JPS60232952A - Polyester laminated molded shape and use 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 [Industrial Field of Application] The present invention provides polyester laminate molding which has excellent melt moldability, excellent mechanical strength, transparency and gas barrier properties, and has performance that can pass as a material for containers. It concerns the body and its uses.

[Conventional technology]

Traditionally, glass has been widely used as a container material for seasonings, oils, beer, alcoholic beverages such as sake, soft drinks such as carbonated drinks, cosmetics, detergents, and other products. However, although glass containers have excellent gas barrier properties, they are expensive to manufacture, so a method has been adopted in which empty containers are usually collected after use and recycled for reuse.

However, glass containers are heavy, which increases shipping costs, and they also have drawbacks such as being easily damaged and inconvenient to handle.

In order to overcome the aforementioned disadvantages of glass containers, there is a growing shift from glass containers to various plastic containers. Various plastics are used as materials depending on the type of stored item and its intended use. Among these plastic materials, polyethylene terephthalate has excellent gas barrier properties and transparency, and is therefore used as a material for containers for seasonings, soft drinks, detergents, cosmetics, and the like. However, polyethylene terephthalate is still not sufficient for beer and carbonated beverage containers, which require the most stringent gas barrier properties, and it is necessary to use thicker polyethylene terephthalate for use in these containers. The gas barrier properties had to be improved by increasing the amount of carbon. Currently, the demand for polyester containers is increasing, and in order to expand their use, there is a strong demand for polyester molded articles with excellent gas barrier properties and melt moldability.

Conventionally, various polyesters have been known, and among these polyesters, polyethylene terephthalate is the most widely used, but modified polyethylene terephthalate, which is obtained by cocondensation polymerization of a third component during the production of polyethylene terephthalate, is also used. Various proposals have been made. for example,
In modified polyethylene terephthalate, an aromatic dicarboxylic acid component unit other than terephthalic acid is used as the third component.

There are many proposals regarding the method of cocondensation polymerization, but the modification obtained by any of these proposals, W')'
, ``'''' terephthalates have excellent stretchability, but it cannot be said that any of the two-wheeled stretched containers formed from these modified polyethylene terephthalates have sufficient gas barrier properties.

Conventionally, in order to improve the gas barrier properties of polyesters such as polyethylene terephthalate, partially saponified products of ethylene/vinyl acetate copolymers, styrene/acrylonitrile copolymers, diamines mainly composed of metaxylylene diamine, and fats have been added to the polyesters. Laminated molded products in which various high gas barrier resins such as co-condensed polyamides made of group dicarboxylic acids are laminated have also been proposed.

Among these laminate molded products, polyester laminate molded products in which a partially saponified product of ethylene/vinyl acetate copolymer is laminated are difficult to mold because the partially saponified product of ethylene/vinyl acetate copolymer has poor thermal stability. It sometimes tends to decompose and has difficulty in moldability.

In addition, a polyester laminate formed by laminating a styrene/acrylonitrile copolymer can be efficiently (stretched) because the styrene/acrylonitrile copolymer has a high glass transition temperature. However, it has the disadvantage that it is not possible to form a stretched laminate molded product with excellent mechanical strength.Furthermore, it has the disadvantage that it is not possible to form a stretched laminate molded product with excellent mechanical strength.Furthermore, it has the disadvantage that a polyester laminate in which a co-condensed polyamide consisting of a diamine whose main component is metaxylylene diamine and an aliphatic dicarboxylic acid is laminated. Since the co-condensed polyamide is highly crystalline, the molded product is susceptible to whitening during molding.
The disadvantage is that it is difficult to form a laminated molded product with excellent transparency, and the adhesion between both side resin layers is also poor, making it difficult to obtain a laminated molded product with excellent mechanical strength. be.

[Problem that the invention seeks to solve]

The present inventors have recognized that the technology for laminated molded products made of polyester, particularly polyester stretched multilayer blow-molded containers, is in the above situation, and has developed a polyester polyester laminate that has excellent melt moldability, stretch moldability, and gas barrier properties, and As a result of studying the development of a polyester laminate molded product that can exhibit excellent performance as a blow-molded container, we have developed a dicarboxylic acid component unit whose main component is isophthalic acid, and a diamine component unit whose main component is metaxylylenediamine component unit. , and if necessary, a polyester laminate formed from a co-condensed polyamide layer having a specific composition consisting of a specific aminocarboxylic acid component unit and a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit achieves the above object. They discovered this and arrived at the present invention. Furthermore, the stretched molded body made of the polyester laminate molded body, the preform for a multilayer hollow molded body having the laminated structure, and the stretched multilayer hollow molded body formed from the preform have melt moldability, mechanical strength, transparency, The inventors have discovered that the material has excellent properties in terms of properties and gas barrier properties, making it excellent as a material for multilayer hollow molded bodies, particularly stretch-blow molded containers, and have thus arrived at the present invention.

