JPS61241147A - Polyester laminated molded shape and application thereof - Google Patents

Abstract

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

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyester laminate that has excellent melt moldability, excellent mechanical strength and gas barrier properties, and has properties suitable as a material for containers. be.

[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. 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, so it is used as a material for containers for seasonings, soft drinks, detergents, cosmetics, etc.

has been adopted. However, polyethylene terephthalate is still not sufficient for beer and carbonated beverage containers, which require the most stringent gas barrier properties (although polyethylene terephthalate does not have enough wall thickness to be used in these containers). At present, the demand for polyester containers is increasing, but in order to expand their use, it is necessary to improve the gas barrier properties by increasing the gas barrier properties and melt moldability. There is a strong demand for superior polyester.

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

Japanese Unexamined Patent Publication No. 59-670 filed by the same applicant as the above application
Publication No. 49 discloses a multilayer packaging material made of a layer made of polyisophthalate or a copolymer thereof as described above and a layer made of a polyterephthalate such as poly(ethylene terephthalate) or a copolymer thereof, and a molded product made thereof, such as a bottle. ing.

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

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

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

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

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

Additionally, the Journal of Applied Polymer Science
lymerScience), Volume 7, 2135~
2144 (1963), the following formula prisoners, 1000 -E -0-CIl2-CIl-CI+2+...
・(C) 1 "H Here, E is CH, ct 1-L3H. The gas barrier properties of homopolyhydroxy ethers represented by the following are disclosed. The one with the lowest oxygen permeability is E.
is of 0.5cc-wit/10
0in'/24hr/atm. The one with the lowest water vapor mobility CH3 α 4 α C1 (.

The value is 100°F190%R, Il,
3 g-mil/100in for 24h under conditions of
It is r.

The Journal of Applied Polymer Science
ymerScience), Volume 7, 2145-2
152 (1963), has the following formula CB) -R-0C112CIl CH20-R2-0CII2
C1l CH20-...[F]) where R3 is (However, R1 and R2 are not the same)
'Svalya properties are disclosed. The one with the lowest oxygen permeability is the one where R6 is H3 CH3, and the value in both cases is 5g-11/10
0in/24hr/ato+. The lowest water vapor mobility is the one where R, is 1-13 CH3, which is 4 g-ml/100 in2/24 hr under each condition of 100°F and 190% RH.

[Problem that the invention seeks to solve]

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

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

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

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

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

[Means and effects for solving the problems] The above objects and advantages of the present invention are as follows: First, polyalkylene terephthalate (A) having ethylene terephthalate as a main constituent unit and co-condensed polyester (
A polyester laminate molded product comprising a polyester composition layer consisting of B) and a polyalkylene terephthalate layer having ethylene terephthalate as a main constituent unit,
The co-condensed polyester (B) contains (a) 25 to 48 mol% of aromatic dicarboxylic acid component units mainly composed of isophthalic acid component units, (b)
l 45 to 50 mol% of diol component units mainly composed of ethylene glycol component units, (C) 2 to 25 mol% of aromatic oxycarboxylic acid component units having 12 or less carbon atoms, and (d) carbon O to 2 mol% of polyfunctional compound component units having an atom number in the range of 3 to 15 and having 3 or more carboxyl groups or hydroxyl groups, and (e) 0.5 to 1.5 Fi in the range of d1/g
This is achieved by a laminate, characterized in that it is a substantially linear polyester having a limiting viscosity Crt) and (f) a glass transition temperature in the range from 50 to 120C.

The co-condensed polyester used in the present invention is: Aromatic dicarboxylic acid component unit (a) mainly composed of isophthalic acid component unit, Diol component unit (b) mainly composed of ethylene glycol component unit, Aromatic oxycarboxylic acid component unit (b) It can be a ternary co-condensed polyester consisting of carboxylic acid component units (C), and aromatic dicarboxylic acid component units (al) having isophthalic acid component units as the main component, ethylene glycol component units as the main component. Diol component unit (b)
, a quaternary co-condensation polyester consisting of an aromatic oxycarboxylic acid component unit (C) and a polyfunctional compound initial component unit (d). In either case, in the co-condensed polyester of the present invention, adjacent carboxyl groups and hydroxyl groups of each component unit are condensed to form an ester bond, and adjacent phenolic hydroxyl groups and hydroxyl groups of the diol component unit are condensed. A polymer molecular chain is formed by condensing and forming an ether bond. Any of the above component units may be arranged at the molecular terminal of the co-condensed polyester. Furthermore, the carboxyl group present at the end of the molecule may be esterified with another lower alcohol, and similarly the hydroxyl group present at the end of the molecule may be esterified with another lower carboxylic acid or with another alcohol. May be etherified. The diol component unit (b) mainly composed of ethylene glycol component units constituting the co-condensed polyester has a small portion (for example, 10 mol% or less) that forms an ether bond through a reaction between diol component units such as diethylene glycol component units. There is no problem even if a diol component unit having the following is formed.

