JPH0367501B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a polyester laminate molded product having excellent melt moldability, excellent mechanical strength and gas barrier properties, and suitable performance as a material for containers, and uses thereof. [Prior Art] Glass has been widely used as a material for containers for seasonings, oils, beer, alcoholic beverages such as Japanese sake, soft drinks such as carbonated drinks, cosmetics, detergents, and the like. However, although glass containers have excellent gas barrier properties, they are expensive to manufacture, so a method has been adopted in which empty containers are usually collected after use and recycled for reuse. In addition, glass containers are heavy, which increases shipping costs, and they also have drawbacks such as being easily damaged and inconvenient to handle. There is a growing shift from glass containers to various plastic containers as a solution to the aforementioned drawbacks of glass containers. Various plastics are used as the material, depending on the type of stored item and its intended use. Among these plastic materials, polyethylene terephthalate has excellent gas barrier properties and transparency, so it is used as a material for containers for seasonings, soft drinks, detergents, cosmetics, etc. However, polyethylene terephthalate is still not sufficient for beer and carbonated beverage containers, which require the most stringent gas barrier properties.
In order to be used in these containers, it was necessary to improve the gas barrier properties by increasing the wall thickness. Currently, the demand for polyester containers is increasing, and in order to expand these uses, there is a strong demand for polyester molded articles with excellent gas barrier properties and excellent 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, there are many proposals for co-condensation polymerization of aromatic dicarboxylic acid component units other than terephthalic acid as the third component in modified polyethylene terephthalate, but none of these proposals can produce polyethylene terephthalate. Although modified polyethylene terephthalate also has excellent stretchability, it cannot be said that any biaxially 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 molded product made by laminating a styrene/acrylonitrile copolymer is
Since the glass transition temperature of acrylonitrile copolymer is high, a laminate with polyester such as polyethylene terephthalate cannot be efficiently stretched, and a stretched laminate with excellent mechanical strength cannot be formed. be. Furthermore, a polyester laminate formed by laminating a co-condensed polyamide consisting of a diamine whose main component is meta-xylylene diamine and an aliphatic dicarboxylic acid may whiten during molding because the co-condensed polyamide is highly crystalline. It is difficult to easily form a laminate molded product with excellent transparency, and the adhesion between both resin layers is also poor, so it is difficult to obtain a laminate molded product with excellent mechanical strength. be. In addition, JP-A-58-183243 discloses that a polyester composition consisting of a co-condensed polyamide consisting of a diamine and an aliphatic dicarboxylic acid whose main component is metaxylylene diamine component and polyethylene terephthalate is used as an intermediate layer, and a polyethylene terephthalate layer is formed. A biaxially stretched blow-molded bottle has been proposed that has both inner and outer surface layers, but the middle layer of this multilayer blow-molded bottle contains a highly crystalline co-condensed polyamide containing a xylylenediamine component as described above. Because of this, it is easy to cause whitening phenomenon during molding, making it difficult to mold a multilayer blow-molded bottle with excellent transparency, and the co-condensed polyamide and polyethylene terephthalate are not compatible with each other. This multilayer blow-molded bottle has a problem in that it does not necessarily have sufficient mechanical strength. [Problems to be Solved by the Invention] The present inventors have recognized that the technology regarding polyester molded articles having gas barrier properties, particularly polyester multilayer blow-molded containers, is in the above-mentioned situation, and has improved melt moldability and stretch moldability. As a result of studying the development of a polyester composition that has excellent gas barrier properties and can exhibit excellent performance as a material for a gas barrier layer for stretched multilayer blow-molded containers, we found that dicarboxylic acid containing a specific proportion of isophthalic acid component units A polyester composition consisting of a co-condensed polyamide consisting of an acid component unit, a diamine component unit whose main component is metaxylylene diamine component unit, and optionally an aminocarboxylic acid component unit, and a polyalkylene terephthalate whose main constituent unit is ethylene terephthalate. has been found to achieve the above object, and furthermore, a laminate molded product comprising the polyester composition layer and a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit, a stretched laminate molded product thereof, and a laminate structure