[Summary of the invention]

To summarize the present invention, the present invention provides a polyester laminate molded product comprising a co-condensed polyamide layer and a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit, wherein the co-condensed polyamide is (al isophthalic acid 30 to 70 mol% of component units
Dicarboxylic acid component units contained within the range of 35 to 5
0 mol%, (b) 35 to 50 mol% of diamine component units mainly composed of metaxylylene diamine component units, and (C1 carbon atoms in the range of 5 to 12 aminocarboxylic acid component units of O to 12) A substantially linear co-condensed polyamide consisting of 30 mol%, whose physical properties are +dl and whose intrinsic viscosity [η] is 0.4 to 3.0 dl/g.
and (e) having a glass transition temperature in the range of 50°C to 150°C. A second gist of the invention is a polyester stretch laminate molded product composed of a polyalkylene terephthalate layer, which has a laminate structure composed of the co-condensed polyamide layer and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate. A third aspect of the invention is a preform for a polyester multilayer hollow molded body, and a fourth invention is a stretched polyester multilayer hollow molded body composed of the co-condensed polyamide layer and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate. This is the gist of the report.

c. Means and action for solving the problem] The co-condensed polyamide constituting the laminate molded product of the present invention has dicarboxylic acid component units (al and metaxylylene diamine component units) containing isophthalic acid component units in a specific composition. It may be a binary co-condensed polyamide consisting of a diamine component unit (b) whose main component is a dicarboxylic acid component unit containing isophthalic acid component units in a specific composition + a),
Diamine component units (bl) and aminocarboxylic acid component units (C
In some cases, it is a ternary co-condensed polyamide consisting of 1.

In either case, the co-condensed polyamide of the present invention forms a polymer molecular chain by condensing adjacent carboxyl groups and amino groups of each component unit to form an amide bond. The molecular terminal of the co-condensed polyamide may be arranged with any of the above-mentioned component units, and the carboxyl group present at the molecular terminal may be amidated with another lower amine; The amino group present in may also be amidated with other lower carboxylic acids.

The co-condensed polyamide of the present invention has a substantially linear structure. Here, the term "substantially linear structure" means a linear or branched chain-like structure, and a gel-like crosslinked structure (
This means that it does not have a network structure. This is confirmed by the fact that the co-condensed polyamide of the present invention is completely dissolved in sulfuric acid, trifluoroacetic acid, dimethylacetamide/lithium chloride mixed solvent, N-methylpyrrolidone/lithium chloride mixed solvent, etc.

The composition of the co-condensed polyamide constituting the polyester laminate molded product of the present invention is: +a) 30 to 70 mol% of isophthalic acid component units
Dicarboxylic acid component units contained within the range of 35 to 5
0 mol%, preferably in the range of 40 to 50 mol%, (bl) diamine component units mainly composed of metaxylylenediamine component units in the range of 35 to 50 mol%, preferably 40 to 50 mol%. , and (C1 aminocarboxylic acid component units having 5 to 12 carbon atoms in an amount of O to 30 mol %, preferably O
and 20 mol%. In the co-condensed polyamide, if the content of dicarboxylic acid component units +a) and diamine component units (BL is less than 35 mol% and the content of aminocarboxylic acid component units (C1) is greater than 30 mol%, polyester laminate molding This is not preferable because the gas barrier properties of the body, stretched laminate molded product, and stretched multilayer hollow molded product deteriorate.

Further, the dicarboxylic acid component unit (a) constituting the co-condensed polyamide needs to contain isophthalic acid component units in a range of 30 to 70 mol%, and more preferably 30 to 70 mol%.
It is preferably contained in a range of 30 to 60 mol%, particularly 30 to 60 mol%. Dicarboxylic acid component units other than isophthalic acid component units usually have 5 carbon atoms.
It is an aliphatic, alicyclic or aromatic dicarboxylic acid component unit in the range of from , ω-aliphatic dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, alicyclic dicarboxylic acid such as cyclohexane-1,4-dicarboxylic acid, aromatic such as terephthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, etc. Examples include group dicarboxylic acids. The content of dicarboxylic acid component units other than the isophthalic acid component units in the dicarboxylic acid component units must be 30 to 70 mol%, more preferably 35 to 70 mol%, particularly 40 to 70 mol%. It is preferable that Among the dicarboxylic acid component units other than the above-mentioned isophthalic acid component units, α, ω-aliphatic dicarboxylic acid component units are included in an amount of 30 to all dicarboxylic acid component units.
It is preferable that the content is in the range of 40 to 70 mol%, particularly 40 to 70 mol%, because a polyester laminate molded product having excellent melt moldability, stretch moldability, transparency, and gas barrier properties can be obtained. When the content of isophthalic acid component units in the dicarboxylic acid component units constituting the co-condensed polyamide becomes less than 30 mol% and the content of dicarboxylic acid component units other than the isophthalic acid component units exceeds 70 mol%, the The gas barrier properties, transparency, and interlayer adhesion of polyester laminate molded products, stretched laminate molded products, preforms for stretched multilayer hollow molded products, and stretched multilayer hollow molded products become inferior, and the content of isophthalic acid component units is reduced to 70%. If the content of dicarboxylic acid component units other than isophthalic acid component units is less than 30 mol%, the polyester laminate molded product, stretched laminate molded product, preform for stretched multilayer hollow molded product, stretched multilayer The melt formability and stretch formability of the hollow molded body begin to deteriorate.