The co-condensed polyester used in the present invention has a substantially linear structure. Here, the term "substantially linear structure" means that it consists essentially of a chain structure having a straight chain or a branched chain, and does not mean that it is substantially a gel-like crosslinked structure (network structure). This is confirmed by the fact that the co-condensed polyester of the present invention is substantially completely dissolved in the phenol-tetrachloroethane mixed solvent (weight ratio 1/1). When the co-condensed polyester is a co-condensed polyester consisting of the five constituent components, it is linear;
When it is a co-condensed polyester consisting of the above-mentioned image constituent components, it is branched.

The composition of the co-condensed polyester in the present invention is (a)
Aromatic dicarboxylic acid component units mainly composed of isophthalic acid component units are 25 to 48 mol%, preferably 3
It is in the range of 0 to 48 mol%, and ('b) has 4 diol component units mainly composed of ethylene glycol component units.
5 to 50 mol%, preferably 46 to 50 mol%, and (C) the aromatic oxycarboxylic acid component unit is 2 to 25 mol%, preferably 2 to 2
and +d) O to 2 mol%, preferably 0, of polyfunctional compound component units having a carbon number ranging from 3 to 15 and having 3 or more carboxyl or hydroxyl groups; The composition ranges from 1.5 to 1.5 mol%. In the co-condensed polyester, the content of the aromatic dicarboxylic acid component unit (a) is less than 25 mol% and the aromatic oxycarboxylic acid component unit (C)
If the composition has a content of more than 25 mol%, the esterification reaction, etherification reaction, and polycondensation reaction during the production of the polyester require a long time, and the co-condensed polyester and its stretched product require a long time. The gas barrier property of the co-condensed polyester decreases, which is unfavorable from the viewpoint of productivity and performance.In addition, in the co-condensed polyester, the content of the aromatic dicarboxylic acid component unit (a) is greater than 48 mol% and the aromatic dicarboxylic acid component unit (a) is Those with a composition in which the content of oxycarboxylic acid component units (C) is less than 2 mol % have already been used in the Journal during the polycondensation reaction during the production of the polyester.
al of Polymer 5science+No.40
Vol. (1955), p. 59, a cyclic oligomer of isophthalic acid and ethylene glycol begins to be produced, and as a result of the production of the cyclic oligomer, the polymer yield decreases. This is unfavorable in terms of productivity because it precipitates and sticks to the parts of the polymerization apparatus that are not heated. Furthermore, the oligomer may be mixed in when recovering the co-condensed polyester after the polycondensation reaction, which may cause quality problems, and in order to avoid this, it is necessary to take special measures for the equipment. This is not desirable from an economic point of view. In addition, the content of the polyfunctional compound units constituting the co-condensed polyester is thicker than 2 mol% (if this happens, the co-condensed polyester will contain a large amount of gel-like structure and will no longer be substantially linear; Melt formability begins to deteriorate.

The co-condensed polyester in the present invention has an intrinsic viscosity [phenol-tetrachloroethane mixed medium (weight ratio 1/1
) measured at 25℃] is O05 to 1.5 dl.
/g.

Within this range, it is preferably in the range of 0.6 to 2a/g. Also, its glass transition point is 50 to 120.
It is necessary that the temperature be within the range of ℃. Within this range, the temperature is preferably in the range of 55 to 100°C.

The intrinsic viscosity of the co-condensed polyester is 1.5 dl/g
When it is larger than 0.5 dl/g, the melt moldability of the co-condensed polyester decreases, and furthermore, its stretchability decreases, and when it becomes smaller than 0.5 dl/g, the mechanical strength of the co-condensed polyester and its stretched products decreases. It becomes like this. Further, the glass transition temperature of the co-condensed polyester is 5
If the temperature is lower than 0°C, it is not preferable because it becomes difficult to economically perform the drying process necessary to reduce the molecular weight drop during melt molding of the polyester.

The aromatic dicarboxylic acid component units (Q) constituting the co-condensed polyester in the present invention are mainly composed of isophthalic acid component units, and the ratio of isophthalic acid component units to all aromatic dicarboxylic acid component units is is usually 50 to 100 mol%, preferably 70 to 100 mol%
The range is mole %. Examples of aromatic dicarboxylic acid component units other than isophthalic acid component units include aromatic dicarboxylic acid component units having 8 to 12 carbon atoms such as terephthalic acid, phthalic acid, and 2,6-naphthalene dicarboxylic acid. be able to.

The diol component units fb) constituting the co-condensed polyester used in the present invention are mainly composed of ethylene glycol component units, and the ratio of the ethylene glycol component units to the total diol component units is usually 50 to 100 mol%, It is preferably in the range of 70 to 100 mol%. Examples of diol component units other than ethylene glycol include 1.3-propanediol, 1.
4-butanediol, neopentyl glycol, cyclohexanediol, dichlorohexane dimetatool, 1.
4-bis(β-hydroxyethoxy)benzene, 1.3
-bis(β-hydroxyethoxy)benzene, 2,2-
Examples include diol component units having 3 to 15 carbon atoms such as bis(4-β-hydroxyethoxyphenyl)propane and bis(4-β-hydroxyethoxyphenyl)sulfone.