comprising the same. Preforms for multilayer hollow molded bodies and stretched multilayer hollow molded bodies formed from the preforms have excellent moldability, mechanical strength, and gas barrier properties, so they are suitable as materials for multilayer hollow molded bodies, especially stretch blow molded containers. The present invention was developed based on the discovery that the present invention is excellent. [Summary of the Invention] To summarize the present invention, the present invention comprises a polyester composition layer consisting of polyalkylene terephthalate A containing ethylene terephthalate as a main constituent unit and co-condensed polyamide B; A polyester laminate molded product comprising a terephthalate layer, wherein the co-condensed polyamide B contains (a) 30 to 100 mol% of isophthalic acid component units;
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 (c) 5 to 5 carbon atoms. A substantially linear co-condensed polyamide consisting of 0 to 30 mol% of aminocarboxylic acid component units in the range of The gist of the first invention is a polyester laminate molded product characterized by: (e) having a glass transition temperature in the range of 50°C to 180°C; A second gist of the invention is a polyester stretch laminate molded product composed of a polyester composition layer and a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit, and comprising a polyester composition layer and a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit. A third gist of the invention is a preform for a multilayer hollow molded body having a laminated structure, which is a stretched polyester multilayer hollow molded body comprised of the polyester composition layer and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate. This is the fourth invention and its gist. [Means and effects for solving the problems] The polyester composition layer constituting the polyester laminate molded product of the present invention is a polyester composition composed of polyalkylene terephthalate A and co-condensed polyamide B having ethylene terephthalate as a main constituent unit. It is. The co-condensed polyamide B constituting the polyester composition is a binary system consisting of dicarboxylic acid component units a containing isophthalic acid component units in a specific composition and diamine component units b having metaxylylene diamine component units as the main component. It may also be a co-condensed polyamide containing dicarboxylic acid component units (a) containing isophthalic acid component units in a specific composition, diamine component units (b) containing metaxylylene diamine component units as a main component, and aminocarboxylic acid component units (c). It may also be a ternary co-condensed polyamide consisting of. 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. Any of the above-mentioned component units may be arranged at the molecular terminal of the co-condensed polyamide,
Further, the carboxyl group present at the end of the molecule may be amidated with another lower amine, or may be amidated with another lower amide. Similarly, the amino group present at the end of the molecule may be amidated with another lower carboxylic acid. The co-condensed polyamide B of the present invention has a substantially linear structure. Here, the term "substantially linear structure" means a linear or branched chain structure, and means not having a gel-like crosslinked structure (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 100 mol% of isophthalic acid component units;
(b) 35 to 50 mol% of dicarboxylic acid component units, preferably 40 to 50 mol%, of dicarboxylic acid component units contained in the range of (b) 35 to 50 mol of diamine component units containing metaxylylene diamine component units as a main component. %, preferably in the range from 40 to 50 mol %, and (c) from 0 to 30 mol %, preferably from 0 to 20 mol %, of aminocarboxylic acid component units having from 5 to 12 carbon atoms. , is. In the co-condensed polyamide, when the content of dicarboxylic acid component units a and diamine component units b is smaller than 35% and the content of aminocarboxylic acid component units c is larger than 30 mol%, polyester laminate molded products, stretch laminates, etc. This is not preferable because the gas barrier properties of the molded product and stretched multilayer hollow molded product will be reduced. Further, the dicarboxylic acid component unit a constituting the co-condensed polyamide must contain isophthalic acid component units in the range of 30 to 100 mol%,
Furthermore, 30 to 100 mol%, especially 40 to 100
The content is preferably in the range of mol%. Dicarboxylic acid component units other than isophthalic acid component units are usually aliphatic, alicyclic or aromatic dicarboxylic acid component units having a carbon atom number in the range of 5 to 18, specifically glutamic acid. , adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc., α,ω-aliphatic dicarboxylic acids, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, etc. , terephthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, and other aromatic dicarboxylic acids. The content of dicarboxylic acid component units other than the isophthalic acid component units in the dicarboxylic acid component units is 0 to 70 mol°C.
