JP2001232740A - Plastic laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic laminate, in which both barrier properties against gasoline and gasohol and impact resistance are excellent and also recycling properties are excellent. SOLUTION: This laminated has a layer consisting of a polyolefin resin on both sides of a layer consisting of polytetramethylene terephthalate-based resin. The plastic laminate has an adhesive layer consisting of thermoplastic resin composition which contains at least copolymerized polytetramethylene terephthalate resin and a polyolefin resin having a polar group between a layer consisting of a polytetramethylene terephthalate-based resin and a layer consisting of a polyolefin resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plastic laminate, and more particularly, to a plastic laminate having excellent fuel barrier properties.

[0002]

2. Description of the Related Art Rust-proof steel plates and polyethylene resins are used as materials for automobile fuel tanks. In recent years, the use of resin tanks made mainly of polyethylene has increased due to demands for weight reduction and cost reduction. ing. Polyethylene tanks have a high degree of freedom in shape design and are advantageous not only for storage in complex chassis with various parts mounted, but also because they do not rust like steel plates and also have the strength in the event of a collision. Further, post-weld processing such as a steel plate tank is not required, but a polyethylene tank needs to be thick because of its high gasoline permeability.

In order to improve the barrier property against fuel such as gasoline, for example, Japanese Patent Application Laid-Open No. 7-40517 discloses that a polyethylene layer and a barrier layer of a polyamide resin, a saponified ethylene vinyl acetate copolymer or a thermoplastic polyester are used. A multilayer hollow molded article formed from a multilayer laminated material obtained by laminating is disclosed. However, the polyamide resin has a high affinity with gasohol obtained by mixing methanol or ethanol with gasoline, which is a fuel suitable for cleaning exhaust gas, and has a problem that gasohol is easily permeated.

Although the saponified ethylene-vinyl acetate copolymer has a better barrier property against gasohol than the polyamide-based resin, it has a disadvantage that the extrusion failure is likely to occur due to the generation of a cross-linked resin in continuous extrusion molding, and polyethylene terephthalate which is a polyester resin is used. The resin and the polytetramethylene terephthalate resin are difficult to adhere to the polyolefin resin, and when a recycled resin is used, the impact strength of the multilayer hollow molded article is disadvantageously reduced.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a plastic laminate having excellent barrier properties and impact resistance to gasoline and gasohol and excellent recyclability.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and the gist of the present invention is to provide a layer (a) made of polytetramethylene terephthalate resin.
Having a layer (b) made of a polyolefin resin on both sides thereof, wherein at least a copolymerized polytetramethylene terephthalate is provided between a layer (a) made of a polytetramethylene terephthalate-based resin and a layer (b) made of a polyolefin resin. A plastic laminate comprising an adhesive layer (c) made of a thermoplastic resin composition containing a resin and a polyolefin resin having a polar group.

Hereinafter, the present invention will be described in detail. The polytetramethylene terephthalate resin in the present invention is a polytetramethylene terephthalate resin obtained by polycondensing a dicarboxylic acid component whose main component is terephthalic acid or an ester derivative thereof and a glycol component whose main component is tetramethylene glycol. is there.

Preferably, the polytetramethylene terephthalate resin is a polytetramethylene terephthalic acid or an ester derivative thereof obtained by polycondensing a dicarboxylic acid component of 70 mol% or more and a glycol component of 70 mol% or more of tetramethylene glycol. A methylene terephthalate resin, more preferably a polytetramethylene terephthalate resin obtained by condensation polymerization of terephthalic acid or an ester derivative thereof with a dicarboxylic acid component of 90 mol% or more and a glycol component of 90 mol% or more of tetramethylene glycol It is.

Examples of the dicarboxylic acid component other than terephthalic acid include aromatic dicarboxylic acids other than terephthalic acid, aliphatic dicarboxylic acids and alicyclic dicarboxylic acids. As aromatic dicarboxylic acids other than terephthalic acid,
Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (4
4'-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and ester derivatives thereof. Examples of the aliphatic dicarboxylic acid include adipic acid, sebacic acid, azelaic acid, dimer acid and the like and ester derivatives thereof. 1,4 as alicyclic dicarboxylic acids
Examples include cyclohexanedicarboxylic acid, 4,4'-dicyclohexyldicarboxylic acid, and ester derivatives thereof.