The aromatic oxycarboxylic acid component unit (C) constituting the co-condensed polyester in the present invention is an aromatic oxycarboxylic acid component unit having a carbon atom number in the range of 7 to 12. More specifically, salicylic acid, 4-methylsalicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 4-
Examples include hydroxy-1-naphetic acid and 6-methyl-4-hydroxy-1-naphetic acid, and a mixture of two or more of these may be used.

The polyfunctional compound component unit +d) constituting the co-condensed polyester in the present invention is a trifunctional or higher polyfunctional compound component having three or more carboxyl groups or hydroxyl groups having a carbon number of 3 to 15. unit, and the carboxyl group and hydroxyl group together are 3
It also includes polyfunctional compound component units having more than one. 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 acids, phloroglucin, aromatic polyols such as 1.2.4.5-tetrahydroxybenzene, aliphatic polyols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tartaric acid, malic acid, etc. Examples include oxypolycarboxylic acids.

The co-condensed polyester used in the present invention can be produced according to the conventionally known polycondensation method employed in the production of polyethylene terephthalate.

The aromatic dicarboxylic acid component unit as a component can be used in the reaction system, for example, as the aromatic dicarboxylic acid, as its dialkyl ester, or as an ester of a diol such as bis β-hydroxyethyl ester of the aromatic dicarboxylic acid. It can be formed by supplying it to - The diol component unit of the constituent component can be formed by supplying it to the reaction system, for example, as a diol or in the form of a diol ester of the carboxylic acid of the constituent component.

In addition, the aromatic oxycarboxylic acid component unit as a component may be, for example, the aromatic oxycarboxylic acid, the alkyl ester of the aromatic oxycarboxylic acid, or the ether form of the aromatic oxycarboxylic acid with a diol. Furthermore, it can be formed by supplying it to the reaction system as a diol ester of an aromatic oxycarboxylic acid.

As the catalyst for copolycondensation, for example, a catalyst consisting of antimony, germanium, titanium, or a compound thereof and a phosphorus compound is used. As the form of the antimony, germanium or titanium compound, oxides, hydroxides, halides, inorganic acid salts, organic acid salts, complex salts, double salts, alcoholades, phenolates and the like are used. These catalysts can be used alone or as a mixture of two or more. The proportion of metals or their compounds used in these catalysts is
The atomic ratio of antimony, germanium or titanium to 1 mole of aromatic dicarboxylic acid and aromatic oxycarboxylic acid in total is usually 10 to 10.
Gram atoms, preferably from 5 x 10-5 to 5 x 10
It is in the gram atom range. Phosphorus compounds are used in the form of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, various esters thereof, phosphines, phosphites, and the like. The proportion of the phosphorus compound to be used is usually 101 to 10-2, preferably 2 x 10 to 5 x 10 gram atoms, as an atomic ratio of phosphorus to 1 mole of aromatic dicarboxylic acid and aromatic oxycarboxylic acid in total. range.

These catalysts can be supplied to the polycondensation system from the initial stage of the etherification reaction, esterification reaction or transesterification reaction, or they can be supplied to the reaction system before proceeding to the polycondensation reaction stage. It can also be supplied to the reaction system.

In addition, during co-condensation, various additives are used such as polyethylene terephthalate, a transesterification catalyst used in the production of esters, diethylene glycol generation inhibitors, heat stabilizers, light stabilizers, lubricants, pigments, and dyes. be able to.

Metal compounds such as calcium, agnesium, lithium, zinc, cobalt, and manganese can be used as catalysts for these transesterification reactions. The forms of these compounds include oxides, hydroxides, halides, inorganic acid salts, and organic acid salts. As the diethylene glycol production inhibitor, amines such as triethylamine and tri-n-butylamine, and quaternary ammonium compounds such as tetraethylammonium hydroxide and tetrabutylammonium hydroxide can be used. In addition, as stabilizers such as heat stabilizers,
Phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, or esters thereof can be used.

The co-condensed polyester in the present invention is produced by a conventionally known melt polycondensation method, and in some cases by employing a solid phase polycondensation method after the melt polycondensation method. As the melt polycondensation method, a so-called direct polycondensation method or a so-called transesterification polycondensation method can be employed. The melt polycondensation method uses, for example, isophthalic acid or an aromatic dicarboxylic acid whose main component is isophthalic acid or an ester derivative thereof, ethylene glycol or a diol whose main component is isophthalic acid, an aromatic oxycarboxylic acid, or its dicarboxylic acid. The condensate, and optionally a polyfunctional compound containing three or more carboxyl groups or hydroxyl groups, are esterified and etherified or transesterified simultaneously or sequentially preferably at a temperature of 100 to 280°C. An initial polycondensate is formed, which is then heated to a temperature above its melting point, preferably between 200 and 300°C.
Polycondensation can be carried out at 00° C. under vacuum or inert gas flow without stirring.