More preferably, it is in the range of 0 to 65 mol%, particularly 0 to 60 mol%. Among the dicarboxylic acid component units other than the above-mentioned isophthalic acid component units, α,ω-aliphatic dicarboxylic acid component units are contained in the range of 0 to 70 mol%, particularly 0 to 60 mol%, based on the total dicarboxylic acid component units. When it is contained, a polyester laminate molded product having excellent melt moldability, stretch moldability, and gas barrier properties can be obtained, which is preferable. When the content of isophthalic acid component units in the dicarboxylic acid component units constituting the co-condensed polyamide is less than 30 mol% and the content of dicarboxylic acid component units other than isophthalic acid component units is greater than 70 mol%, the The gas barrier properties and interlayer adhesion properties of polyester laminate molded products, stretched laminate molded products, preforms for stretched multilayer hollow molded products, and stretched multilayer hollow molded products become inferior. The diamine component unit a constituting the co-condensed polyamide has a meta-xylylene diamine component unit as a main component, and may be the sole component of meta-xylylene diamine, or a diamine component unit a containing a meta-xylylene diamine component unit as a main component. In addition, it may be a mixed component consisting of diamine component units other than metaxylylene diamine component units. 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, diamine component units other than metaxylylene diamine component units include xylylene diamines such as para-xylylene diamine and orthoxylylene diamine;
-Diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane and other aliphatic diamines having a carbon atom number ranging from 4 to 12. Examples include diamines, and among these diamines, xylylene diamine is preferred. Further, the aminocarboxylic acid component unit c optionally contained in the co-condensed polyamide is an aminocarboxylic acid component unit having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and is not limited to aminocarboxylic acids but also aminocarboxylic acid component units having 5 to 12, preferably 6 to 10 carbon atoms. Also included are lactams that form aminocarboxylic acid component units in the condensed polyamide molecule.
Specifically, the aminocarboxylic acid component unit is:
δ-aminovaleric acid, ε-aminocaproic acid, ω-
Examples include aminocaprylic acid and ω-aminocapric acid. N,N-dimethylacetamide-lithium chloride mixed solvent (weight ratio 100:5) of the co-condensed polyamide
The intrinsic viscosity [η] measured at 25℃ is 0.2 to
It is necessary to be in the range of 2.5 dl/g, and more preferably in the range of 0.3 to 2.0 dl/g. When the intrinsic viscosity [η] is larger than 2.5 dl/g, the melt moldability of the co-condensed polyamide becomes poor, and when the intrinsic viscosity [η] is smaller than 0.2 dl/g, the polyester laminate molded product Stretch laminate molded products, preforms for multilayer hollow molded products,
The mechanical strength of the stretched multilayer hollow molded product becomes inferior. Furthermore, the glass transition temperature of the co-condensed polyamide is
It is necessary to be in the range of 50 to 180℃,
More preferably, the temperature is in the range of 60 to 170°C. The glass transition temperature of the co-condensed polyamide is
When the temperature is higher than 180°C, the melt moldability of the co-condensed polyamide becomes poor, and melt molding is difficult when producing the polyester laminate molded product, stretched laminate molded product, preform for multilayer hollow molded product, and stretched multilayer hollow molded product. This results in poor elasticity and stretch formability. Furthermore, if the glass transition temperature is lower than 50° C., the co-condensed polyamide cannot be easily and economically dried. Polyalkylene terephthalate A constituting the polyester composition is a polyester containing ethylene terephthalate as a main constituent unit. The content of ethylene terephthalate structural units in the polyalkylene terephthalate is usually 50 mol% or more, preferably 70 mol% or more. The dicarboxylic acid component units constituting the polyalkylene terephthalate may contain a small amount of other aromatic dicarboxylic acid component units in addition to the terephthalic acid component units. Specific examples of aromatic dicarboxylic acid component units other than the terephthalic acid component units include isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid. The diol 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, cyclohexanedimethanol,
1,4-bis(β-hydroxyethoxy)benzene, 1,3-bis(β-hydroxyethoxy)benzene, 2,2-bis(4-β-hydroxyethoxyphenyl)propane, bis(4-β-hydroxy) Examples include diol component units having 3 to 15 carbon atoms such as (ethoxyphenyl) sulfone. In addition, the polyalkylene terephthalate has
