyalkylene terephthalate (a) constituting the polyester composition layer (6) 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 7
It is in the range of 0 molti 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-hydroxyethoxy)benzene, 1.3-bis(β-hydroxyethoxy)benzene, 2.2-bis(4-β-hydroxyethoxyphenyl)propane, bis(4-β-hydroxyethoxyphenyl)sulfone, etc. Examples include diol component units having 3 to 15 carbon atoms.

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, 3e3'
l Aromatic polybasic acids such as 515'-tetracarboxydiphenyl, aliphatic polybasic acids such as butanetetracarboxylic acid, phloroglucin, aromatic polyols such as 1.2.4.5-tetrahydroxybenzene, glycerin , trimethylolethane, trimethylolpropane, aliphatic polyols such as pentaerythritol, and oxypolycarboxylic acids such as tartaric acid and malic acid.

The composition of the constituent components of the polyalkylene terephthalate is:
The content of terephthalic acid component units is usually 50 to 100.
The content of aromatic dicarboxylic acid component units other than terephthalic acid component units is usually 0 to 50 mol%, preferably 0 to 30 mol%, and the content of ethylene The content of 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 in the range of 1 to 50 mol%, preferably 0 to 30 mol%. The molar range and the content of polyfunctional compound component units are usually in the range of 0 to 2 mol, preferably in the range of 0 to 1 mol. Further, the intrinsic viscosity [η] of the polyalkylene terephthalate (value measured at 25°C in a mixed solvent of phenol and tetrachloroethane (weight ratio 1/1)) is usually 0.5 to 1.5 dt/g, preferably 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 5o to 120°C, preferably 60 to 100°C. range.

In the polyester composition, the blending ratio of the polyamide (a) is 100% of the polyalkylene terephthalate (a).
Usually 2 to 500 parts by weight, preferably 3 to 300 parts by weight, particularly preferably 5 to 1 part by weight.
00 parts by weight.

In addition to the polyalkylene terephthalate (a) and the polyamide 0), the polyester composition may optionally contain conventionally known nucleating agents, inorganic fillers, lubricants, slip agents, anti-blocking agents, stabilizers, and charging agents. Appropriate amounts of various additives such as inhibitors, antifogging agents, and pigments may be blended.

The polyester composition can be used in an unstretched state as a material for films, sheets, fibers, containers, and other molded bodies of various shapes by ordinary molding methods. Furthermore, when the polyester composition is molded into a film, sheet, or container in a stretched state, a molded article with even better gas barrier properties can be obtained.

Next, the polyester laminate molded product of the present invention, which is composed of a polyester composition layer (g) and a polyalkylene terephthalate layer 0 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 of the polyester composition layer and the polyalkylene terephthalate layer, the polyester composition layer is the middle layer, and both side layers are the laminate molded product. A three-layer laminate molded product having a polyalkylene terephthalate layer, a three-layer laminate molded product having the polyalkylene terephthalate layer as an intermediate layer and both side layers having the polyester composition layer, the polyester composition layer and the polyalkylene terephthalate layer, A multilayer laminate molded product having a four-layer structure or more in which the polyester composition layers and the polyalkylene terephthalate layers are alternately laminated; A multilayer laminated molded product having a layer structure or more, in which both outermost layers are composed of the polyester composition layer, a four-layer structure or more in which the polyester composition layer and the polyalkylene terephthalate layer are alternately laminated. Examples include multi-layer molded products in which the outermost layer is composed of the polyester composition layer and the polyalkylene terephthalate layer. 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 polyester composition layer (A) constituting the laminate molded product
J and the thickness of the polyalkylene terephthalate layer 0 are appropriately determined depending on the use of the laminate molded product and are not particularly limited. When the laminate molded product is the three-layer laminate molded product, the thickness of the polyester composition layer is in the range of ordinary to 350μ, preferably 2 to 200μ, and the thickness of the polyalkylene terephthalate layer is It ranges from 8 to 600μ, preferably from IO 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 350 μm, preferably 2 μm.
The thickness of each outer layer of the polyalkylene terephthalate layer is usually between 4 and 300μ, preferably between 5 and 250μ.