The glycol components other than tetramethylene glycol include ethylene glycol, trimethylene glycol, propylene glycol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, 1,4 -Cyclohexanedimethanol, 4,4'-
Dicyclohexylhydroxymethane, 4,4'-dicyclohexylhydroxypropane, bisphenol A ethylene oxide added diol, halogenated bisphenol A ethylene oxide added diol, polyethylene oxide glycol, polypropylene oxide glycol, polytetramethylene oxide glycol, and the like. Examples include triols such as methylolpropane and the like, and further, a mixed system thereof.

If a large amount of the asymmetric chemical structural component or the copolymer component having a high molecular weight is used in a large amount, the crystallinity is deteriorated, heat resistance is reduced, fuel permeability is increased, and elastic modulus is increased. It is not preferable because it decreases. The polytetramethylene terephthalate resin is produced by a condensation polymerization method known to those skilled in the art.

The intrinsic viscosity [η] of the polytetramethylene terephthalate resin is preferably about 0.7 to 2.0, as measured at 30 ° C. using a 50/50 weight ratio of tetrachloroethane and phenol as a solvent. The melting point of the polytetramethylene terephthalate-based resin is determined by a DSC heating rate of 20.
In the measurement of the melting peak temperature when measured at ° C./min,
It is about 220 to 230 ° C. The flexural modulus of polytetramethylene terephthalate resin is 1/4 "according to ASTM method.
It is preferably about 2.0 to 3.0 GPa as measured by a test piece.

The polytetramethylene terephthalate resin is preferably a polytetramethylene terephthalate resin. The solution viscosity [η] of the polytetramethylene terephthalate resin is preferably from 0.7 to 2.0 as measured at 30 ° C. using a 50/50 weight ratio of tetrachloroethane and phenol as a solvent.
In the measurement of the melting peak temperature measured at a C method heating rate of 20 ° C./min, it is preferably 222 to 227 ° C.,
The flexural modulus is preferably from 2.2 to 2.7 GPa, as measured on an ASTM 1/4 "test piece.

The polyolefin resin in the present invention includes a polyethylene resin, a polypropylene resin and the like, and preferably a polyethylene resin. As the polyethylene resin, preferably, the density is 0.920 to
0.928, melt flow rate (hereinafter sometimes abbreviated as MFR), low density polyethylene resin of about 0.3 to 5, density of 0.920 to 0.928, MFR of 0.7 to 3
Α-olefin copolymerized linear low-density polyethylene resin having a density of 0.94 to 0.96 and an MFR of 0.05 to 0.
35 high density polyethylene resin for hollow molding, density 0.9
Examples include HDPE for extrusion molding having an MFR of about 4 to 0.96 and an MFR of about 1.0 to 0.05, and those having excellent stress cracking resistance are preferable. A polyethylene resin polymerized with a metallocene catalyst or the like can also be used. Preferably, the polypropylene resin has a density of 0.9 to 0.91, MFR
A polypropylene resin of about 0.5 to 10 is exemplified.
A heat stabilizer, a filler, a pigment such as carbon black, or the like can be appropriately blended with these polyolefin resins and used.

[0015] The thermoplastic resin composition used as the adhesive layer is a thermoplastic resin composition containing at least a copolymerized polytetramethylene terephthalate resin and a polyolefin resin having a polar group. As the thermoplastic resin composition containing a copolymerized polytetramethylene terephthalate resin and a polyolefin resin having a polar group, preferably, a thermoplastic resin comprising a copolymerized polytetramethylene terephthalate resin, a polyolefin resin having a polar group, and a polyolefin resin A composition. The polyolefin resin is used for adjusting the adhesion to the polyolefin resin layers on both sides of the layer made of polytetramethylene terephthalate resin in the laminate.

The proportions of the copolymerized polytetramethylene terephthalate resin, the polar group-containing polyolefin resin and the polyolefin resin in the thermoplastic resin composition are preferably 40 to 80% by weight of the copolymerized polytetramethylene terephthalate resin and the polar group-containing resin. 20-60% by weight of polyolefin resin and 0-30 of polyolefin resin
%, More preferably 39 to 80% by weight of a copolymerized polytetramethylene terephthalate resin, 19 to 60% by weight of a polyolefin resin having a polar group, and 1 to 30% by weight of a polyolefin resin.