Diamine component unit (a) constituting the co-condensed polyamide
is a diamine component whose main component is a metaxylylene diamine component unit, and may be a single component of metaxylylene diamine, or a diamine component whose main component is a metaxylylene diamine component unit and other than the metaxylylene diamine component unit. A mixed component consisting of units is also acceptable. The content of metaxylylenediamine component units in the diamine component units is usually in the range of 50 to 100 mol%, preferably 70 to 100 mol%. Specifically, the diamine component units other than metaxylylenediamine component units are:
Xylylene diamines such as baraxylylene diamine and orthoxylylene diamine, 1,4-diaminobutane, 1
, 6-diamithexane, 1,8-diaminooctane,
(2) Examples include diamines having 4 to 12 carbon atoms such as aliphatic diamines such as 10-diaminodecane and 1,12-diaminododecane, and among these diamines, xylylene diamine is preferable. .

In addition, an aminocarboxylic acid component unit (C1 is an aminocarboxylic acid component unit having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms), which is optionally contained in the co-condensed polyamide; Also included are lactams that form aminocarboxylic acid component units in the co-condensed polyamide molecule.

Specific examples of the aminocarboxylic acid component unit include δ-aminovaleric acid, ε-aminocaproic acid, ω-aminocaprylic acid, ω-aminocapric acid, and the like.

N,N-dimethylacetamide of the co-condensed polyamide
25°C in lithium chloride mixed solvent (weight ratio 100:5)
The intrinsic viscosity [η] measured at is 0.4 to 3.0 dl/
It is necessary to be in the range of 0.5 to 2.541/g, and more preferably in the range of 0.5 to 2.541/g. When the intrinsic viscosity [η] is larger than 3.0 dl/g, the melt moldability of the co-condensed polyamide becomes poor, and the polyester laminate molded product, stretched laminate molded product, preform for multilayer hollow molded product, stretched multilayer Melt formability and stretch formability when producing a hollow molded body become inferior. Moreover, when the intrinsic viscosity [η] is smaller than 0.4 dl/g, the mechanical strength of the co-condensed polyamide becomes poor. Further, the glass transition temperature of the co-condensed polyamide is 50 to 150°C.
It is necessary to be in the range of 60 to 1
Preferably, the temperature is in the range of 40°C. When the glass transition temperature of the co-condensed polyamide is higher than 150°C, the stretch moldability of the co-condensed polyamide becomes poor, and the polyester laminate molded product, stretched laminate molded product, preform for multilayer hollow molded product, This results in poor moldability when producing a stretched multilayer hollow molded body. In addition, the glass transition temperature is 50℃
If it is lower than , the co-condensed polyamide cannot be easily and economically dried.

The polyalkylene terephthalate constituting the polyester laminate molded product of the present invention is a polyester containing ethylene terephthalate as a main constituent unit.

The content of ethylene terephthalate structural units in the polyalkylene terephthalate is usually 50 mol% or more,
Preferably it is in the range of 70 mol% or more.