In addition, when the outer laminate molded product is the latter of the three-layer laminate molded product, the thickness is in the range of 10 to 500 μm, and the thickness of both outer layers made of the polyester composition is usually 1 to 1 μm.
00μ, preferably in the range of ~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 the polyalkylene terephthalate constituting the polyester composition layer)
It does not necessarily have to be the same as (a). 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 article of the present invention has excellent properties such as melt moldability, stretchability, mechanical strength, transparency, and gas repellency, so it can be used for various purposes.

Next, the polyester stretch laminate molded product of the present invention, which is composed of the polyester composition layer (5) and the polyalkylene terephthalate layer 0 whose main constituent unit is ethylene terephthalate, will be described. The polyester stretch laminate molded product of the present invention is a polyester laminate molded product comprising the polyester composition layer window and the polyalkylene terephthalate layer, and has the above-mentioned laminate structure, and at least one of the polyalkylene terephthalate layers This is a polyester stretch laminate molded product in a stretched state.

Preferably, the polyester laminate molded product is composed of the polyester composition layer (6) and the polyalkylene terephthalate layer (c) and has the above-mentioned laminate structure, and at least all of the polyalkylene terephthalate layers are stretched. The polyester stretch laminate molded article is particularly preferably the polyester composition layer (8).
and the polyalkylene terephthalate layer 0,
The polyester laminate molded article has the above-mentioned laminate structure, and all of the polyester composition layer and the polyalkylene terephthalate 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.
．． 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
．． 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-like product or a sheet-like product, any conventionally known method can be employed as a manufacturing method thereof.

Generally, the polyester composition and the polyalkylene terephthalate are melted in separate extruders, and formed into a multilayer laminated film-like product (laminate sheet-like product) by a melt coextrusion method from a multilayer T-die. remain heated or once the temperature is below the glass transition point ζ
A method is adopted in which the material is cooled, solidified, further heated, and then subjected to a stretching treatment. In addition, as another method, there is a method in which the polyester composition is extruded or sandwich laminated onto a film-like material (sheet-like material) previously formed from the polyalkylene terephthalate, but in this case, polyalkylene terephthalate is A film-like material (sheet-like material) made of terephthalate may be uniaxially or biaxially stretched before being laminated, or it may be subjected to a similar stretching treatment after lamination. . In addition, a film-like product (sheet-like product) pre-formed from the polyester composition
There is a method in which the polyalkylene terephthalate is made into an extrusion laminate or a sandwich laminate, and in this case, the film-like material (sheet-like material) made of the polyester composition may be uniaxially stretched before being made into the laminate. It does not need to be stretched, and it does not matter if it is biaxially stretched, or it may be similarly stretched after lamination.

Among these stretching methods, the first coextrusion method in which a cumulative layer molded product is formed and then stretched is used to produce a polyester stretched laminate molded product with a simple process and excellent interlayer adhesion. This is particularly preferred because it provides the following.

In addition, when producing the polyester stretch laminate molded product,
When the original molded product is a film-like product (sheet-like product), the stretching treatment can be performed by stretching the original molded product in a uniaxial direction (-axial stretching), or after stretching it in the longitudinal direction. A method of further stretching in the transverse direction (biaxial stretching), a method of simultaneously stretching in the longitudinal and transverse directions (biaxial stretching), a method of repeating sequential stretching in any one direction after biaxial stretching, Examples include a method in which the material is biaxially stretched and then further stretched in both directions, and a so-called vacuum forming method in which stretch-forming is performed by reducing the pressure in the space between the original 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 original molded article, 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 preform for a polyester multilayer hollow molded body of the present invention is a preform for a multilayer hollow body 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 plastic linacom 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, 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 the middle layer and the outer side layer. When a stretched multilayer hollow molded body is formed from a preform having a layered structure composed of three polyalkylene terephthalate layers, the stretched multilayer hollow molded product 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.