If the proportion of the copolymerized polytetramethylene terephthalate resin in the thermoplastic resin composition is too small, the adhesion between the adhesive layer in the laminate and the layer made of the polytetramethylene terephthalate resin tends to decrease.
If the amount is too large, the adhesiveness to the layer made of the polyolefin resin tends to be reduced. If the proportion of the polyolefin resin having a polar group and the polyolefin resin in the thermoplastic resin composition is too small, the adhesion between the adhesive layer and the layer made of the polyolefin resin in the laminate is likely to be reduced, and if the ratio is too large, the thermoplastic resin composition Uniformity is impaired. On the other hand, if the proportion of the polyolefin resin having a polar group in the thermoplastic resin composition is too small, the adhesiveness between the adhesive layer and the layer made of the polyolefin resin in the laminate tends to decrease.

The copolymerized polytetramethylene terephthalate resin in the thermoplastic resin composition includes a dicarboxylic acid component composed of terephthalic acid and an aromatic dicarboxylic acid other than terephthalic acid and a diol component composed of tetramethylene glycol and a diol other than tetramethylene glycol. And a dicarboxylic acid component consisting of 50 to 90 mol% of terephthalic acid and 50 to 10 mol% of an aromatic dicarboxylic acid other than terephthalic acid, and tetramethylene. A copolymerized polytetramethylene terephthalate resin obtained by a condensation reaction of 90 to 50 mol% of a glycol and a diol component of 10 to 50 mol% comprising a diol other than tetramethylene glycol.

If the proportion of terephthalic acid is less than 50 mol%, the crystallinity and the melting point are lowered, and the production and handling become difficult due to blocking. If it exceeds 90 mol%, the compatibility of the composition is lowered and tetramethylene glycol is reduced. If the proportion of the component is less than 50 mol%, the crystallinity and the melting point decrease, and the production and handling become difficult due to blocking. If it exceeds 90 mol%, the flexibility decreases.

The aromatic dicarboxylic acids other than terephthalic acid include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (4,4'-carboxyphenyl) methane, anthracenedicarboxylic acid Examples thereof include acids, 4,4'-diphenylether dicarboxylic acid, and ester derivatives thereof, and preferably, isophthalic acid.

As glycol components other than tetramethylene glycol, ethylene glycol, trimethylene glycol, propylene glycol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, 1,4 -Cyclohexanedimethanol, 4,4'-
Dicyclohexylhydroxymethane, 4,4'-dicyclohexylhydroxypropane, bisphenol A ethylene oxide added diol, halogenated bisphenol A ethylene oxide added diol, polyethylene oxide glycol, polypropylene oxide glycol, polytetramethylene oxide glycol, and the like. Triols such as methylolpropane are also included.

The glycol component other than tetramethylene glycol is preferably diethylene glycol,
Low molecular weight glycols such as 1,6-hexanediol,
High molecular weight glycols such as polytetramethylene oxide glycol having an average molecular weight of about 500 to 6000 are mentioned, and more preferably, a combination of diethylene glycol and polytetramethylene oxide glycol having an average molecular weight of 500 to 6000 is used. Average molecular weight 500
The proportion of polytetramethylene oxide glycol of ６6000 is preferably not more than 10 mol% of the total diol component. By using polytetramethylene oxide glycol as a copolymer component, the flexibility of the adhesive layer is improved.
If it exceeds 0 mol%, the thermal stability will decrease.

The melting point of the copolymerized polytetramethylene terephthalate resin is preferably about 90 to 160 ° C.
If the melting point is less than 90 ° C., the workability is reduced due to the blocking property of the resin, and if it exceeds 160 ° C., the adhesiveness tends to be reduced. The solution viscosity [η] of the copolymerized polytetramethylene terephthalate resin is preferably about 0.5 to 1.5.

