ITTO990395A1 - THERMOPLASTIC POLYESTER LAYERED PRODUCT INCLUDING AN EXPANDED LAYER AND ITEM INCLUDING IT - Google Patents

Description

DESCRIPTION of the industrial invention entitled: "Stratified product of thermoplastic polyester comprising an expanded layer and article that comprises it"

BACKGROUND OF THE INVENTION A. Technical field

The present invention refers to a stratified article of thermoplastic polyester, comprising an expanded layer, which is for example used for interior decoration materials, packaging materials, thermal insulators, shock absorbers.

B. Prior art

An expanded sheet of a thermoplastic polyester has excellent adiabatic, sound absorbing and light weight properties, and also has heat and chemical resistance (these resistances are properties of thermoplastic polyesters) and has excellent printability. Therefore it is the subject of much attention. For example, Japanese Patent No. 2847 723 proposes a technique in which, in order to make good use of such advantages for interior decoration materials of automobile trunk compartments, surface materials made of fabric, such as non-woven fabric, are coated. with, a layer of expanded thermoplastic polyester.

The foamed thermoplastic polyester sheet has the advantages mentioned above, but has disadvantages which are peculiar to foamed materials. Therefore it is desired to overcome these disadvantages.

For example JP-A-170999/1994 proposes a technique according to which a layer of polyester resin is formed on at least one side of an expanded thermoplastic polyester sheet, whereas irregularities on the surface of the expanded thermoplastic polyester sheet determine the formation of small holes when the foam sheet is hot stamped. JP-A-300585/1996 proposes a technique in which a layer of unexpanded polyester resin is formed on the surface of the foamed thermoplastic polyester sheet in order to improve the printability of the surface of the foamed thermoplastic polyester sheet. JP-A-156005/1997 proposes a technique in which a layer of unexpanded polyester resin is formed on one side of the foamed thermoplastic polyester sheet in order to improve the appearance as well as the thermal resistance of cooking vessels. JP-A-180952/1998 proposes a technique in which an unexpanded thermoplastic polyester film, an ethylene-vinyl alcohol copolymer resin film and another unexpanded thermoplastic polyester film are sequentially laminated onto one side of the sheet. of expanded thermoplastic polyester in order to improve the barrier properties against gases.

Incidentally, one of the disadvantages of the expanded thermoplastic polyester sheet is that the mechanical strength is low. The aforementioned JP-A-180952/1998 reports that the multilayer structure mentioned above can have a good resistance. However, this multilayer structure is complex and further improving the mechanical strength is not sufficient.

If these mechanical strength problems are solved, the expanded thermoplastic polyester sheet is effectively usable for various products, such as automotive interior decoration materials, heated food containers, packaging materials, shock absorbers, home interior decoration material (e.g. e.g. floor mats), and laminates for electronic components, making use of the excellent printability, adiabatic and sound absorbing properties, and further, the excellent heat resistance and chemical resistance of the expanded thermoplastic polyester sheet. The foamed thermoplastic polyester sheet is excellent in light weight properties, so that it is particularly suitable for large products.

SUMMARY OF THE INVENTION

A. Purpose of the invention

An object of the present invention is to improve the mechanical strength of the expanded thermoplastic polyester layer, thus allowing the expanded thermoplastic polyester layer to be used for various purposes.

B. Presentation of the invention

In the present invention, a fiber reinforced layer of a thermoplastic polyester is layered on one or both sides of an expanded layer of a thermoplastic polyester in order to undoubtedly improve the mechanical strength of the expanded thermoplastic polyester layer.

If both the expanded layer and the fiber reinforced layer comprise the same material, i.e. thermoplastic polyester, then the adhesion between these layers is improved.

If both the expanded layer and the fiber-reinforced layer comprise the same material, i.e. thermoplastic polyester, then the selection at disposal becomes unnecessary, so that the recycling properties are improved.

These and other objects and advantages of the present invention will become more fully apparent from the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a perspective view of an automotive roof material, such as the molded article of Example 3,

Figure 2 is a perspective view of an L-shaped channel, such as the molded article of the example DETAILED DESCRIPTION OF THE INVENTION In the following the constituents of the present invention are described in detail.