Further, the co-condensed polyester of the present invention can be produced by further subjecting the polyester obtained by the melt polycondensation method to solid phase polycondensation to increase the molecular weight. For example, in the solid phase polycondensation method, polyester obtained by the melt polycondensation method is made into fine particles,
It is heated at a temperature below its melting point, preferably between 180 and 240℃.
It can be carried out by a method of holding the reaction at a temperature of 0.degree. C. under vacuum or under an inert gas flow.

Polyalkylene terephthalate (A), which is the other component constituting the polyester composition layer, is a polyester containing ethylene terephthalate as a main constitutional 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 unit constituting the polyalkylene terephthalate may contain a small amount of other aromatic dicarboxylic acid component units in addition to the terephthalic acid component unit. Specifically, the group dicarboxylic acid component units include isophthalic acid, phthalic acid,
Examples include naphthalene dicarboxylic acid.

The diol component units constituting the polyalkylene terephthalate may contain small amounts of other diol component units in addition to ethylene glycol component units.

Specifically, other diol component units other than ethylene glycol component units include 1,3-propanediol, 1
, 4-pukundiol, neopentyl glycol, cyclohexanediol, cyclohexane dimetatool, 1
．． 4-bis(β-hydroxyethoxy)benzene, l,
3~bis(β-hydroxyethoxy)benzene, 2.2
Examples include diol component units having 3 to 15 carbon atoms such as -bis(4-β-hydroxyethoxyphenyl)propane and bis(4-β-hydroxyethoxyphenyl)sulfone.

In addition, the polyalkylene terephthalate may contain a small amount of a polyfunctional compound, if necessary, in addition to the aromatic dicarboxylic acid component unit and the diol component unit. Specifically, the polyfunctional compound component units include trimellitic acid, trimesic acid, 3.3',
5. Aromatic polybasic acids such as 5'-tetracarboxydiphenyl, aliphatic polybasic acids such as butanetetracarboxylic acid, aromatic polyols such as fluorocunrescin, 1,2,4.5-tetrahydroxybenzene, Examples include aliphatic polyols such as glycerin, trinotylolethane, trimethylolpropane, and pentaerythritol, and oxypolycarboxylic acids such as tartaric acid and malic acid.

The composition of the constituent components of the polyalkylene terephthalate is:
The content of terephthalic acid component units is usually 5° 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 30 mol %, preferably 0 to 2 mol %, preferably O to 1 mol %. In addition, 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 The melting point is usually in the range of 210 to 265°C, preferably 220 to 260°C, and the glass transition temperature is usually in the range of 50 to 120°C, preferably 60 to 100°C. range.

In the above polyester composition, the blending ratio of the co-condensed polyester (B) is usually 2 to 500 parts by weight, preferably 3 to 300 parts by weight, per 100 parts by weight of the polyalkylene terephthalate (A). Preferably it is in the range of 5 to 100 parts by weight.

The polyester composition includes the polyalkylene terephthalate (A) and the co-condensed polyester (B).
In addition, appropriate amounts of various conventionally known additives such as nucleating agents, inorganic fillers, lubricants, slip agents, anti-blocking agents, stabilizers, antistatic agents, antifogging agents, and pigments are added as necessary. There's no harm in it.

The above-mentioned polyester composition can be used in an unstretched state as a raw material for molded articles of various shapes such as refilms, sheets, fibers, containers, and others by ordinary molding methods. Furthermore, by molding the polyester composition in a stretched state into a film, sheet, or container, a molded product with even better gas barrier properties can be obtained.

Next, a polyester laminate molded article of the present invention comprising a polyester composition layer and a polyalkylene terephthalate layer having 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 both side layers having the polyester composition layer, the polyester composition layer and the polyalkylene terephthalate layer. A multilayer laminate molded product having a four-layer structure or more in which both outermost layers are composed of the polyalkylene terephthalate layer, the polyester composition layer and the polyalkylene terephthalate layer are alternately laminated. A multilayer laminate molded product having a four-layer structure or more, in which both outermost layers are composed of the polyester composition layer, a multilayer laminate molded product having a four-layer structure or more, in which the polyester composition layer and the polyalkylene terephthalate layer are alternately laminated. Examples include a multilayer laminate molded product in which the outermost layer is composed of the polyester composition layer and the polyalkylene terephthalate layer. The laminated molded product can be applied not only to sheet-like objects, plate-like objects, and tubular objects, but also to various hollow bodies, containers, structures of various shapes, and the like. The laminate can be manufactured by a conventionally known method.