Both the polyester composition and the polyalkylene terephthalate constituting the preform for a multilayer blow molded body of the present invention may be added with conventionally known nucleating agents, inorganic fillers, lubricants, slip agents, anteblocking agents, stabilizers, etc., as necessary. There is no problem even if appropriate amounts of various additives such as antistatic agents, antistatic agents, antifogging agents, and pigments are 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 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 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 Preferably, it is a stretched three-layer hollow molded body in which the layers are an inner layer and an outer layer. The stretched multilayer hollow molded product may be a uniaxially stretched product or a biaxially stretched product, but generally a biaxially stretched product has excellent mechanical strength and gas barrier properties. Therefore, it is suitable. 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 body of the present invention is produced by stretch blow molding the preform for the polyester multilayered hollow molded body. Examples of this method include a method in which a preform at the above temperature is stretched in the longitudinal direction, and then further stretched in the transverse direction by blow molding (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.

Next, the present invention will be specifically explained using examples. In addition, in Examples and Comparative Examples, performance evaluation was performed according to the following method.

The intrinsic viscosity [η] of the polyamide was measured at 25° C. in a mixed solvent of N,N-dimethylformamide and lytecum chloride (weight ratio 100:5).

The glass transition temperature of polyamide 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 PERMA-TRAN CJ device manufactured by MOCON.

Example 1 Polyethylene terephthalate (trade name, Mitsui PE'rJ12s) 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
0 parts by weight of malic acid vacuum-dried at 50°C for 12 hours, polyamide produced from hexamethylene diamine, intrinsic viscosity [η10.38 dl/9, glass transition temperature (Tg) 84°C 5 parts by weight] The mixture is melt extruded at about 260° C. using a separate extruder to produce a sillette of the composition, and pellets of the composition and about 260° C.
A press sheet having a thickness of about 100 μm was produced by press molding at 0° C. Furthermore, the press sheet of the polyethylene terephthalate and the press sheet of the composition of polyethylene terephthalate and polyamide are superimposed, and about 2
Press molding was performed at 60° C. to produce a two-layer, two-layer laminate sheet with a thickness of about 150 μm. The obtained laminated sheet has good adhesion between the polyethylene terephthalate layer and the composition layer, and its carbon dioxide gas permeability coefficient is 2.7
m!・da) r-atm, and oxygen gas permeability coefficient 0.
It was 52 mg・proverb/m''-day-atm.

Examples 2 to 8 The thickness was changed in the same manner as in Example 1 except that a press sheet of polyethylene terephthalate listed in Table 1 or a press sheet of a composition of polyethylene terephthalate and polyamide listed in Table 1 was used in accordance with Example 1. is about 150μ
A two-layer, two-layer laminate sheet was prepared. All of the obtained laminate sheets had good adhesion between the polyethylene terephthalate layer and the composition layer, and the carbon dioxide gas permeability coefficients of these laminate sheets were as shown in Table 1.

5j! Example 9 Instead of polyethylene terephthalate used in Example 1, polyethylene terephthalate isophthalate (ratio (mole ratio) of terephthalic acid component units to isophthalic acid component units) 90/10, intrinsic viscosity [v] o, s s
In the same manner as in Example 1 except that at 7g) was used,
A two-layer, two-layer laminate sheet having a thickness of approximately 150 μm was prepared, comprising a polyethylene terephthalate/inphthalate layer and a composition layer of polyamide and polyethylene terephthalate/isophthalate. The adhesion between the polyethylene terephthalate inphthalate layer and the composition layer of this laminated sheet was good. Further, the carbon dioxide gas permeability coefficient of this laminated sheet was 1□+j -67 m''·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 gas permeability coefficient of this press sheet is 25-m/m"・day-atm, and the oxygen gas permeability coefficient is 4.51・yl/rn"
・It was day-a-tIn.