Thermoplastic polyester

The thermoplastic polyester, as used in the present invention, is a polycondensed product mainly of an acid component and a glycol component. Examples of the acid component include: dicarboxylic acids, such as terephthalic acid, isophthalic acid, naphthalendicarboxylic acid, and dicarboxylic acid of diphenyl ether and dicarboxylic acid derivatives such as dimethylterephthalate. These can be used either alone or in combination with each other. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol. These can be used both alone and respectively in combination with each other.

Among the polycondensed products mentioned above, in light of the high industrial exploitation value, polyethylene terephthalate and polybutylene terephthalate are preferable, and polyethylene terephthalate is the most preferable.

Furthermore, the aforementioned thermoplastic polyesters can be developed by means of various procedures for increasing the molecular weight and then used. Examples of molecular weight raising processes include solid state polycondensation processes and processes involving the use of various chain extenders. However, in the light of the stabilization of the quality, a thermoplastic polyester having an increased molecular weight following the addition of a polycarboxylic anhydride is preferable, and furthermore, in the light of a few drawbacks such as gelling, a thermoplastic polyester of high molecular weight is more preferable. obtained by addition of a polycarboxylic anhydride by means of a polyaddition reaction in the solid state. The use of thermoplastic polyesters with an increased molecular weight as described above further improves the rigidity of the fiber-reinforced thermoplastic polyester layer, and increases the printability in the expanded state of the expanded thermoplastic polyester layer. Recycled thermoplastic polyester resins, such as recovered from beverage bottle waste, can also be developed by means of the above mentioned molecular weight increase procedures and therefore used to advantage.

In view of the printability and recycling properties, it is preferable that the thermoplastic polyesters of the fiber reinforced layer and the foamed layer, when adhered, conform to each other in such a way that the acid components or glycol components, which must form repeating units of the thermoplastic polyester of the fiber reinforced layer, whether the same as the acid components or glycol components, which must form the repeating units of the thermoplastic polyester of the expanded layer, in the ratio usually 50 mol% or more, preferably 70 mol% or more, further preferably 80 mol% or more, or that the difference between the melting points of the thermoplastic polyesters is within 30 ° C. In light of the recycling properties, the thermoplastic polyester of the fiber reinforced layer and the foam layer are more preferably the same in the ratio of 100 mol%, and more preferably both layers comprise polyethylene terephthalate (PET) in the ratio of 100 mol% such as polyester thermoplastic.

Although not limitingly, the thermoplastic polyester as used in the present invention is preferably a thermoplastic polyester having an increased molecular weight by a process including the melt-kneading step of a blend including a thermoplastic polyester and an anhydride. polycarboxylic so as to cause a chain elongation reaction, since the melt-state mixing of the thermoplastic polyester together with the polycarboxylic anhydride, so as to determine the chain elongation reaction, increases the molecular weight of the thermoplastic polyester more safely.

As polycarboxylic anhydrides usable in the present invention, the aromatic tetracarboxylic dianhydrides, in particular pyromellitic anhydride, are preferable. Examples of other useful dianhydrides include 3,3 ', 4,41-diphenyltetracarboxylic acid, (perylene-3,4,9,10) tetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid , 2,2-bis (3,4-dicarboxiphenylpropane, bis (3,4-dicarboxiphenyl) ether, bis (3,4-dicarboxyphenyl) sulfone, 1,2,3,4-cyclobutanotetracarboxylic acid and 2,3,4,5-tetracarboxyhydrofuran The amount of polycarboxylic anhydride as used is usually in the range of 0.05 to 2 parts by weight per 100 parts by weight of the thermoplastic polyester.