The 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 in the range of ordinary thickness to 350μ, preferably 2 to 200μ,
The thickness of the polyalkylene terephthalate layer is between 8 and 6
00μ, 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 1 to 350μ, preferably 2 to 200μ.
The thickness of each of the outer layers of the polyalkylene terephthalate layer is usually between 4 and 300μ, preferably between 5 and 250μ. Further, when the laminate molded product is the latter of the three-layer laminate molded products, the thickness of the intermediate layer consisting of the polyalkylene terephthalate layer is usually in the range of 8 to 800μ, preferably 10 to 500μ. The thickness of both outer layers of the polyester composition typically ranges from 100 µm to 100 µm, preferably from 100 µm to 50 µm. Even when the laminate molded product is a multilayer laminate molded product having a four-layer structure or more, the thickness of the intermediate layer and the outermost layer made of the polyester composition layer, and the thickness of the intermediate layer and the outermost layer made of the polyalkylene terephthalate layer. The thickness of the layer can be chosen as before.

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

Next, the polyester stretch laminate molded product of the present invention, which is composed of a polyester composition layer and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate, will be described. The polyester stretch laminate molded product of the present invention is
A polyester laminate molded product consisting of the polyester composition layer and the polyalkylene terephthalate layer and having the above-mentioned laminate structure, and having a polyester stretched laminate in which one of the polyalkylene terephthalate layers is in a stretched state. A molded article. A polyester laminate molded article comprising the polyester composition layer and the polyalkylene terephthalate layer and having the aforementioned laminated structure, and at least all of the polyalkylene terephthalate layers are stretched. A poly stretched laminate molded article, particularly preferably consisting of the polyester composition layer and the polyalkylene terephthalate layer,
All of the polyester composition layer and the polyalkylene terephthalate layer having the above-mentioned laminated structure are in a stretched state. The stretched layer may be in a −axially stretched state or in a biaxially stretched state. In addition, the form of the polyester stretched laminate molded product may be any shape such as a film or a sheet. If the resin layer constituting the polyester stretched laminate molded product is uniaxially stretched, the stretching ratio is usually 1
．． It is in the range of 1 to 10 times, preferably 1.2 to 8 times, particularly preferably 1.5 to 7 times. When the constituent resin layer is a biaxially stretched layer, the stretching ratio in the vertical axis direction is usually 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5. In the horizontal direction, it is usually 1.1 to 8 times, preferably 1.2 to 7 times, particularly preferably 1.5 to 6 times. Furthermore, the polyester stretch laminate molded product can be heat set depending on its intended use.

When the polyester stretched molded product is a film-like product or a sheet-like product, any conventionally known method can be adopted as a manufacturing method thereof.

Generally, the polyester composition and the polyalkylene terephthalate are each melted in an MII solid extruder, and a raw laminate such as a multilayer laminate film (laminated sheet) is formed by melt coextrusion from a multi-NT die. A method is adopted in which the molded product is kept in a heated state or is once cooled and solidified to a temperature below the glass transition point, and then further heated and then subjected to a stretching treatment. 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 stretched or biaxially stretched before lamination, or may be similarly stretched after lamination. In addition, there is a method of extrusion laminating the polyalkylene terephthalate on a film-like material (sheet-like material) previously formed from the polyester composition, 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 subjected to stretching, produces a polyester stretched laminate with a simple process and excellent glabella adhesive strength. This is particularly preferred because it provides the following.

In addition, when producing the polyester stretch laminate molded product,
When the seat molded product is a film-like material (sheet-like material), the stretching treatment may be performed by stretching the seat molded product in a uniaxial direction (-axial stretching) or further stretching the seat molded product in the longitudinal direction. A method of stretching in the horizontal axis direction (two-wheel stretching), a method of simultaneously stretching in the longitudinal and horizontal directions (two-wheel stretching), a method of repeating sequential stretching in any one direction after biaxial stretching, How to further stretch in both directions afterwards
Examples include the so-called vacuum forming method in which stretch forming is performed by reducing the pressure in the space between the seat 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 molded seat, preferably 80° C. higher than the glass transition point or glass transition point.

In order to heat set the polyester stretched laminate molded product, an appropriate short-time heat treatment is performed at the stretching temperature or a higher temperature.

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

The preform for a polyester multilayer hollow molded body of the present invention is a preform for a multilayer hollow body having a laminated structure composed of the polyester composition layer and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate. This is a multilayer hollow molded preform 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 foams 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 sides. When a stretched multilayer hollow molded body is formed from a preform having a laminated structure consisting of three layers of the polyalkylene terephthalate layer, the stretched multilayer hollow molded body has excellent properties such as excellent mechanical strength, transparency, and gas barrier properties. This is preferred because a multilayer hollow molded body can be obtained.