In addition to the aromatic dicarboxylic acid component unit and the diol component unit, it may contain a small amount of a polyfunctional compound as required. Specifically, the polyfunctional compound component unit includes aromatic polybasic acids such as trimellitic acid, trimesic acid, 3,3',5,5'-tetracarboxydiphenyl, and aliphatic acids such as butanetetracarboxylic acid. polybasic acid,
Phloroglucin, aromatic polyols such as 1,2,4,5-tetrahydroxybenzene, aliphatic polyols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, oxypolycarboxylic acids such as tartaric acid, malic acid, etc. can be exemplified. The composition of the constituent components of the polyalkylene terephthalate is such that the content of terephthalic acid component units is usually 50
from 100 mol%, preferably from 70 to 100 mol%
The content of aromatic dicarboxylic acid component units other than terephthalic acid component units is usually in the range of 0 to 50 mol%, preferably 0 to 30 mol%, and the content of ethylene glycol component units is usually in the range of 0 to 30 mol%. 50 to 100 mol%, preferably 70 to 100
The content of diol component units other than ethylene glycol component units is usually 0 to 50 mol%, preferably 0 to 30 mol%, and the content of polyfunctional compound component units is usually 0.
It ranges from 0 to 2 mol%, preferably from 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 dl/g, preferably
It ranges from 0.6 to 1.2 dl/g, and the melting point is usually
210 to 265°C, preferably 220 to 260°C, glass transition temperature usually 50 to 120°C,
Preferably it is in the range of 60 to 100. In the polyester composition, the proportion of the co-condensed polyamide B is usually 2 to 500 parts by weight per 100 parts by weight of the polyalkylene terephthalate A.
Parts by weight are preferably in the range from 3 to 300 parts by weight, particularly preferably from 5 to 100 parts by weight. The polyamide composition includes the polyalkylene terephthalate A and the co-condensed polyamide B.
In addition, if necessary, nucleating agents, inorganic fillers,
Appropriate amounts of various additives such as lubricants, slip agents, antiblocking agents, stabilizers, antistatic agents, antifogging agents, and pigments may be blended. The polyester composition can also be used in an unstretched state as a raw 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 product with even better gas barrier properties can be obtained. Next, a polyester laminate molded product composed of a polyester composition layer of the present invention and a polyalkylene terephthalate layer containing ethylene terephthalate as a main constituent unit will be described. Specifically, the laminate molded product is a two-layer laminate molded product composed of two layers, the polyester composition layer and the polyalkylene terephthalate layer, the polyester composition layer is the middle layer, and both outer layers are the polyester composition layer and the polyalkylene terephthalate layer. A three-layer laminate molded product having an alkylene terephthalate layer, a three-layer laminate molded product having the polyalkylene terephthalate layer as an intermediate layer and the polyester composition layer on both sides, and alternating the polyester composition layer and the polyalkylene terephthalate layer. A multilayer laminate molded product having a four-layer structure or more, in which both outermost layers are composed of the polyalkylene terephthalate layer, and a four-layered product in which the polyester composition layer and the polyalkylene terephthalate layer are alternately laminated. A multilayer laminate molded product having a structure or more, in which both outermost layers are composed of the polyester composition layer, a laminate molded product having a four-layer structure or more in which the polyester composition layers and the polyalkylene terephthalate layers are alternately laminated. For example, a multilayer laminate molded product having a body whose outermost layer is composed of the polyester composition layer and the polyalkylene terephthalate layer. The laminate molded product is a sheet-like product,
It can be applied not only to plate-shaped objects and tubular objects, but also to various hollow objects, containers, and structures of various shapes. The laminate molded product can be manufactured by a conventionally known method. The thicknesses of the polyester composition layer and the polyalkylene terephthalate layer constituting the laminate molded product are appropriately determined depending on the use of the laminate molded product, and are not particularly limited. When the laminate molded product is the two-layer laminate molded product, the thickness of the polyester composition layer is usually in the range of 1 to 350μ, preferably 2 to 200μ, and the thickness of the polyalkylene terephthalate layer is 8 to 600μ,