When the aforementioned melt mixing is carried out, other substances may be added if necessary. Examples of these other substances include: olefins, such as polyethylene, polypropylene and polybutylene; and other thermoplastic resins, such as vinyl chloride resins, polyvinyl acetal, polyvinyl alcohol, polystyrene, AS resins, ABS resins, polyamide, polycarbonate and thermoplastic elastomers; ..and further fillers, such as calcium carbonate and talc; and additives, such as nucleating agents for crystals, crystallization promoters, plasticizers, antioxidants, stabilizers, pigments, flame retardants and mold release agents. Although in a non-limiting manner, the thermoplastic polyester, as used in the present invention, is preferably a thermoplastic polyester having an increased molecular weight by a process which comprises at least the step of mixing in the melt state of a mixture comprising a thermoplastic polyester and a polycarboxylic anhydride. . The aforementioned melt mixing is more preferably carried out by melt dispersion mixing with a twin screw extruder.

This two-screw extruder is not to be understood in a limiting sense, but examples include a two-screw co-rotating extruder with vents, a two-screw non-intersecting co-rotating extruder with vents, an extruder with two counter-rotating intersecting screws with vents, an extruder two non-intersecting counter-rotating screws with vents, one extruder with two intersecting co-rotating screws without vents, one extruder with two non-intersecting co-rotating screws without drains, one extruder with two counter-rotating intersecting screws without vents, one extruder with two non-intersecting counter-rotating screws without vents. Among these, the extruder with two non-intersecting counter-rotating screws with vents is particularly preferable. Furthermore, the mixing temperature of the melt is different according to the melting point of the polymer or copolymer used, but is preferably in the range from 240 to 300 ° C. Furthermore, the residence time in the extruder is preferably in the range from 20 to 100 seconds.

The mixture, as obtained by the mixing of the melt described above, is preferably in the form of pellets, if the polyaddition reaction treatment in the solid state mentioned below has been provided. When using the two screw extruder for melt mixing mentioned above, the above mentioned mixture is extruded from the extruder in the form of filaments (preferably 1 to 10 mm in diameter, more preferably 3 to 5 mm in diameter), and then pelletized by cutting with a pelletizer, thus obtaining solid chip-shaped pellets (preferably from 1 to 20 mm in length, more preferably from 2 to 10 mm).

Although in a non-limiting manner, the thermoplastic resin, as used in the present invention, is preferably a thermoplastic polyester as obtained by a process which comprises the aforementioned melt mixing step and further the step of carrying out a solid state polyaddition reaction. of the melt mixed mixture after the melt mixing step, as the solid state polyaddition reaction further increases the molecular weight.

When the solid state polyaddition reaction is carried out, it is preferable that the melt mixed mixture is molded in the form of pellets and then used for the reaction.

The use of the mixture in the form of pellets has the economic advantage of making a large reaction space unnecessary. The mixture is heated in the range of 180 to 230 ° C in a solid state polyaddition reaction vessel or under an inert gas stream under normal pressure, or under reduced pressure, thereby carrying out the solid state polyaddition reaction. The aforementioned inert gas stream or reduced pressure effectively removes the volatile components or water from the aforementioned mixture.

The thermoplastic polyester, as used in the present invention, is preferably a thermoplastic polyester as obtained from the polyaddition reaction of the solid state in a pelletized state. The reason for this is as follows. A process in which a melt mixing reaction of the mixture including a thermoplastic polyester and a polycarboxylic anhydride is carried out may also be considered, but the possibility exists that the reaction proceeds so excessively that three-dimensionalization could take place. , since the reaction is carried out at a temperature higher than the melting point of the thermoplastic polyester. As a result, a bleed occurs within the extruder, or a swelling effect during extrusion leads to a manufactured article of uneven thickness so as to cause fracture or local elongation. Also, for example, the intrinsic viscosity (IV) distribution of a high molecular weight PET may be non-uniform. However, the solid state polyaddition reaction can increase the molecular weight of the thermoplastic polyester so as to have a sufficiently high intrinsic viscosity without causing the above mentioned problems. Thus a preferable method of increasing the molecular weight usable in the present invention is the polyaddition reaction in the solid state, more preferably that in the pelletized state. Furthermore, thermoplastic polyester, as obtained by the solid-state polyaddition reaction, has a preferable structure as a molding material, since this thermoplastic polyester has such a high molecular weight that its intrinsic viscosity (IV) is measurable, and since this thermoplastic polyester is of the non-tri-dimensional type and therefore has certain printability properties. As a result this molding material exhibits little sink lowering and can therefore give a molded product with good printability and appearance in extrusion molding.