The polyester composition and the polyalkylene terephthalate constituting the preform for a multilayer hollow molded body of the present invention may optionally contain conventionally known nucleating agents, inorganic fillers, lubricants, slip agents, anti-blocking agents, etc. Appropriate amounts of various additives such as 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 stretched polyester multilayer hollow molded body of the present invention is a stretched multilayer hollow molded body composed of the polyester composition layer and the polyalkylene terephthalate layer, and is produced by stretch blow molding the preform for the multilayer hollow molded body. be done. The polyester stretched multilayer hollow molded body may be a stretched two-layer hollow molded body composed of the polyester composition layer and the polyalkylene terephthalate layer, or the polyester composition layer and the polyalkylene terephthalate layer may be It may be a stretched three-layer hollow molded product composed of three layers 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 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. , the polyester composition layer may be an inner layer and the polyalkylene terephthalate layer may be an 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 three-layer hollow molded body in which the polyester composition layers are 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 stretched multilayer hollow molded bodies of the present invention, it is preferable that the inner layer is a stretched multilayer hollow molded body whose inner layer is a polyalkylene terephthalate layer, and in particular, the polyester composition layer is an intermediate layer and the polyalkylene terephthalate layer is a stretched multilayer hollow molded body. Preferably, the three-layer stretched hollow molded body is an inner layer and an outer layer. The stretched multilayer hollow molded product may be a uniaxially stretched 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 polyester composition and the polyalkylene terephthalate can be used 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 (two-wheel 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 has excellent mechanical strength, heat resistance properties, and gas barrier properties, and therefore can be used for various purposes.

In particular, the biaxially stretched multilayer blow-molded container of the present invention has excellent gas barrier properties, so it can be used for containers for seasonings, oils, alcoholic beverages such as beer and Japanese sake, soft drinks such as cola, Saigu, and juice, cosmetics, detergents, etc. However, especially when used as a container for beer or carbonated drinks, it becomes possible to reduce the wall thickness of the container and extend the shelf life.

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

The intrinsic viscosity [η] of the co-condensed polyester and the intrinsic viscosity [η] of the polyalkylene terephthalate were determined using a phenol-tetrachloroethane mixed solvent (weight ratio 100:1).
00) at 25°C. The glass transition temperature of the co-condensed polyester and the glass transition temperature and melting point of the polyalkylene terephthalate were determined by heating the sample to a molten fluid state and then rapidly cooling it to room temperature. /mi
It was determined by measuring at a heating rate of n.

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 using an OXTRAM device manufactured by CON).
) manufactured by PERMATRAN C-I
Each measurement was performed at 25° C. using a V apparatus.

〔Example〕

Example 1 Polyethylene terephthalate (trade name, three-layer PETJ135) dried at 150°C for 10 hours was press-molded at about 260°C to produce a press sheet with a thickness of about 100μ. Polyethylene terephthalate (trade name, three-layer PET J 135) separately dried at 150°C for 10 hours
Isophthalic acid/p-hydroxybenzoic acid/ethylene glycol co-condensed polyester (composition (molar ratio) 43:48, intrinsic viscosity [η] 0.76 d!) was dried under reduced pressure at 55°C for 12 hours based on 100 parts by weight. / g, glass transition temperature (Tg) 65°C] A mixture of 40 parts by weight was melt extruded at about 270°C using another extruder, cut after cooling, and co-condensed with polyethylene terephthalate. Pellets of the polyester composition were produced, and the pellets of the composition were press-molded at about 60° C. to produce a press sheet with a thickness of 100 μm.Furthermore, a press sheet of the above polyethylene terephthalate and a press sheet of the above composition were prepared. were stacked together and press-molded again at about 260°C to produce a two-layer, two-layer laminate sheet with a thickness of about 150μ. The oxygen gas permeability coefficient is 2.6m!-m/
rd-day-atm, and the carbon dioxide permeability coefficient was 13 mf-fin/rd-day-atm.

Examples 2 to 8 The thickness was changed in the same manner as in Example 1 except that in Example 1, a press sheet of polyethylene terephthalate listed in Table 1 or a press sheet of a composition of polyethylene terephthalate and co-condensed polyester listed in Table 1 was used. Approximately 1
A press sheet of two types and two layers having a thickness of 50μ was produced. All of the obtained laminate sheets had good adhesion between the polyethylene terephthalate layer and the composition layer, and the carbon dioxide gas permeability coefficients of these laminate sheets were as shown in Table 1.

Comparative Example 1 Using the polyethylene terephthalate in Example 1, a single-layer press sheet with a thickness of about 150 μm was produced in the same manner as in Example 1. The carbon dioxide permeability coefficient of this press sheet is 25if-tm/cd・day-atI
I+, and the oxygen gas permeability coefficient is 4.5 1 m
m/rd °day = at+w.

Example 9 Polyethylene terephthalate (trade name, three-layer PETJ155) dried at 150°C for 10 hours was melted using an extruder at a molding temperature of about 270°C, and a mixture of polyethylene terephthalate and co-condensed polyester in Example 1 was separately prepared. is melted at about 270°C using another extruder, fed to two-layer coat hanger type T-dies and extruded into sheets, and further cooled with rolls to form polyethylene terephthalate layers of about 100 μm and polyethylene A two-layer, two-layer laminate sheet was prepared in which the composition layer of terephthalate and co-condensed polyester had a thickness of approximately 100 μm.