It is preferably in the range of 10 to 500μ. When the laminate molded product is the former of the three-layer laminate molded product, the thickness of the intermediate layer consisting of the polyester composition layer is usually in the range of 1 to 350μ, preferably 2 to 200μ, and 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 in the range of 8 to 600μ, preferably 10 to 500μ. The thickness of both outer layers of the polyester composition layer generally ranges from 1 to 100 microns, preferably from 1 to 50 microns. Even when the laminate molded product is a multilayer laminate molded product having the four-layer structure, 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. The same polyalkylene terephthalate as polyalkylene terephthalate A used as a structural unit can be exemplified. The polyalkylene terephthalate constituting the polyalkylene terephthalate layer of the polyester laminate molded product does not need to be the same as the polyalkylene terephthalate A constituting the polyester composition layer. The polyalkylene terephthalate constituting the polyalkylene terephthalate layer may contain nucleating agents, inorganic fillers, lubricants, antiblocking agents, stabilizers, antistatic agents, and antifogging agents that are blended into conventional polyesters as necessary. There is no problem even if appropriate amounts of various additives such as agents, pigments, etc. are blended. The polyester laminate molded product of the present invention has excellent properties such as melt moldability, stretchability, mechanical strength, transparency, and gas barrier properties, so it can be used for various purposes. A polyester stretch laminate molded product comprising a polyester composition layer of the present invention and a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit will be described. The polyester stretch laminate molded product of the present invention is a polyester laminate molded product comprising the polyester composition layer and the polyalkylene terephthalate layer, and has the above-described laminate structure, and at least one of the polyalkylene terephthalate layers is stretched. A polyester stretch laminate molded product in a state where the polyester composition layer and the polyalkylene terephthalate layer are formed, preferably the polyester laminate molded product has the above-mentioned laminate structure, and at least all of the polyalkylene terephthalate layer. A polyester stretch laminate molded product in which the layer is in a stretched state, particularly preferably a polyester laminate molded product having the above-mentioned laminate structure, comprising the polyester composition layer and the polyalkylene terephthalate layer, and the polyester composition layer is in a stretched state. All layers of the polyalkylene terephthalate layer and the polyalkylene terephthalate layer are in a stretched state. The stretched layer may be in a uniaxially 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 stretch laminate is uniaxially stretched, the stretching ratio is usually 1.1 to 10 times, preferably 1.2 to 8 times, particularly preferably 1.5 to 7 times. In addition, when the constituent resin layer is a biaxially stretched layer, the stretching ratio in the longitudinal axis direction is usually 1.1 to 8 times, preferably 1.2 to 7 times,
Particularly preferably, it is in the range of 1.5 to 6 times,
Usually 1.1 to 8 times, preferably
The range is from 1.2 to 7 times, particularly preferably from 1.5 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 the manufacturing method. In general, the polyester composition and the polyalkylene terephthalate are melted in separate extruders and molded by melt coextrusion from a multilayer T-die to form an original laminate, such as a multilayer laminate film (laminated sheet). A method is adopted in which the material is kept in a heated state or is once cooled and solidified to a temperature below the glass transition point, and then stretched after being reheated. In addition, as another method, there is a method of extrusion laminating the polyester composition on a film-like material (sheet-like material) previously formed from the polyalkylene terephthalate, or a method of sandwich laminating the polyester composition. The film-like material (sheet-like material) may be uniaxially or biaxially stretched before lamination, or may be similarly stretched after lamination. Furthermore, there is a method of extrusion laminating the polyalkylene terephthalate on a film-like product (sheet-like product) previously formed from the polyester composition, or a method of sandwich laminating the polyalkylene terephthalate. The (sheet-like material) may be uniaxially stretched 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 preferable because it provides the following. In addition, when producing the polyester stretched laminate molded product, the method for applying the stretching treatment includes, when the original molded product is a film-like product (sheet-like product),