Furthermore, the solid state polyaddition reaction can be carried out in the present invention for a molding material comprising a mixture of the thermoplastic polyester and glass fibers, and, for example, it can be carried out for a thermoplastic, pelletized polyester molding material containing glass fibers.

The solid state polyaddition reaction produces a high molecular weight thermoplastic polyester with increased intrinsic viscosity and increases the intrinsic viscosity of the thermoplastic polyester to preferably at least 0.5 dl / g, more preferably up to 0.5-1.8 dl / g, even more preferably up to 0.6-1.8 dl / g.

Expanded layer

Various conventional processes are available as a process for forming the expanded layer of the thermoplastic polyester, and this process is therefore not subject to particular limitations. An example of this is described in detail below.

The expanded thermoplastic polyester layer, as used in the present invention, can for example be obtained by means of a process which includes the steps of: mixing the thermoplastic polyester and additives such as thickeners in an extruder in the molten state; mixing the resulting melt mixed mixture with a blowing agent under high pressure;, extruding the resulting mixture into a low pressure area such as the atmosphere, thereby expanding the mixture in the form of a sheet.

Examples of the aforementioned extruders include extrusion molding machines, such as single screw extruders, multiple screw extruders, tandem extruders. When using these extruders, the aforementioned melt blended mixture is extruded from dies in the low pressure area.

Examples of the aforementioned blowing agents include physical blowing agents which have the property of gasifying or swelling upon heating.

Typical examples of the aforementioned blowing agents include: inert gases, such as carbon dioxide gas and nitrogen gas, saturated hydrocarbons, such as methane, ethane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, 2-methylpentane , 3-methylpentane, 2,2-dimethylbutane and 3, 3-dimetributane; saturated alyclic hydrocarbons, such as methylcyclopropane, cyclopentane, ethylcyclobutane and 1,1,2-trimethylcyclopropane; aromatic hydrocarbons such as benzene; halogenated hydrocarbons such as trichloromonofluoromethane, dichlorofluoromethane, monochlorodifluoromethane, trichlorotrifluroethane and dichlorotetrafluoroethane; ethers such as dimethylether and 2-ethoxyethanol; ketones, such as acetone, methylethyl ketone and acetylacetone. These can be used either alone or respectively in combination with each other.

The amount of the aforementioned blowing agents as used is preferably 0.5 parts by weight or more, in particular 1 part by weight or more, per 100 parts by weight of the melt mixed mixture, as obtained by melt mixing a mixture comprising the thermoplastic polyester to obtain the expanded thermoplastic polyester layer, so that the resulting expanded thermoplastic polyester layer may have a desirable expansion ratio. Furthermore, the amount of blowing agent is preferably 10 parts by weight or less, in particular 7.5 parts or less, per 100 parts of the aforementioned melt-mixed mixture, so that the dimensional stability of the expanded thermoplastic polyester layer does not deteriorate. during extrusion molding.

The thickness of the expanded thermoplastic polyester layer, as obtained in the aforementioned manner, can be conveniently adjusted according to the intended use of the thermoplastic polyester laminate product, but is usually preferably in the range of from about 0.5 to about 5 mm. . Furthermore, the expansion ratio of the expanded thermoplastic polyester layer can be conveniently adjusted according to the purpose of use of the thermoplastic polyester layered product, but is, for example, in the range of from 1.5 to 20 times.

The expanded layer, as used in the present invention, may further comprise additives such as stabilizers, pigments, fillers, flame retardants and antistatic agents.