The obtained laminated sheet had good adhesion between the polyethylene terephthalate layer and the composition layer, and its oxygen gas permeability coefficient was 2.4 ml·w/rd·day −a.
tm, and the carbon dioxide permeability coefficient is 13if-m/cd.
-day -atn+.

Example 10 The polyethylene terephthalate in Example 1 was melted at a molding temperature of about 270°C using an extruder, and the mixture of polyethylene terephthalate and co-condensed polyester in Example 1 was separately melted at a molding temperature of about 270°C using another extruder. The material is melted and fed into a three-layer coat hanger type T-die so that the upper and lower layers are polyethylene terephthalate, and the middle layer is the composition, extruded into a sheet, and further cooled with rolls. An 81 m sheet of two types and three layers, each having a polyethylene terephthalate layer with a thickness of about 75μ and a composition layer with a thickness of about 75μ, was prepared. The obtained laminated sheet has good adhesion between the polyethylene terephthalate layer and the co-condensed polyester layer, and its carbon dioxide gas permeability coefficient is 15mf-+u/rd-da.
It was y-atm.

Example 11 The laminated sheet consisting of the polyethylene terephthalate layer and the composition layer in Example 1 was simultaneously stretched 3 times in the vertical and horizontal directions using a biaxial stretching device, and
A biaxially stretched film was produced. The obtained two-wheel stretched film had a thickness of about 17 μm and was uniformly two-wheel stretched. Furthermore, this biaxially stretched film had good glabellar adhesion between the polyethylene terephthalate layer and the composition layer. Further, the carbon dioxide gas permeability coefficient of this biaxially stretched film was 9.6 layers 1 mm/rrLday -atm.

Examples 12 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 11, except that the laminated sheets listed in Table 2 were used instead of the laminated sheets in Example 11. . All of the obtained biaxially stretched films had average thicknesses as shown in Table 2, and were uniformly stretched.

In addition, all of these two-wheel stretched films also had good adhesion between the glabella between the polyethylene terephthalate layer and the composition layer. Furthermore, the carbon dioxide gas permeability coefficients of these biaxially stretched films were as shown in Table 2.

Comparative Example 2 The press sheet of polyethylene terephthalate in Comparative Example 1 was simultaneously biaxially stretched by three times in the vertical axis direction and the horizontal axis direction in the same manner as in Example 11 to produce a two-wheel stretched film. The thickness of this biaxially stretched film is about 17μ, and its carbon dioxide permeability coefficient is 15mf-w/rd-
day・It was ATM.

Example 19 Using a two-layer injection molding machine, the polyethylene terephthalate in Example 1 was melted at a molding temperature of about 270°C, and the mixture of the polyethylene terephthalate and co-condensed polyester in Example 1 was separately melted. Melted with another injection molding machine at a molding temperature of about 270℃,
Two layers are injection molded into a single cooled preform mold, with the inner layer made of polyethylene terephthalate (approximately 1.6 m thick).
m), and the outer 7 layers are a composition of polyethylene terephthalate and co-condensed polyester) (thickness approximately 1.6
A two-layer preform consisting of s heavy weight) was produced. Then, using a biaxial stretch blow molding machine (manufactured by Koho Blast Co., Ltd., LBOI), it was biaxially stretched to about 2.5 times in length and about 4 times in width.
A multilayer container with an internal volume of about 12 was produced. The average thickness of the polyethylene terephthalate layer of this multilayer container is approximately 150μ
Moreover, the average thickness of the composition layer was about 150 μm, and it was confirmed that it was stretched uniformly. Also, the carbon dioxide permeability of this multilayer container is 2.7 ml/day-bot.
It was tle-atm.

Comparative Example 3 The polyethylene terephthalate in Example 1 was injection molded to have the same thickness as the preform in Example 19 (about 3 mm,
A preform consisting only of a polyethylene terephthalate layer with a 2 m diameter was prepared. This preform was then stretch-blown in the same manner as in Example 19 to produce a stretched bottle having a minimum wall thickness of approximately 300 μm and an internal volume of approximately 1j2. Furthermore, as a result of measuring the carbon dioxide permeability coefficient of this stretched bottle, it was 4.0 *1- *m/ rrr -day
-It was an ATM.

Example 20 The inner layer was made of polyethylene terephthalate (polyethylene terephthalate ( A two-layer preform was prepared, with a thickness of approximately 1.6 m) and an outer layer of the composition (approximately 1.6 mm thick), and then stretched and blow-molded on two wheels in the same manner as in Example 19 to reduce the inner volume. Approximately 11 multilayer containers were made.

The average thickness of the polyethylene terephthalate layer of this multilayer container is about 150 μm, and the average thickness of the composition layer is about 15 μm.
It was confirmed that the film was stretched uniformly. In addition, the carbon dioxide permeability of this multilayer container is 2.8 mff.
1/day-bottle-at+a.