Comparative Example 2 Polymethaxylylene adipamide ([η] o, 83 dt/9, Tgs produced from adipic acid and metaxylylene diamine instead of the polyamide in Example 1)
The polyethylene terephthalate layer and the composition layer were each prepared in the same manner as in Example 1 except that the temperature was
A laminated sheet of two types and two layers of μ was prepared. The carbon dioxide gas permeability coefficient of the obtained laminated sheet was 13 ml-w/m”・
It was day-aim.

Example 1O A biaxially stretched film was produced by simultaneously stretching the laminated sheet consisting of the polyethylene terephthalate layer and the composition layer in Example 1 to 3 times each in the vertical axis direction and the horizontal axis direction using a biaxial stretching device. 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 interlayer adhesion between the polyethylene terephthalate layer and the composition layer. Furthermore, the carbon dioxide permeability coefficient of this biaxially stretched film is 2. ．． 4aj-67m”-
It was a day-atm.

Examples 11 to 17 Biaxially stretched films having the stretching ratios shown in Table 2 were produced by simultaneous biaxial stretching in the same manner as in Example 1O, except that the laminated sheets listed in Table 2 were used instead of the laminated sheets in Example 1O. . The obtained biaxially stretched films all had the thicknesses shown in Table 2 and were uniformly stretched. In addition, all of these biaxially stretched films had good interlayer 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 2.

Comparative Example 4 The press sheet of polyethylene terephthalate in Comparative Example 1 was simultaneously stretched 3 times in the vertical and horizontal directions to produce a biaxially stretched film in the same manner as in Example 1O. This biaxially stretched film has a thickness of about 17 μm and a carbon dioxide gas permeability coefficient of 15 at-t/m”
-day-atm.

Example 18 Using a two-layer injection molding machine, the polyethylene terephthalate in Example 1 was melted at a molding temperature of about 270°C, and the mixture of polyethylene terephthalate and boryamide in Example 1 was separately melted. The inner layer is made of polyethylene terephthalate (about 1.6 + u
) Kara f! Also, the outer layer is a composition of polyethylene terephthalate and polyamide (thickness approximately i, s M )
A two-layer preform consisting of Then, using a biaxial stretch blow molding machine (LBol, manufactured by Cohoplast Co., Ltd.), it was biaxially stretched about 2 to 5 times in length and about 4 times in width to produce a multilayer container with an internal volume of about lt. The average thickness of the polyester terephthalate layer of this multilayer container was about 150 μm, and the average thickness of the composition layer was about 150 μm, and it was confirmed that the polyester terephthalate layer was stretched uniformly. Also, the carbon dioxide gas permeability of this multilayer container is 0.8 M1g/m"-day-at
It was m.

Example 19 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 polyethylene terephthalate and polyamide was melted using a separate extruder at a molding temperature of about 260°C, and the outer layer and inner layer were made of polyethylene terephthalate, and the middle layer was made of polyester terephthalate and polyamide. The polyethylene terephthalate layers each have a composition of about 1.2
yux, and an outer diameter of 24 where the composition layer is about 1.2 wx.
．． A two-type, three-layer pipe with a diameter of 8 mm and a thickness of 3.6 mm was fabricated.

Next, this pipe was cut, one end was heated and melted to form a bottom part, and the other end was similarly heated and melted to form a plug part, thereby producing a preform having a total length of 18.5 cm and a weight of 501 cm. Then, using a biaxial stretch blow molding machine (manufactured by Koho Blast Co., Ltd., LBOI), the mixture was biaxially stretched approximately 25 times in length and approximately 4 times in width to produce a multilayer container with an internal volume of approximately 1.5 tons. The average thickness of the polyethylene terephthalate layer of this multilayer container was approximately 120 μm for both the outer layer and the inner layer, and the average thickness of the composition layer was approximately 120 μm, which confirmed that the polyethylene terephthalate layer was uniformly stretched. Also, the carbon dioxide permeability of this multilayer container is Q, 5 w=l/day・bott
It was le-atm. Furthermore, in a drop test, the product did not break down at a drop of 2 meters or less. Furthermore, no f-lamination was observed in each layer.