The dicarboxylic acid component units constituting the polyalkylene terephthalate may contain a small amount of other aromatic dicarboxylic acid component units in addition to the terephthalic acid component units. Specific examples of aromatic dicarboxylic acid component units other than terephthalic acid component units include isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid. The luciol component units constituting the polyalkylene terephthalate may contain a small amount of diol component units other than ethylene glycol component units. Specifically, other diol component units other than ethylene glycol component units include 1,3-propanediol, 1,4-butanediol, neopentyl glycol, cyclohexanediol, cyclohexane dimetatool, 1.4-bis(β Carbon atoms such as -hydroxyethoxy)benzene, 1,3-bis(β-hydroxyethoxy)benzene, 2,2-bis(4-β-hydroxyethoxyphenyl)propane, bis(4-β-hydroxyethoxyphenyl)sulfone, etc. number 3 or 1
The diol component and 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°,
Aromatic polybasic acids such as 5,5"-tetracarboxydiphenyl, aliphatic polybasic acids such as butanetetracarboxylic acid, aromatic acids such as Furo-T2-JLt-syn, and 1,2,4.5-tetrahydroxybenzene. family polyols, aliphatic polyols such as glycerin, trino, tyrolethane, trimethylolpropane, and pentaerythritol;
Examples include 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%. , 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 2 mol%, preferably 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. ! M1/g, preferably in the range of 0.6 to 1.2 dl/g, melting point usually in the range of 210 to 265°C, preferably 220 to 260°C, and glass transition temperature usually in the range of 50 to 120°C, preferably ranges from 60 to 100.

Next, a polyester laminate molded article composed of a co-condensed polyamide layer of the present invention and a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit will be described. Specifically, the laminate molded product includes a two-layer laminate molded product composed of two layers of the co-condensed boria FFi and the polyalkylene terephthalate layer, the co-condensed polyamide layer as an intermediate layer, and both outer layers as the polyamide layer. A three-layer laminate molded product having an alkylene terephthalate layer, a three-layer laminate molded product having the polyalkylene terephthalate layer as an intermediate layer and both side layers being the co-condensed polyamide layer, the co-condensed polyamide layer and the polyalkylene terephthalate layer, A multilayer laminate molded product having a four-layer structure or more alternately laminated, the outer layer of which is composed of the polyalkylene terephthalate layer, a four-layered molded product in which the co-condensed polyamide layer and the polyalkylene terephthalate layer are alternately laminated. A multilayer laminate molded product having a structure or more, the outer layer of which is composed of the co-condensed polyamide layer, a laminate molded product having a four-layer structure or more in which the co-condensed polyamide layer and the polyalkylene terephthalate layer are alternately laminated. Examples include a multilayer laminate molded product in which the outermost layer is composed of the co-condensed polyamide layer and the polyalkylene terephthalate layer.

The laminated molded product is not only sheet-like, plate-like, and tubular, but also various hollow bodies, containers, structures of various shapes, etc. ,,−
kl! Jll? -01-6Uo9. -7.

It can be manufactured by a known method.

The thicknesses of the co-condensed polyamide 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 co-condensed polyamide layer is usually 1 to 35 cm.
0μ, preferably in the range from 2 to 200μ, and the thickness of the polyalkylene terephthalate layer is from 8 to 600μ.
μ, preferably in the range of 10 to 500 μ. When the laminate molded product is the former of the three-layer laminate molded product, the thickness of the intermediate layer consisting of the co-condensed polyamide layer is usually in the range of 1 to 350 μm, preferably 2 to 200 μm; The respective thicknesses of the two outer layers of polyalkylene terephthalate layers usually range from 4 to 300 microns, preferably from 5 to 250 microns. Further, when the laminate molded product is the latter of the three-layer laminate molded products, the thickness of the intermediate layer consisting of the polyalkylene terephthalate layer is usually 8 to 600μ, preferably 10 to 500μ.
The thickness of both outer layers of the co-condensed polyamide layer is usually in the range of 1 to 100 microns, preferably 2 to 50 microns. Even when the laminate molded product is a multilayer laminate molded product having a four-layer structure or more, the thickness of the intermediate layer and the outermost layer made of the co-condensed polyamide 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 polyester laminate molded product has excellent properties such as stretchability, mechanical strength, transparency, and gas barrier properties, so it can be used for various purposes.

The polyester stretch laminate molded product of the present invention comprising a co-condensed polyamide layer and a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit will now be described. Polie of the present invention.

The Stell stretch laminate molded product is a polyester laminate molded product that is composed of the co-condensed polyamide layer and the polyalkylene terephthalate layer and has the above-mentioned laminate structure, and at least one of the polyalkylene terephthalate layers is stretched. It is a polyester stretch laminate molded product, preferably composed of the co-condensed polyamide layer and the polyalkylene terephthalate layer, and has the above-mentioned laminate structure, and has a small amount (not to mention all of the polyalkylene terephthalate layer). A polyester stretch laminate molded product in which the layers are in a stretched state, and particularly preferably a polyester laminate molded product having the above-mentioned laminate structure, comprising the co-condensed polyamide layer and the polyalkylene ethylene reflex acid layer. All layers of the condensed polyamide 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 molded product is uniaxially stretched, the stretching ratio is usually 1.1 to 10 times, preferably 1.2 to 8 times, particularly preferably 1. If the constituent resin layer is a biaxially stretched layer, the stretching ratio in the longitudinal direction is usually 1.1 to 8 times, preferably 1.2 to 8 times. 7 times, particularly preferably in the range of 1.5 to 6 times, and usually 1.1 to 8 times in the horizontal direction,
Preferably 1.2 to 7 times, particularly preferably 1.5
It is in the range of 6 to 6 times. Furthermore, the polyester stretch 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 polyamide and the polyalkylene thirefrate are melted in separate extruders, and the polyamide is melted in separate extruders.
The original laminate molded product, such as a multilayer laminate film (laminated sheet), formed from a die by melt coextrusion is heated or once cooled to a temperature below the glass transition point to solidify it, and then reheated and then stretched. A method of applying treatment is adopted.