A method of stretching the original molded product in a uniaxial direction (uniaxial stretching), a method of stretching in the longitudinal direction and then further stretching in the transverse direction (biaxial stretching), a method of simultaneously stretching in the longitudinal and transverse directions (biaxial stretching) axial stretching), biaxial stretching followed by repeated stretching in one direction, biaxial stretching followed by further stretching in both directions, reducing the pressure in the space between the original molded product and the mold. For example, a so-called vacuum forming method in which stretch forming is performed. 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 excellent properties such as mechanical strength, transparency, and gas barrier properties, and therefore 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 molded 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 includes the above-mentioned preform. This is a preform for a multilayer hollow molded body having a 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 preform having four or more layers. I can give an example. Among these preforms for multilayer blow 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 both outer layers as the polyalkylene terephthalate layer. When a stretched multilayer hollow molded body is formed from a preform having a laminated structure composed of three polyalkylene terephthalate layers, the stretched multilayer hollow molded body has excellent properties such as excellent mechanical strength, transparency, and gas barrier properties. This is preferable because it allows you to obtain A nucleating agent, an inorganic filler, a lubricant, and a slip agent, which are blended into conventional polyester or polyamide as necessary, are added to both the polyester composition and the polyalkylene terephthalate constituting the preform for a multilayer blow molded article of the present invention. , anti-blocking agent, stabilizer, antistatic agent, anti-fog agent,
Appropriate amounts of various additives such as pigments may be blended. The polyester multilayer hollow molded preform of the present invention is produced by a conventionally known method. For example, the preform for a polyester multilayer hollow molded article of the present invention can be obtained by molding the tubular article having the laminated structure. The polyester stretched multilayer hollow molded article of the present invention is
This 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 stretched multilayer hollow molded body. 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 alternately laminated, 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 a hollow layer and the polyalkylene terephthalate layer as an inner layer and an outer layer. The polyester composition layer may be a stretched multilayer hollow molded body in which the polyester composition 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 polyester composition layer may be the inner layer, and the polyalkylene terephthalate layer may be the inner layer. It may be. Among the polyester stretch laminate molded products of the present invention, a stretched multilayer hollow molded product in which the inner layer is a polyalkylene terephthalate layer is preferable, and in particular, the polyester composition layer is an intermediate layer and the polyalkylene terephthalate layer is a polyester composition 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 biaxially stretched product, but generally a biaxially stretched product has excellent mechanical strength and gas barrier properties. suitable. As for the stretching ratio of the stretched multilayer hollow molded product, the stretching ratio described for the stretched laminate molded product made of the polyester composition and the polyalkylene terephthalate is applied as is. The polyester stretched multilayer hollow molded article of the present invention is produced by stretch-blow molding the preform for the polyester multilayered hollow molded article. Examples of this method include a method (biaxial stretch blow molding) in which a preform at the above temperature is stretched in the longitudinal 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 is
It has excellent mechanical strength, heat resistance, and gas barrier properties, so it can be used for a variety of purposes. In particular, the biaxially stretched multilayer blow-molded container of the present invention has excellent gas barrier properties, so it can be used for seasonings,
It is excellent as a container for oil, alcoholic beverages such as beer and sake, soft drinks such as cola, cider, and youth, cosmetics, and detergents, but especially when used as a container for beer or carbonated beverages, the wall thickness of the container may need to be made thinner. This makes it possible to extend the best-before period. Next, the present invention will be specifically explained using examples. In addition, in the examples and comparative examples, performance evaluation was performed according to the following method. The intrinsic viscosity [η] of the co-condensed polyamide is N, N