Furthermore, the amount of the aforementioned blowing agents as used is preferably in the range of from 0.5 to 10 parts by weight, more preferably from 1 to 10 parts by weight, per 100 parts by weight of the thermoplastic polyester. In the event that the amount of the blowing agent is too large, the expansion takes place so excessively during molding that the dimensional stability of the resulting layered product or foamed layer is deteriorated.

Additionally, conventional foam nucleation agents, such as talc and various metal salts, can be added to refine the foam layer.

The amount of the foam nucleation agent, as added, is preferably in the range of 0.01 to 5 parts by weight per 100 parts by weight of the thermoplastic polyester. Furthermore, when extrusion and expansion molding is performed, conventional reaction promoters can also be used so as to improve the moldability in the extrusion. Examples of reaction promoters include: metal compounds of groups I, II and III, such as sodium carbonate, and organometallic compounds such as aluminum stearate. The amount of the reaction promoter, as added, is preferably in the range of 0.01 to 5 parts by weight per 100 parts by weight of the thermoplastic polyester.

Fiber reinforced layer

The reinforcing fiber can be, for example, either an inorganic fiber, such as glass fiber, carbon fiber or metal fiber, or an organic fiber which does not melt at the molding temperature of the matrix resin, such as thermoplastic polyester fiber or polyamide fiber. Among these, glass fiber is excellent in terms of strength and stiffness, and furthermore presents no particular problems if it is recycled into the same fiber-reinforced thermoplastic polyester. In addition, the thermoplastic polyester fiber is excellent in its recycling properties as its material is the same as the matrix resin.

Although in a non-limiting way, the length of the fibers is preferably in the range of from 0.1 to 5 mm, more preferably from 0.2 to 1.0 mm.

Although in a non-limiting manner, the amount of the fibers is preferably in the range of from 1 to 45% by weight, more preferably from 5 to 45% by weight.

The aforementioned thermoplastic polyester and the aforementioned fibers are blended and, if necessary, other materials are further blended as mentioned in the above explanation of the foam layer, and the resulting blend is for example printed in the form of a 0.3 thickness sheet at 20 mm, preferably from 0.3 to 10 mm, at temperatures from 240 to 280 ° C using a sheet extruder, thus obtaining the fiber-reinforced layer. Furthermore, the aforementioned thickness must not be understood in a limiting sense, since it can be freely changed according to the purpose for which the layered product is used.

Stratified product

The thermoplastic polyester layered product according to the present invention is characterized by comprising a layered structure which includes a fiber-reinforced layer of a thermoplastic polyester and an expanded layer of a thermoplastic polyester, in which the fiber-reinforced layer and the expanded layer are layered. on top of each other, in other words either in which the fiber reinforced layer is layered on the foam layer, or in which the foam layer is layered on the fiber reinforced layer. Incidentally here the term "layered product" means a unified product of two or more layers which are layered on top of each other. Specifically, if the fiber reinforced layer is marked with A and if the foam layer is marked with B, the thermoplastic polyester laminate product includes at least one AB stratified structure in the whole stratified structure, for example an AB stratified structure, a stratified structure ABA, an ABAB layered structure.

As far as strength is concerned, it is preferable that the thermoplastic polyester layered product according to the present invention comprises the above-mentioned three-layer ABA structure, or a series of the aforementioned AB-layered structures. However, the layered product of thermoplastic polyester is not limited to these examples.

The thermoplastic polyester layered product according to the present invention comprises a layering of the aforementioned expanded layer and the aforementioned fiber-reinforced layer. If necessary, the ornamental layer mentioned below or an unexpanded thermoplastic polyester film can be further layered on at least one side of the thermoplastic polyester layered product.

The ornamental layer or the unexpanded thermoplastic polyester film is used as the outermost layer of the thermoplastic polyester laminate product according to the present invention, if necessary. The ornamental layer comprises a textile product, such as non-woven fabric, or brushed fabric and improves the aesthetic properties when a thermoplastic polyester layered product according to the present invention is for example used for interior decoration *. The thickness of the ornamental layer is not particularly limited. The unexpanded thermoplastic polyester film serves, for example, to improve properties, printability, imprinting and adhesion, and to improve surface protection, such as waterproofing the main body of the layered product. Regarding the unexpanded thermoplastic polyester film, there are no limitations in relation to transparency, the presence or absence of extension, the degree of crystallinity, surface hardness and thickness.