Other methods include extrusion lamination or sandwich lamination of the co-condensed polyamide on a film-like product (sheet-like product) formed from the polyalkylene terephthalate. The shaped product (sheet-like product) may be uniaxially or biaxially stretched before laminating, or may be similarly stretched after laminating. In addition, there is a method of extrusion laminating the polyalkylene terephthalate on a film-like material (sheet-like material) previously formed from the co-condensed polyamide, or a method of sandwich laminating the polyalkylene terephthalate. The material may be uniaxially or biaxially stretched before laminating, or may be similarly stretched after lamination. Among these stretching methods, the first method, in which an original laminate is formed by coextrusion and then stretched, produces a polyester stretched laminate 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 (two-wheel 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,
(7) It has excellent transparency and gas barrier properties, so 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 co-condensed polyamide layer and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate, and further This is a preform for a multilayer hollow molded body having the above-mentioned laminate structure. Examples of the preform having a laminate structure include the two-layer laminate preform exemplified in the laminate molded product of the present invention described above, a similar three-layer laminate preform, and a similar multilayer laminate molded product having four or more layers. Renovation can be similarly exemplified. Among these preforms for multilayer hollow molded bodies, there are preforms having a laminated structure consisting of two layers, the co-condensed polyamide layer and the polyalkylene telescopic layer, and the co-condensed polyamide as an intermediate layer. When a stretched multilayer hollow molded product is formed from a preform having a laminated structure in which both outer layers are made of three layers of the polyalkylene terephthalate layer, it has excellent mechanical strength, transparency, gas barrier properties, etc. This is preferred because a stretched multilayer hollow molded article with excellent properties can be obtained.

A nucleating agent, an inorganic filler, a lubricant, and a slip are blended into the conventional polyamide or polyester as necessary in both the cocondensed polyamide and the polyalkylene terephthalate constituting the preform for a multilayer blow molded body of the present invention. Appropriate amounts of various additives such as anti-blocking agents, stabilizers, antistatic agents, antifogging agents, and pigments may be blended.

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

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

The polyester stretched multilayer hollow molded body of the present invention is a stretched multilayer hollow molded body composed of the cocondensed polyamide 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 product is
It may be a stretched two-layer hollow molded product composed of the co-condensed polyamide layer and the polyalkylene terephthalate layer, or it may be composed of three layers in which the co-condensed polyamide layer and the polyalkylene terephthalate layer are alternately laminated. It may be a stretched three-layer hollow molded body, or it may be a stretched multilayer hollow molded body composed of four or more layers in which the co-condensed polyamide layer and the polyalkylene terephthalate layer are alternately laminated. . 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 co-condensed polyamide 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 co-condensed polyamide layer is the inner layer and the polyalkylene terephthalate layer is the outer layer. In addition, in the case where the stretched multilayer hollow molded body is the above-mentioned three (i) hollow molded body, a stretched three-layer hollow molded body in which the co-condensed polyamide layer is a hollow layer and the polyalkylene terephthalate layer is an inner layer and an outer layer. It may be a molded body or a stretched three-layer hollow molded body in which the co-condensed polyamide layer is an inner layer and an outer layer. When the stretched multilayer hollow molded body is a stretched multilayer hollow molded body composed of four or more layers, the co-condensed polyamide layer may be the inner layer (and the polyalkylene terephthalate layer is the inner layer). It may be a layer.Among the polyester stretched multilayer hollow molded articles of the present invention, it is preferable that the inner layer is a stretched multilayer hollow molded article whose inner layer is a polyalkylene terephthalate layer.In particular, it is preferable that the inner layer is a polyalkylene terephthalate layer. and the polyalkylene terephthalate layer.

A three-layer stretched hollow molded body comprising an inner layer and an outer layer is preferred. The stretched multilayer hollow molded product may be a uniaxially stretched product or a two-wheel stretched product,
Generally, biaxially oriented materials have good 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 above-mentioned co-condensed polyamide and the polyalkylene ethylene reflectorate 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 (biaxial stretch blow molding) in which a preform at the above temperature is stretched in the vertical axis direction and then further blow molded to stretch it in the horizontal axis direction.