The polar group of the polyolefin resin having a polar group in the thermoplastic resin composition includes an epoxy group,
Carboxyl group, carboxylic anhydride group and the like,
Preferably, an epoxy group is used. The polyolefin resin having a polar group is a copolymer of a monomer having a polar group and ethylene or polypropylene, and can be polymerized by a method such as a high-pressure radical polymerization method, a solution polymerization method, or an emulsion polymerization method. Examples of the monomer having the above functional group copolymerizable with ethylene include α, β-unsaturated carboxylic acid glycidyl ester, α, β-unsaturated glycidyl ether, α, β-unsaturated carboxylic acid and anhydride thereof. Is mentioned.

Specific examples of the monomer having a polar group include, for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride And hymic anhydride, and the like, and preferred are monomers having an epoxy group such as glycidyl acrylate and glycidyl methacrylate. The proportion of the monomer having a polar group is about 0.01 to 20 mol%, preferably about 0.1 to 10 mol%, of the polyolefin resin having a polar group.

MF of polyolefin resin having polar group
R is preferably from 0.1 to 50 g / 10 minutes, and more preferably from 0.5 to 20 g / 10 minutes. The polyolefin resin having a polar group is preferably a polyethylene resin having a polar group, and more preferably a copolymerized polyethylene resin obtained by reacting ethylene, vinyl acetate and a (meth) acrylate having an epoxy group. is there.

The polyolefin resin having a polar group is preferably a polyethylene resin having a polar group when the resin of the layer (b) composed of the polyolefin resin in the plastic laminate is a polyethylene resin. When the resin of the layer (b) is a polypropylene resin, it is preferably a polypropylene resin having a polar group.

Examples of the polyolefin resin in the thermoplastic resin composition include low-density polyethylene, α-olefin copolymerized low-density polyethylene, high-density polyethylene, polypropylene and the like. Among them, ethylene-vinyl acetate copolymer, aromatic vinyl compound and Copolymers with ethylene, ethylene- (meth) acrylate copolymers and the like may be used, and the ethylene content of these copolymers is preferably 50%.
Mol% or more. As the polyolefin resin, preferably, a polyethylene resin is used. The MFR of the polyolefin resin is preferably about 0.1 to 50 g / 10 minutes, and more preferably about 0.5 to 20 g / 10 minutes.

When the polyolefin resin in the thermoplastic resin composition is a polyethylene resin, the resin of the polyolefin resin layer (b) in the plastic laminate is:
The resin is preferably a polyethylene resin, and when the resin of the polyolefin resin layer (b) in the plastic laminate is a polypropylene resin, the resin is preferably a polypropylene resin.

The layer structure of the plastic laminate of the present invention is as follows: layer (b) composed of polyolefin resin / adhesive layer (c) / layer (a) composed of polytetramethylene terephthalate resin / adhesive layer (c) / polyolefin resin Basically, five layers of the layer (b) are used, but a recycled resin can be used. The recycled resin is a pinch-off waste material generated during molding, or a crushed product such as a sprue or a runner, and is a heat containing polytetramethylene terephthalate-based resin, polyolefin resin, and at least polytetramethylene terephthalate resin having copolymerization and a polyolefin resin having a polar group. It consists of a mixture of plastic resin composition resins. The recycled resin in the present invention is excellent in miscibility of a polytetramethylene terephthalate resin, a polyolefin resin and a thermoplastic resin composition containing at least a copolymerized polytetramethylene terephthalate resin and a polyolefin resin having a polar group, and delamination. , And the impact resistance of the plastic laminate is also excellent.

As a method using a recycled resin, for example,
A method of mixing with the layer (b) made of a polyolefin resin,
A method in which a layer made of a regenerated resin is used between the layer (b) made of a polyolefin resin and the adhesive layer (c), and a method in which a layer made of a regenerated resin is used outside the layer (b) made of a polyolefin resin. Preferably, a method is used in which a layer made of a recycled resin is laminated on the outside of a layer made of a polyolefin resin.

The thickness of the plastic laminate of the present invention depends on the required strength and fuel barrier properties.
It is about 10 mm, more preferably about 2 to 6 mm. The thickness of the layer made of polytetramethylene terephthalate resin is preferably about 50 to 500 μm, and more preferably about 100 to 300 μm. If the layer made of polytetramethylene terephthalate resin is too thin, the fuel impermeability tends to be insufficient,
If it is too thick, the workability of lamination molding will be reduced.