Examples of a method for layering the layers, such as the aforementioned expanded layer, the fiber reinforced layer or the aforementioned film, in the present invention include methods by heat sealing and methods by adhesion. In the case where the adhesion process is used, the adhesive layer is not considered as a layer in the thermoplastic polyester layered product according to the present invention.

Incidentally, the layered product according to the present invention can for example be called a multilayer product, a multilayer article or a laminated layer.

Item

The type of article according to the present invention is not limiting if this article comprises the aforementioned thermoplastic polyester layered product according to the present invention. The stratified product of thermoplastic polyester, as used for articles according to the present invention, has sufficient strength thanks to the fiber-reinforced layer together with lightness, adiabatic and sound-absorbing properties thanks to the expanded layer. Therefore, the article comprising this layered product is suitable for example for automotive interior decoration materials, home interior decoration materials, and various box-type heat-insulating vessels, but the use of the product is not limited thereto. Particularly because the aforementioned layered product has sufficient strength, the article comprising this product is equally applicable to large size molded products.

Examples of the article mentioned above include the following.

Automobile components:

car interior decoration materials, car exterior decoration materials, bumpers, exterior panels, instrument panels, chassis, seats, roof materials, trunk mats, cowlings, wheel seat covers, seat backs, frames of seats, floor mats, sun visors, molded doors, pillar trim, door trim, small pillar trim, cable protection devices, radiators, thermal insulation, trunk sides, head restraints, armrests, tool boxes in the trunk, side impact pads, B-pillar liners, air filters, acoustic panels, gaskets, dust covers, impact pads, helmets, upholstery, roof sides, trunk hatches, drips, door frames.

Components for cars, planes or ships:

car interior decoration materials, car exterior decoration materials, chassis, exterior panels, core materials, seats, partitions, inspection openings, floor sound insulation, subway support layers, refrigerated vehicles, cooled vehicles, spars, decks, aircraft fuselages, containers, galleys, various packaging, heated pipe insulation, cowlings.

Household electrical equipment:

enclosures, enclosures for electrical appliances, color TVs, refrigerators, receptacles designed to maintain temperature, indoor and outdoor units of air conditioners, vacuum cleaners, washing machines, supports for electronic parts, thermal insulators for instruments designed to save energy.

Components for office automation items: casings, personal computers, word processors. speaker grilles.

Materials for buildings and public works: thermal insulation for buildings, thermal insulation for homes, thermal insulation for non-residential use, construction materials for the decoration of the interior of buildings, construction materials for the decoration of the exterior of buildings, furniture, upholstery, insulating floors, containment boxes for sub-floors, blocks, external verandas, materials, for floors, waterproofing layers for floor materials, waterproof and moisture-proof thermal insulators, heat-insulating materials and suitable for preventing the fall of dew for roofs of large dimensions, thermal insulation and waterproof materials for roofing, connection materials, waterproof layers for surface coverings, pitched roof materials, thermal insulation for hydraulic works and hot water pipes, thermal insulation for bathrooms, materials to prevent percolation humidity for sinks, joining materials for window frames, mat supporting tubes, tunnel materials, floor heating mats, thermal insulation for toilet tanks, veneer combination products, common beams, kitchen cabinets, containment boxes, thermal insulation panels with functional shapes, thermal insulation panels, piping panels, acoustic panels, partitions, edging materials or decoration of furniture and building materials, plinths, circular verandas, dividing verandas, stair handrails, bathroom door frames, window frames, opening frames, window frames, planks for pediments, front curtain boards, fascia boards, top rails, warehouses, roof cladding, ceilings, walls and floors, door panels, connecting panels, artificial wood, fire doors, protective and side walls of runways rapid, electric wave absorbers, drying ovens, heating ovens, conduits, unit baths, box conduits, prefabricated houses you, home panels, waterproof panels and cups.