The polyester stretched multilayer hollow molded article of the present invention has excellent mechanical strength, heat resistance, gas barrier properties, and transparency, and can therefore be used for various purposes. In addition, the two-wheel stretch multilayer blow-molded container of the present invention has excellent gas barrier properties, so it can be used for seasonings, oils, alcoholic beverages such as beer and sake, soft drinks such as cola, Saigu, and juice, cosmetics, detergents, etc. It is excellent as a container, but especially when used as a container for beer or carbonated drinks, it becomes possible to reduce the wall thickness of the container and extend its 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 co-condensed polyamide is determined by the N,N-dimethylacetamide-lithium chloride mixed solvent (weight ratio 100
:5) by measuring at 25°C. The glass transition temperature and melting point of the co-condensed polyamide were determined by measuring with a differential scanning calorimeter.

The composition of the co-condensed polyamide, as in the case of conventional polyamides, is determined by the ratio of raw material monomers used during production, and this indicates that the nuclear magnetic resonance spectra of the co-condensed polyamide in trifluoroacetic acid solution or deuterated sulfuric acid solution, etc. This can be confirmed by measuring.

The intrinsic viscosity [η] of the polyalkylene terephthalate is determined by the phenol-tetrachloroequene mixed solvent (weight ratio too
: 100) at 25°C.

The glass transition temperature and melting point of the polyalkylene thirefrate were determined by measuring with a differential scanning calorimetry needle.

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

〔Example〕

Example 1 Polyethylene terephthalate (trade name, Mitsui PET J135 (η) 0.83d) dried at 150°C for 5 hours
l/g) using an extruder at a molding temperature of 275°C,
Isophthalic acid/adipic acid/methaxylylene diamine co-condensed polyamide separately dried under reduced pressure at 80°C for 12 hours [composition (mole ratio) 17:33:50, intrinsic viscosity [η] 0.
80d! /g, glass transition temperature (Tg) 96°C) was melted at 280°C using a separate extruder, fed to a two-layer coat hanger type T die, extruded into a sheet, and further cooled with a roll. The polyethylene terephthalate layer is about 100μ and isophthalic acid, adipic acid,
The metaxylylene diamine co-condensed polyamide layer is about 100
A two-layer, two-layer laminate sheet of μ was prepared. The obtained laminated sheet had excellent transparency, and also had good adhesion between the glabella between the polyethylene terephthalate layer and the co-condensed polyamide layer. Furthermore, the gas barrier of this multilayer sheet
The crystal whose properties were measured, the oxygen gas permeability coefficient was 0.08+wl
mm/nf, day, atm, and carbon dioxide permeability coefficient is 1.21111 tam/nf-day-at
Examples 2 to 10 The thickness of the co-condensed polyamide layer was determined in the same manner as in Example 1 except that the polyamide or polyethylene terephthalate listed in Table 1 was used instead of the co-condensed polyamide or polyethylene terephthalate in Example 1. A two-layer, two-layer laminate sheet was prepared in which the thickness of the polyethylene terephthalate layer was approximately 100μ and the thickness of the polyethylene terephthalate layer was approximately 100μ.

All of the obtained laminated sheets had excellent transparency and also had good adhesion between the glabella between the co-condensed polyamide layer and the polyethylene terephthalate layer. Furthermore, the carbon dioxide gas permeability coefficients of these multilayer sheets are
A two-layer, two-layer laminate sheet having a polyamide layer and a polyethylene terephthalate acid layer each having a thickness of approximately 100 μm was prepared in the same manner as in Example 1, except that the polyamide layer and the polyethylene terephthalate acid layer were each approximately 100 μm in thickness. The obtained laminated sheet is Example 1
The transparency was slightly lower than that of the laminated sheet, and it easily peeled off between the eyebrows when folded.

Comparative Example 2 Instead of the co-condensed polyamide in Example 1, diisophthalic acid/adipic acid/methaxylylene diamine co-condensed polyamide [composition (mole ratio) 25:25:50, (t
A two-layer, two-layer laminate sheet having a co-condensed polyamide layer and a polyethylene terephthalate layer each having a thickness of 100 μm was prepared in the same manner as in Example 1, except that t) 0.32 a/g, 116° C.] was used. In the obtained laminated sheet, cracks were easily generated in the co-condensed polyamide layer by bending or the like.