As the layer composition ratio in the plastic laminate of the present invention, the thickness of the layer (a) composed of polytetramethylene terephthalate resin is preferably 1 to 50% of the thickness of the plastic laminate, and more preferably 3%. ~ 3
0%, and the thickness of the adhesive layer (c) is preferably 1 to 20% of the thickness of the plastic laminate, more preferably 3 to 15%, and the total thickness of the layer (b) made of a polyolefin resin. Is preferably 90 to 50% of the thickness of the plastic laminate, more preferably 95 to 60%.
It is about. The thickness ratio of each outer layer of the polyolefin resin layer is preferably about 1/1 to 1/2.

As a method for producing the thermoplastic resin composition for the adhesive layer in the present invention, there is a method in which the above components are heated and melt-kneaded using a single-screw extruder, a twin-screw extruder, a Banbury mixer, a hot roll or the like. No. The mixing of each component may be simultaneous or divided, and the melting and kneading temperature is 15
The temperature is about 0 ° C. to 250 ° C., and the kneading time is about 30 seconds to 20 minutes. By such melt-kneading, a terminal resin group or a terminal carboxyl group or terminal hydroxyl group of the copolymerized polytetramethylene terephthalate resin reacts with a polar group of the polyolefin resin to obtain a thermoplastic resin composition which is compatible and dispersed. If necessary, stabilizers such as antioxidants and ultraviolet absorbers, lubricants, inorganic fillers, pigments, and the like may be added to the thermoplastic resin composition.

Examples of the method for forming the plastic laminate of the present invention include a multilayer extrusion blow molding.
Each resin is melt-kneaded and extruded into an extruder, combined in a multilayer circular die, co-extruded to form a parison, led to a mold, pinched off, and then blow-up to form a container. It is preferable that waste material generated by pinch-off during parison molding be cooled, pulverized, melt-extruded and pelletized and used as a recycled resin. As a method using a recycled resin, a method of blending into a layer made of a polyolefin resin, a method used as a layer made of a recycled resin between a polyolefin layer and an adhesive layer, outside the layer made of a polyolefin resin,
Examples include a method of further laminating a layer made of a recycled resin, and preferably, a method of further laminating a layer made of a recycled resin outside the layer made of a polyolefin resin.

As a method for molding the plastic laminate of the present invention, when the plastic laminate is a cylindrical body, for example, it is extruded from a multilayer circular die using a tube molding machine, cooled with a sizing tube, and continuously applied. Shape. The extruder is heated by 10 to 50 ° C. higher than the melting point of the resin, and the temperature after the melting zone is set to a temperature about 10 to 20 ° C. higher than the melting point of the resin. The temperature of the joint, the adapter, and the die is set to a temperature higher by about 10 to 20 ° C. than the melting point of the resin. The temperature of the shaping mold is about 50 ° C. or lower than the melting point of the resin of the outermost layer. However, in the case of cylindrical molding without blow-up, the temperature is cooled to about 20 to 80 ° C. In the case of compression molding, there is also a method of forming a plastic laminated sheet by a T-die method, performing compression drawing, and then forming a hollow body by a welding method.

[0037]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. The measuring methods used in the examples and comparative examples are shown below. (1) Fuel permeability (g / m ² · day): Fuel permeability was quantified using simulated gasoline and simulated gasohol (simulated gasoline + alcohol). A test piece having a diameter of 80 mm is cut out from a single-layered or laminated molded product, and has an inner diameter of 38 mm.
mm on an aluminum cup flange surface. The following simulated gasoline was filled in advance in the aluminum cup, and the weight loss was determined over time over two months at 60 ° C. to determine the permeability per area. Fuel A (simulated gasoline): isooctane / toluene = 1/1
(Volume) Fuel B (simulated alcohol-added gasoline): Simulated gasoline was mixed with 15% by volume of methyl alcohol.

(2) Impact resistance: A 100 mm square test piece was cut out from a single-layered or laminated molded article.
After leaving at 3 ° C for 1 day, immersing in Fuel B at -40 ° C for 1 day,
After immersing the fuel B at 0 ° C. for 1 month and leaving it at 23 ° C. for 1 day,
Each 1 kg steel ball was dropped from a predetermined height, and the presence or absence of breakage of the test piece was observed. ○ No destruction, × destruction,
The delamination was rated as Δ.