Industrial materials:

pipe covers, packaging materials, bearing materials, heat insulating instruments, plant services, thermal insulators for air conditioning systems, freezing prevention means, thermostats, thermal insulators for refrigerant air conditioning instruments, dividing strips, partitions, reaction wood, and dewdrop prevention materials, storage tanks, piping equipment, formwork, rooms kept free of dust, roentgen radiation installations.

Containers ·.

tableware, dishes for food, cups, ornamental containers, folding boxes, packaging materials, fishing boxes, materials for wrapping, buckets for commercial use, pallets, containers, agro-medical boxes, thermal insulators for frozen foods, ice boxes, cooler boxes, core materials for bags, medical instrument containers, tool boxes, production line plates, display plates, transport boxes, delivery boxes, tanks.

Various and different items:

display materials, sporting goods, bedding, core materials for Japanese floor mats (tatami mats), bicycle parts, mattresses, closed sheets, recycled sheets, cassette tape wrappers, bathroom mats, kitchen mats, sanitary mats, desk pads, heated swimming boards, gymnastics mats, toys, teaching materials, cut letters, support layers for artificial lawns, composite mats, surfboards, ski boards, ballast base materials, bottom materials for support parts, poles for signs, signs, agricultural and horticultural thermal insulators, filing cabinets, films, albums, covers, POP materials, sheets for the prevention of blows, models, advertising signs, cohesive materials, vending machines, displays, tables of panels, sliding materials, picture frames, sideboard frames, surface materials, mirror frames, swimming pools, water tanks, sofas, waterproof layers for foundations, floor chairs, legless chairs, cushions, rackets, table tops, models, furniture surface materials, flotation materials, interior materials.

Incidentally, these examples of uses of articles according to the present invention are provided for illustrative purposes only and not for the purpose of limiting the invention. The molded article having the layered structure of the layered product of the present invention can be obtained with any shape, for example using a predetermined mold.

Effects and advantages of the invention

Thanks to the inclusion of the expanded layer, the thermoplastic polyester layered product according to the present invention has excellent adiabatic and sound absorbing properties and is light weight. Furthermore, thanks to the inclusion of the fiber-reinforced layer, the thermoplastic polyester layered product according to the present invention has a high mechanical strength. The thermoplastic polyester layered product according to the present invention further has excellent heat resistance and chemical resistance. The layered product of thermoplastic polyester according to the present invention is excellent as regards the printability and is therefore usable as a component of various articles. Thus the layered product according to the present invention has sufficient strength together with lightness, adiabatic and sound absorbing properties, so that this layered product is equally particularly suitable for large size printed products. Additionally this layered product has good recycling properties.

DETAILED DESCRIPTION OF THE PREFERRED FORMS OF IMPLEMENTATION

In the following the present invention is illustrated more specifically by means of the following examples of some preferred embodiments in comparison with comparative examples realized in a way different from the invention. However, the invention is not limited to the examples reported below.

EXAMPLE 1

The fiber reinforced thermoplastic polyester as used was produced as follows. Polyethylene terephthalate (hereinafter referred to as PET) (intrinsic viscosity = 0.6 dl / g) to the extent of 69.05% by weight, pyromellitic dianhydride (hereinafter referred to as PMDA) to the extent of 0.25% by weight, cut glass fibers (length: 3 mm, trade name: CS-3J-941, produced by Nitto Boseki Co., Ltd.) to the extent of 30% by weight, and talc (trade name: LMP-100, made by Fuji Tale Co., Ltd.) (as a nucleating agent) in the measure of 0.7% by weight, were mixed in melt dispersion (temperature = 270 ° C, residence time = 30 seconds) with an extruder at two screws (L / D = 48) using a gravimetric feeder and the resulting mixture was extruded from spinnerets in the form of filaments. The extruded filaments were cooled in water and then pelletized with a cutting device, thus obtaining pellets. The resulting pellets were loaded into a rotary drum reactor so as to carry out a reaction under the conditions of rotation speed = 10 rpm, temperature = 220 ° C, pressure = 1 Torr, solid state polyaddition time = 6 hours, raising thus the intrinsic viscosity of the above mentioned pellets at 0.79 dl / g. The resulting pellets were dried at 160 ° C under decompression for 6 hours, and then introduced into an extrusion molding machine (L / D = 24) in order to carry out an extrusion molding (temperature = 270 ° C, permanence = 45 seconds), thus obtaining a printed product in the form of a flat plate with a thickness of 3 mm (hereinafter referred to as reinforced PET).