Example 11 The polyethylene terephthalate in Example 1 was melted at a molding temperature of 275°C using an extruder, and the co-condensed polyamide in Example 1 was separately melted at a molding temperature of 275°C using another extruder.
Melt it at 80°C, feed it into a three-layer coat hanger type T-die so that the upper and lower layers are polyethylene terephthalate, and the middle layer is co-condensed polyamide, extrude it into a sheet, and then cool it with a roll. Accordingly, each polyethylene terephthalate layer has a thickness of about 75
In addition, a two-type, three-layer laminate sheet was prepared in which the co-condensed polyamide layer had a thickness of about 75 μ.The resulting laminate sheet had excellent transparency, and the adhesiveness between the eyebrows between the polyethylene terephthalate layer and the co-condensed polyamide layer was also excellent. It was good. Further, this laminated sheet carbon Example 12 The laminated sheet consisting of the polyethylene terephthalate layer and the co-condensed polyamide layer in Example 1 was simultaneously stretched by three times in the -axial direction and the transverse axis direction using a two-wheel stretching device. A biaxially stretched film was produced. The resulting biaxially stretched film had a thickness of about 11 μm for both the polyethylene terephthalate layer and the co-condensed polyamide layer, and was uniformly biaxially stretched. Further, this biaxially stretched film had excellent transparency, and also had good glabellar adhesion between the polyethylene terephthalate layer and the co-condensed polyamide layer. Furthermore, the carbon dioxide permeability coefficient of this biaxially stretched film was 1.1 ml mm/rrr-day, a'tm.

Examples 13 to 18 Biaxially stretched films having the stretching ratios shown in Table 2 were produced by simultaneous biaxial stretching in the same manner as in Example 12, except that the laminated sheets listed in Table 2 were used instead of the laminated sheets in Example 12. . The resulting biaxially stretched films each had a polyethylene terephthalate layer and a co-condensed polyamide layer having approximately the same thickness as shown in Table 2, and were uniformly biaxially stretched. In addition, all of these biaxially oriented films had poor transparency, and the adhesiveness between the polyethylene terephthalate layer and the co-condensed polyamide layer was also good. The permeability coefficients are shown in Table 2 Comparative Example 3 Instead of the co-condensed polyamide in Example 1, isophthalic acid/adipic acid/methaxylylene diamine co-condensed polyamide [composition (mole ratio) 45:10:50, [η
) 0.85d! / g, Tg 151° C.] was used in the same manner as in Example 1, to produce a two-type, two-layer laminate sheet in which the co-condensed polyamide layer had a thickness of about 100 μm and the polyethylene terephthalate layer had a thickness of about 100 μm. Furthermore, simultaneous biaxial stretching of this laminated sheet was attempted in the same manner as in Example 12. However, the polyethylene terephthalate layer of the stretched film was not uniformly stretched.

Furthermore, when the stretching temperature was lowered to achieve uniform stretching, the extruded sheet broke and could not be stretched.

Example 19 Using a two-layer injection molding machine, the polyethylene terephthalate in Example 1 was molded at a molding temperature of 2.
Separately, the co-condensed polyamide in Example 1 was melted at 75°C and then melted at a molding temperature of 280°C using another injection molding machine, and then injection molded in two layers into a cooled single preform mold to form an inner layer. is polyethylene terephthalate (thickness approx. 1
, 6 mm), and the outer layer was made of co-condensed polyamide (about 1.6 mm thick).

Next, a two-wheel stretch-blow molding machine (manufactured by Kohoplast Co., Ltd., LB
OI) was used to stretch the two wheels approximately 2.5 times vertically and approximately 4 times horizontally, resulting in an internal volume of approximately 1. A multilayer container of Ol was prepared. The average thickness of the polyethylene terephthalate layer of this multilayer container was about 150 μm, and the average thickness of the co-condensed polyamide layer was about 150 μm, and it was confirmed that the polyethylene terephthalate layer was stretched uniformly. In addition, this multilayer container has excellent transparency, and its oxygen gas permeability is 0.02 m1/day, bottl.
e-atm, and carbon dioxide permeability is 0.23 m1/d
It was an ay-bottle ATM. Furthermore, when we determined the minimum height at which this multilayered container would break by filling it with 0°C water, we found that it did not break at a height of 2 m or less. Furthermore, no delamination was observed in each layer.