The raw materials used in the examples and comparative examples are shown below. (3) Polyolefin resin (PE1): melt index 0.05, density 0.947 g / cm ³ , melting point 118
℃, high-density polyethylene with a flexural modulus of 0.85 GPa. (4) Polytetramethylene terephthalate resin (PB
T1): PBT polymerized from dimethyl terephthalate and tetramethylene glycol, [η] 1.4, melting point 225 ° C., flexural modulus 2.42 GPa.

(5) Thermoplastic resin composition (MPBT
1): terephthalic acid (85 mol%), isophthalic acid (1
5 mol%), tetramethylene glycol (57 mol%), diethylene glycol (40 mol%), intrinsic viscosity 1.1 synthesized from polytetramethylene oxide glycol (3 mol%) having a number average molecular weight of 1,000, melting point 13
65 parts by weight of 6 ° C copolymerized polyester resin, 3 g of MFR
/ 10 minute polar group-containing polyolefin resin (glycidyl methacrylate 12% by weight, vinyl acetate 5% by weight copolymerized polyethylene resin) 20 parts by weight, density 0.923, M
MFR produced by blending 15 parts by weight of low-density polyethylene with FR 3.8 g / 10 min and melt-kneading using a biaxial kneader.
7 g / 10 minutes thermoplastic resin composition.

(6) Polyamide resin (PA6): solution viscosity ηrel 4.5 (JIS K-6810), melting point 2
Nylon 6 resin having a flexural modulus of 2.35 GPa at 24 ° C. (7) Adhesive (AD): Modified olefin adhesive for PA / PE.

[Example 1] PE1, PBT1 and MPB
T1 was melt-kneaded at 220 ° C., 260 ° C., and 180 ° C. with a single screw extruder, and coextruded with a three-layer, five-layer multilayer T-die.
A sheet-like plastic laminate having a thickness of mm was prepared.
Each layer thickness ratio is: PE1 layer / MPBT1 layer / PBT1 layer / MPBT1 layer / PE1 layer = 40/5/10/5/40
And The T-die temperature was 240 ° C. The cooling roll temperature was 80 ° C. Table 1 shows the evaluation results.

Example 2 A sheet-like plastic laminate having a thickness of 2 mm was produced in the same manner as in Example 1 except that the layer composition ratio was changed as shown in Table 1. Table 1 shows the evaluation results. [Example 3] The plastic laminate obtained in Example 1 was pulverized, extruded at 240 ° C using a twin-screw kneader, and pelletized, and used as a recycled resin. A sheet-like plastic laminate having a thickness was obtained. The composition ratio of each layer is: recycled resin layer / PE1 layer / MPBT
1 layer / PBT1 layer / MPBT1 layer / PE1 layer = 15/2
It was 5/5/10/5/40. Table 1 shows the evaluation results.

Comparative Example 1 A single-layer sheet having a thickness of 2 mm was formed using PE1. Table 1 shows the evaluation results. Comparative Example 2 As shown in Table 1, a sheet-shaped plastic laminate having a layer composition ratio of 2 mm was produced. The extrusion temperature of the layer composed of PA6 and the AD layer was 250 ° C.
0 ° C. Table 1 shows the evaluation results.

[0045]

[Table 1]

[0046]

The plastic laminate of the present invention has extremely low fuel permeability, excellent alcoholic fuel permeability, excellent impact resistance at room temperature and low temperature, and excellent impact strength after immersion in fuel. , And also excellent in adhesion between each layer,
It is also excellent in recyclability using recycled resin. Therefore, the plastic laminate of the present invention is useful as a fuel-barrier laminate for fuel tanks, fuel transport pipes, and the like, and is suitable for automotive fuel tanks and peripheral parts thereof as a material that complies with automobile transpiration regulations. .