Example 21 The polyethylene terephthalate in Example 1 was melted using an extruder at a molding temperature of about 270°C, and separately prepared in Example 5.
A mixture of polyethylene terephthalate and co-condensed polyester was molded using a separate extruder at a temperature of about 270°C.
By melting at ℃ and extruding it by feeding it into a three-layer pipe die so that the outer layer and inner layer are made of polyethylene terephthalate, and the middle layer is made of a composition of polyethylene terephthalate and co-condensed polyester, and further cooled. A pipe of two types and three layers with an outer diameter of 24.8 mm and a thickness of 3.6 m, each having a polyethylene terephthalate layer of about 1.2 mm and a composition layer of about 1.2 mm, was prepared. 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 approximately 50 g. Then, using a biaxial stretch blow molding machine (manufactured by Kohoplast, LBOI), the mixture was biaxially stretched 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 composition layer was approximately 120 μm, indicating that it was uniformly stretched. In addition, the carbon dioxide permeability of this multilayer container is 3.1mff1/day-bo
It was ttle・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 stretch laminate molded product, preform for a polyester multilayer hollow molded product, and polyester stretched multilayer hollow molded product of the present invention all have excellent melt moldability, stretch moldability, and gas barrier properties.

(1 other person)

Claims (4)

[Claims] (1) Polyester laminate molding consisting of a polyester composition layer consisting of polyalkylene terephthalate (A) whose main constituent unit is ethylene terephthalate and a co-condensed polyester (B) and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate and the co-condensed polyester (B) contains (a) 25 to 48 mol% of aromatic dicarboxylic acid component units mainly composed of isophthalic acid component units, and (b) ethylene glycol component units as the main component. 45 to 50 mol% of diol component units, and (c) 2 aromatic oxycarboxylic acid component units having 12 or less carbon atoms.
and (d) 0 to 2 mol% of polyfunctional compound component units having a carbon number in the range of 3 to 15 and having 3 or more carboxyl groups or hydroxyl groups, and (e) Intrinsic viscosity in the range of 0.5 to 1.5 dl/g [
η] and (f) a glass transition temperature in the range of 50 to 120°C. (2) A polyester stretched laminate composed of a polyester composition layer consisting of polyalkylene terephthalate (A) whose main constituent unit is ethylene terephthalate and a co-condensed polyester (B) and a polyester composition layer whose main constituent unit is ethylene terephthalate. A molded article, wherein the co-condensed polyester (B) contains (a) 25 to 48 mol% of aromatic dicarboxylic acid component units mainly composed of isophthalic acid component units, (b) mainly ethylene glycol component units. 45 to 50 mol% of diol component units as a component; (c) 2 aromatic oxycarboxylic acid component units having 12 or less carbon atoms;
and (d) 0 to 2 mol% of polyfunctional compound component units having a carbon number in the range of 3 to 15 and having 3 or more carboxyl groups or hydroxyl groups, and (e) Intrinsic viscosity in the range of 0.5 to 1.5 dl/g [
and (f) a substantially linear polyester having a glass transition temperature in the range of 50 to 120°C. (3) Polyester multilayer hollow consisting of a polyester composition layer consisting of polyalkylene terephthalate (A) whose main constituent unit is ethylene terephthalate and a co-condensed polyester (B), and a polyester composition layer whose main constituent unit is ethylene terephthalate A preform for a molded article, the co-condensed polyester (B)
(a) 25 to 48 mol% of aromatic dicarboxylic acid component units mainly composed of isophthalic acid component units, (b) 45 to 50 mol% of diol component units mainly composed of ethylene glycol component units, (c) 2 aromatic oxycarboxylic acid component units having 12 or less carbon atoms
and (d) 0 to 2 mol% of polyfunctional compound component units having a carbon number in the range of 3 to 15 and having 3 or more carboxyl groups or hydroxyl groups, and (e) Intrinsic viscosity in the range of 0.5 to 1.5 dl/g [
η] and (f) a glass transition temperature in the range of 50 to 120°C. (4) Polyester multilayer hollow consisting of a polyester composition layer consisting of polyalkylene terephthalate (A) whose main constituent unit is ethylene terephthalate and co-condensed polyester (B) and a polyalkylene terephthalate layer whose main constituent unit is ethylene terephthalate A molded article, wherein the co-condensed polyester (B) contains (a) 25 to 48 mol% of aromatic dicarboxylic acid component units mainly composed of isophthalic acid component units, and (b) mainly ethylene glycol component units. 45 to 50 mol% of diol component units as a component; (c) 2 aromatic oxycarboxylic acid component units having 12 or less carbon atoms;
and (d) 0 to 2 mol% of polyfunctional compound component units having a carbon number ranging from 3 to 15 and having 3 or more carboxyl groups or hydroxyl groups; (e) Intrinsic viscosity in the range of 0.5 to 1.5 dl/g [
η] and (f) a glass transition temperature in the range of 50 to 120°C.