Example 20 Example 1 except that the co-condensed polyamide in Example 8 is used instead of the co-condensed polyamide in Example 19
9, the inner layer is made of polyethylene terephthalate (
A biaxially stretched layer preform having a thickness of approximately 1.6+n+++ and an outer layer made of co-condensed polyamide (approximately 1.6 mm thick) was prepared, and then two-wheeled stretch blow molding was performed in the same manner as in Example 19 to obtain an inner volume. A multilayer container with ON of about 1 was produced. The average thickness of the polyethylene terephthalate layer of this multilayer container was about 150 μm, and the average thickness of the co-condensed polyamide layer was about 150 μm, and it was confirmed that the polyethylene terephthalate layer was stretched uniformly. In addition, this multilayer container has excellent transparency, and its oxygen gas permeability is 0.02 m1/day-
bottle-atm, and carbon dioxide permeability is 0.02
m1/day, bottle-at-Ill. Furthermore, in a drop test, it did not break even at a drop of 2 m, and delamination was confirmed in Example 21. It is melted using a separate extruder at a molding temperature of 280 degrees, fed into a three-layer pipe die so that the outer layer and inner layer are polyethylene terephthalate, and the middle layer is polyethylene terephthalate, and extruded, and further cooled. By doing so, two types of three-layer pipes having an outer diameter of 24mm, 8mmφ and a thickness of 3.6IIII, each having a polyethylene terephthalate layer of about 1.2mm thick and a polyamide layer of about 1.2mm thick, were produced.

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 16.5 cm and a weight of 50 g. Then, using a biaxial stretch blow molding machine (manufactured by Kohoplast, LBOI), the mixture was stretched on two wheels to about 2.5 times in length and about 4 times in width to produce a multilayer container with an internal volume of about 1.51. 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 co-condensed polyamide layer was approximately 120 μm, which confirmed that the polyethylene terephthalate layer was stretched uniformly. In addition, this multilayer container has excellent transparency, and its oxygen gas permeability is 0.03 m1/day-bottle-atm, and its carbon dioxide gas permeability is 0.27 m1/day, bottle'
-It was an ATM. Furthermore, in a drop test, the product did not break down at a drop of 2 meters or less. Further, delamination of each layer was not observed.

〔Effect of the invention〕

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

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi

Claims (4)

[Claims] (1) A polyester molded laminate composed of a co-condensed polyamide layer and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate, wherein the co-condensed polyamide contains (a) 30 to 70 isophthalic acid component units; 35 to 50 mol% of dicarboxylic acid component units contained in the range of mol%, (b) 35 to 50 mol% of diamine component units containing metaxylylenediamine component units as a main component, and A substantially linear co-condensed polyamide comprising 2 to 25 mol% of aminocarboxylic acid component units falling within the range of (d) intrinsic viscosity [η] of 0. 4 to 3, 0 a
/ g, and (f) a glass transition point is in the range of 50 to 150°C. (2) A polyester stretch laminate formed from a co-condensed polyamide layer and a polyalkylene terephthalate layer containing ethylene terephthalate as a main constituent unit, wherein the co-condensed polyamide contains 30 to 70 moles of (al) isophthalic acid component units. %
Dicarboxylic acid component units contained within the range of 35 to 5
(b) 35 to 50 mol% of diamine component units mainly composed of metaxylylene diamine component units, and (0 to 50 mol% of aminocarboxylic acid component units having C1 carbon atoms in the range of 5 to 12) 30 mol%, and its physical properties are as follows: (d) the intrinsic viscosity [η] is in the range of 0.4 to 3.0 d!/height; and ( e) A polyester stretch laminate molded product characterized by having a glass transition temperature in the range of 50 to 150°C. (3) A preform for a polyester multilayer blow molded article having a laminated structure composed of a co-condensed polyamide layer and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate, wherein the co-condensed polyamide is (8) isophthalic acid. 30 to 70 mol% of component units
Dicarboxylic acid component units contained within the range of 35 to 5
0 mol%, (bl) 35 to 50 mol% of diamine component units mainly composed of metaxylylene diamine component units, and (C) aminocarboxylic acid component units having a carbon number of 5 to 12. 0 to 30 mol%, a substantially linear co-condensed polyamide comprising: (d) an intrinsic viscosity [η] in the range of 0.4 to 3.0 a/g; (el) A preform for a polyester multilayer hollow molded article, characterized by having a glass transition temperature in the range of 50 to 150°C. (4) A polyester stretched multilayer hollow molded article composed of a co-condensed polyamide layer and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate, wherein the co-condensed polyamide contains (a) 30 to 30 isophthalic acid component units; 70 mol%
(b) 35 to 50 mol% of dicarboxylic acid component units in the range of (b) 35 to 50 mol% of diamine component units mainly composed of metaxylylenediamine component units, and Ic) having 5 to 12 carbon atoms. A substantially linear co-condensed polyamide consisting of O to 30 mol% of aminocarboxylic acid component units within the range, the physical properties of which are: (d) an intrinsic viscosity [η] of 0.4 to 3.0 dl; /'
A polyester stretched multilayer hollow molded article, characterized in that the polyester has a glass transition temperature of 50 to 150°C.