-Dimethylacetamide-lithium chloride mixed solvent (weight ratio 100:5) by measurement 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 proportion of the raw material monomers used during production, which means that the co-condensed polyamide is heated in a nuclear magnetic solution such as a trifluoroacetic acid solution or a deuterated sulfuric acid solution. This can be confirmed by measuring resonance spectra. The intrinsic viscosity [η] of the polyalkylene terephthalate was determined by measurement at 25°C in a phenol-tetrachloroethane mixed solvent (weight ratio 100:100). The glass transition temperature and melting point of the polyalkylene terephthalate were determined by measuring with a differential scanning calorimeter. In addition, regarding the gas barrier properties of polyester laminate molded products, polyester stretched laminate molded products, or polyester stretched multilayer hollow molded products, oxygen gas permeability coefficients were determined using an OXTRAN device manufactured by MOCON, and carbon dioxide gas permeability. The coefficients were each measured at 25° C. using a PERMATRAN C-device manufactured by MOCON. [Example] Example 1 Polyethylene terephthalate (trade name, Mitsui PETJ135 [η] 0.83 dl/
g) is melted using an extruder at a molding temperature of 275°C,
Isophthalic acid/adipic acid/methaxylylene diamine co-condensed polyamide (composition (mol) ) ratio 21:29:50, intrinsic viscosity [η] 0.62 dl/g, glass transition temperature (Tg) 103
°C] A mixture of 40 parts by weight was melted at 275 °C using another extruder, fed to two-layer coat hanger type T-dies, extruded into sheets, and further cooled with rolls. As a result, a two-layer, two-layer laminate sheet was prepared in which the polyethylene terephthalate layer had a thickness of about 100 μm and the composition layer of polyethylene terephthalate and isophthalic acid/adipic acid/methaxylylene diamine cocondensed polyamide had a thickness of about 100 μm. The obtained laminated sheet has good interlayer adhesion between the polyethylene terephthalate layer and the composition layer, and its oxygen gas permeability coefficient is 0.3.
ml・mm/m ²・day・atm, and the carbon dioxide gas permeability coefficient was 3.6ml・mm/m ²・day・atm. Examples 2 to 13 In place of the polyethylene terephthalate supplied to one extruder in Example 1 or the mixture of polyethylene terephthalate and co-condensed polyamide supplied to the other extruder, polyethylene terephthalate or polyethylene terephthalate listed in Table 1 was used, respectively. Example 1 except that the mixture with condensed polyamide was used at the mixing ratio shown in Table 1.
In the same manner as above, a two-layer two-layer laminate sheet was prepared in which the polyethylene terephthalate layer had a thickness of about 100 μm and the composition layer had a thickness of about 100 μm.

【table】

【table】

[Table] Comparative Example 1 Polyethylene was prepared in the same manner as in Example 1 except that a polyamide of adipic acid and metaxylylene diamine [[η] 0.83 dl/g, Tg 86°C] was used instead of the co-condensed polyamide in Example 1. A two-layer, two-layer laminate sheet was prepared in which the terephthalate layer and the composition layer each had a diameter of approximately 100 μm. The carbon dioxide permeability coefficient of the obtained laminated sheet was 7.5ml・mm/m ²・day・
It was hot at the ATM. Comparative Example 2 In place of the co-condensed polyamide in Example 1, isophthalic acid/adipic acid/methaxylylene diamine co-condensed polyamide [composition (mole ratio) 25:25:
50, [η] 0.17 dl/g, 113°C], and Mitsui PETJ105 ([η]: 0.68 dl/g) was used as polyethylene terephthalate to be mixed with this co-condensed polyamide.
A two-layer, two-layer laminate sheet was prepared in the same manner as in Example 1, except that the polyethylene layer and the composition layer each had a diameter of 100 μm. The strength of the composition layer of this laminated sheet was low, and cracks occurred when bent, so that test pieces for measuring gas barrier properties could not be obtained. Example 11 The polyethylene terephthalate in Example 1 was melted at a molding temperature of 275°C using an extruder, and the mixture of polyethylene terephthalate and co-condensed polyamide in Example 1 was separately melted at a molding temperature of 280°C using another extruder. By melting and supplying it to a three-layer coat hanger type T-die so that the upper and lower layers are polyethylene terephthalate and the middle layer is a composition, extrusion into a sheet shape and further cooling with a roll, A laminated sheet of two types and three layers was prepared, each having a polyethylene terephthalate layer having a thickness of approximately 75μ and a composition layer having a thickness of approximately 75μ. The obtained laminated sheet has good interlayer adhesion between the polyethylene terephthalate layer and the co-condensed polyamide layer, and its carbon dioxide permeability coefficient is 5.1ml.