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 23/08 C08L 67/02 67/02 B60K 15/02 A (72) Inventor Nobukatsu Wakabayashi 5 Higashiyawata, Hiratsuka-shi, Kanagawa Prefecture 6-6-2 Mitsubishi Engineering Plastics Co., Ltd. Technical Center F-term (reference) BA15 CB00 EH20 GB32 JA04G JA20A JB16D JB16G JB20 JK10 YY00 YY00A YY00G 4J002 BB08X BB09X CD19X CF05W CF07W GF00 GN00

Claims (18)

[Claims] 1. A laminate comprising a polyolefin resin layer (b) on both sides of a polytetramethylene terephthalate resin layer (a), wherein the polytetramethylene terephthalate resin layer (a) and a polyolefin A plastic laminate comprising an adhesive layer (c) made of a thermoplastic resin composition containing at least a copolymerized polytetramethylene terephthalate resin and a polyolefin resin having a polar group between layers (b) made of a resin. . 2. A polytetramethylene terephthalate resin comprising a polytetramethylene terephthalate resin obtained by polycondensing a terephthalic acid or an ester derivative thereof with a dicarboxylic acid component of 90 mol% or more and a tetramethylene glycol component of 90 mol% or more. The plastic laminate according to claim 1, which is a resin. 3. The plastic laminate according to claim 1, wherein the polytetramethylene terephthalate resin is a polytetramethylene terephthalate resin. 4. The plastic laminate according to claim 1, wherein the polyolefin resin is a polyethylene resin. 5. A copolymerized polytetramethylene terephthalate resin comprising a dicarboxylic acid component comprising 50 to 90 mol% of terephthalic acid and 50 to 10 mol% of an aromatic dicarboxylic acid other than terephthalic acid, and tetramethylene glycol 90.
5. A copolymerized polytetramethylene terephthalate resin obtained by subjecting a diol component consisting of a diol other than tetramethylene glycol to 10 to 50 mol% to a condensation reaction. The plastic laminate according to the above. 6. The plastic laminate according to claim 5, wherein the aromatic dicarboxylic acid other than terephthalic acid in the copolymerized polytetramethylene terephthalate resin is isophthalic acid. 7. The diol other than tetramethylene glycol in the copolymerized polytetramethylene terephthalate resin is diethylene glycol and an average molecular weight of 500 to 500.
The plastic laminate according to claim 5, which is 6000 polytetramethylene oxide glycol. 8. Polytetramethylene oxide glycol having an average molecular weight of 500 to 6000 is 10% of the total diol component.
The plastic laminate according to claim 7, wherein the amount is at most mol%. 9. The plastic laminate according to claim 1, wherein the melting point of the copolymerized polytetramethylene terephthalate resin is 90 to 160 ° C. 10. A thermoplastic resin composition comprising a copolymerized polytetramethylene terephthalate resin and a polar group-containing polyolefin resin, wherein the thermoplastic resin composition comprises a copolymerized polytetramethylene terephthalate resin, a polar group-containing polyolefin resin, and a polyolefin resin. The plastic laminate according to any one of claims 1 to 9, which is a resin composition. 11. A thermoplastic resin composition containing a copolymerized polytetramethylene terephthalate resin and a polar group-containing polyolefin resin, comprising 39 to 80% by weight of the copolymerized polytetramethylene terephthalate resin and a polar group-containing polyolefin resin 19 to 80%. The plastic laminate according to claim 10, which is a thermoplastic resin composition comprising 60% by weight and 1 to 30% by weight of a polyolefin resin. 12. The plastic laminate according to claim 1, wherein the polyolefin resin having a polar group is a polyolefin resin having an epoxy group. 13. The plastic laminate according to claim 1, wherein the polyolefin resin having a polar group is a polyethylene resin having a polar group. 14. The plastic laminate according to claim 10, wherein the polyolefin resin in the thermoplastic resin composition is a polyethylene resin. 15. The thickness of the plastic laminate is 1 to 10
The plastic laminate according to any one of claims 1 to 14, wherein the thickness is in mm. 16. The plastic laminate according to claim 15, wherein the thickness ratio of the layer made of polytetramethylene terephthalate resin is 1 to 50% of the thickness of the plastic laminate. 17. A recycled resin layer comprising a recycled resin which is a mixture of a thermoplastic resin composition containing a polytetramethylene terephthalate-based resin, a polyolefin resin, and a copolymerized polytetramethylene terephthalate resin and a polyolefin resin having a polar group. The plastic laminate according to any one of claims 1 to 16, which is formed by laminating. 18. The plastic laminate according to claim 17, wherein a recycled resin layer is further laminated outside at least one layer of the polyolefin resin layer.