〔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 all have excellent melt moldability, stretch moldability, and gas barrier properties.

(1 other person)

Claims (4)

[Claims] (1) Consisting of (A) a polyester composition layer consisting of polyalkylene terephthalate (a) whose main constituent unit is ethylene terephthalate and polyamide (b), (B) a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate. A polyester laminate molded article, wherein the polyamide contains (a) 35 to 50 mol% of dicarboxylic acid component units containing oxy-saturated dicarboxylic acid component units having 3 to 6 carbon atoms, and (b) a diamine component having 2 to 12 carbon atoms. 35 to 50 mol% units and optionally (c) 0 to 0 to 12 carbon atoms aminocarboxylic acid component units
30 mol%, and (d) has an intrinsic viscosity [η] in the range of 0.2 to 3.0 dl/g, and (e) has a glass transition temperature in the range of 40 to 180°C. A polyester laminate molded product characterized by being made of polyamide shaped like. (2) (A) a polyester composition layer consisting of polyalkylene terephthalate (a) whose main constitutional unit is ethylene terephthalate and polyamide (b); and (B) a polyalkylene terephthalate layer whose main constitutional unit is ethylene terephthalate; A polyester stretch laminate molded product comprising:
The polyamide contains (a) 35 to 50 mol% of dicarboxylic acid component units containing oxysaturated dicarboxylic acid component units having 3 to 6 carbon atoms, (b) 35 to 50 mol% of diamine component units having 2 to 12 carbon atoms, and optionally ( c) 0 to 0 aminocarboxylic acid component units having 5 to 12 carbon atoms
30 mol%, and (d) has an intrinsic viscosity [η] in the range of 0.2 to 3.0 dl/g, and (e) has a glass transition temperature in the range of 40 to 180°C. A polyester stretch laminate molded product characterized by being made of a polyamide shaped like. (3) (A) a polyester composition layer consisting of polyalkylene terephthalate (a) whose main constituent unit is ethylene terephthalate and polyamide (b); and (B) a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate; and A preform for a polyester multilayer blow-molded body consisting of (a) 35 to 50 mol% of dicarboxylic acid component units containing oxy-saturated dicarboxylic acid component units having 3 to 6 carbon atoms (b) number of carbon atoms 2 to 12 diamine component units 35 to 50 mol % and optionally (c) 0 to C 5 to 12 aminocarboxylic acid component units
30 mol%, and (d) has an intrinsic viscosity [η] in the range of 0.2 to 3.0 dl/g, and (e) has a glass transition temperature in the range of 40 to 180°C. A preform for a polyester multilayer hollow molded article, characterized in that it is made of a polyamide with a shape. (4) (A) a polyester composition layer consisting of polyalkylene terephthalate (a) whose main constitutional unit is ethylene terephthalate and polyamide (b); and (B) a polyalkyl terephthalate layer whose main constitutional unit is ethylene terephthalate; A polyester multilayer hollow molded body comprising:
The polyamide contains (a) 35 to 50 mol% of dicarboxylic acid component units containing oxysaturated dicarboxylic acid component units having 3 to 6 carbon atoms, (b) 35 to 50 mol% of diamine component units having 2 to 12 carbon atoms, and optionally ( c) 0 to 0 aminocarboxylic acid component units having 5 to 12 carbon atoms
30 mol%, and (d) has an intrinsic viscosity [η] in the range of 0.2 to 3.0 dl/g, and (e) has a glass transition temperature in the range of 40 to 180°C. A polyester stretched multilayer hollow molded article, which is made of a polyamide shaped like polyester.