It was mm/m ²・day・atm. Example 15 The laminated sheet consisting of the polyethylene terephthalate layer and the composition layer in Example 1 was stretched 3 times each in the vertical and horizontal directions using a biaxial stretching device.
A biaxially stretched film was prepared by simultaneously stretching the film. The resulting biaxially stretched film had a thickness of about 11 μm for both the polyethylene terephthalate layer and the composition layer, 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 gas permeability coefficient of this biaxially stretched film was 3.0 ml·mm/m ² ·day·atm. Examples 16-24 Biaxially stretched films having the stretching ratios shown in Table 2 were produced by simultaneous biaxial stretching in the same manner as in Example 15, except that the laminated sheets listed in Table 2 were used instead of the laminated sheets in Example 15. . As shown in Table 2, the obtained biaxially stretched films each had a polyethylene terephthalate layer and a composition layer having approximately the same thickness, and were uniformly biaxially 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.

〔Effect of the invention〕

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

Claims (1)

[Scope of Claims] 1. Polyester laminate molding consisting of a polyester composition layer consisting of polyalkylene terephthalate A whose main constituent unit is ethylene terephthalate and co-condensed polyamide B, and a polyester composition layer whose main constituent unit is ethylene terephthalate. and the co-condensed polyamide B
(a) 30 to 100 mol% of isophthalic acid component units;
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 (c) 5 to 5 carbon atoms. A substantially linear co-condensed polyamide consisting of 0 to 30 mol% of aminocarboxylic acid component units in the range of (e) having a glass transition point in the range of 50 to 180°C. 2. A polyester stretch molded article composed of a polyester composition layer consisting of polyalkylene terephthalate A having ethylene terephthalate as its main constituent unit and co-condensed polyamide B, and a polyester composition layer having ethylene terephthalate as its main constituent unit, Co-condensed polyamide B
(a) 30 to 100 mol% of isophthalic acid component units;
(b) contains 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 metaxylylene diamine component units; (c) has 5 to 12 carbon atoms; A substantially linear co-condensed polyamide consisting of 0 to 30 mol% of aminocarboxylic acid component units in the range of (d) an intrinsic viscosity [η] of 0.2 to 2.5 dl/g; and (e) a glass transition temperature in the range of 50 to 180°C. 3. A preform for a polyester multilayer blow-molded article, which is composed of a polyester composition layer consisting of polyalkylene terephthalate A having ethylene terephthalate as its main constituent unit and co-condensed polyamide B, and a polyalkylene terephthalate layer having ethylene terephthalate as its main constituent unit. The co-condensed polyamide B contains (a) 30 to 100 mol% of isophthalic acid component units;
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 (c) 5 to 5 carbon atoms. A substantially linear co-condensed polyamide consisting of 0 to 30 mol% of aminocarboxylic acid component units in the range of (e) having a glass transition temperature in the range of 50 to 180°C. 4. A polyester multilayer blow-molded article comprising a polyester composition layer consisting of polyalkylene terephthalate A having ethylene terephthalate as its main constituent unit and co-condensed polyamide B, and a polyalkylene terephthalate layer having ethylene terephthalate as its main constituent unit, The co-condensed polyamide B contains (a) 30 to 100 mol% of isophthalic acid component units;
35 to 35 dicarboxylic acid component units in the range of
50 mol%, (b) 35 to 50 mol% of diamine component units mainly composed of metaxylylene diamine component units, and (c) 0 aminocarboxylic acid component units having a carbon number in the range of 5 to 12. A substantially linear co-condensed polyamide consisting of from 30 mol% to 30% by mole, the physical properties of which are (d) an intrinsic viscosity [η] in the range of 0.2 to 2.5 dl/g, and (e) glass. A polyester stretched multilayer hollow molded article characterized by having a transition temperature in the range of 50 to 180°C.