The expanded thermoplastic polyester as used was produced as follows. PET (intrinsic viscosity = 0.6 dl / g) in the measure of 98.52% by weight, PMDA in the measure of 0.49% in weight and talc (trade name: LMP-100 produced by Fuji Tale Co., Ltd. ) (as nucleating agent) in the measure of 0.99% by weight were mixed in melt dispersion (temperature = 270 ° C, residence time = 27 seconds) with a two-screw extruder (L / D = 48) using a gravimetric feeder and the resulting mixture was extruded from spinnerets in the form of filaments. The extruded filaments were cooled in water and then pelletized with a cutting device, thus obtaining pellets. The resulting pellets were loaded into a rotary drum type reactor so as to carry out a reaction under the conditions of rotation speed = 10 rpm, temperature = 220 ° C, pressure = 1 Torr, solid state polyaddition time = 10 hours. , thus raising the intrinsic viscosity of the above mentioned pellets to 0.95 dl / g. The resulting pellets were dried at 160 ° C under decompression for 6 hours and then introduced into a molding and expansion machine (L / D = 24), in which nitrogen gas was then injected as blowing agent in order to carry out the molding. by extrusion of the foam (temperature = 270 ° C, residence time = 49 seconds), thus obtaining a molded product in the form of a flat plate with an expansion ratio of 10 times and a thickness of 3 mm (hereinafter referred to as Expanded PET).

Both the reinforced PET and the foamed PET were cut in dimensions of 300 x 300 min, one side of each of which was then preheated on a plate heated to 140 ° C of surface temperature for 1 minute. The preheated sides were attached to each other and then quickly compressed to a pressure of 5 kg / cm2 with a press. Further, the other side of the expanded PET was attached to another reinforced PET in the same way described above, thus obtaining a layered product with a reinforced PET / expanded PET / reinforced PET structure.

Membership

With regard to adhesion, the degree of adhesion between the layers of the layered product was evaluated as follows. The related results are shown in Table 1.

O: the adhesion is good and there is no peeling of the layer.

Δ: the adhesion is somewhat bad and you can partially see a peeling of the layer.

X: adhesion is bad and there is a large peeling of the layer.

Fractionation properties during disposal Different materials require fractionation during disposal and recycling. This work is manual and therefore is detested by those engaged in this kind of activity. Thus the fact that fractionation was necessary or not was evaluated with 0 and X (0 shows that fractionation is not necessary). The results of this are shown in Table 1.

Recycling property

The layered product was pulverized without fractionation and then introduced into an extruder in order to carry out a repelletization. In this repelletization, it was evaluated as follows whether recycled pellets that were reusable as starting materials for fiber reinforced polyester resin were obtainable or not. The results of this are shown in Table 1.

O: recycled pellets are obtainable and reusable without problems.

Δ: There is separation of components other than PET, so that the sample is not suitable for reuse.

X: the components decompose in the extruder and therefore no pellets can be obtained so that this sample is absolutely not suitable for reuse.

EXAMPLE 2

The reinforced PET and the expanded PET which were used in Example 1 and further a non-woven fabric made of PET fibers as an ornamental layer (hereinafter referred to as PET non-woven fabric) were layered in the same way as in Example 1. As a result, a layered product with a reinforced PET / expanded PET / non-woven PET structure was obtained (the surface of the non-woven PET was the outermost layer). This layered product was evaluated in the same way as in Example 1. The results of this are shown in Table 1.

COMPARATIVE EXAMPLE 1

The reinforced PET as used in example 1 and an expanded polyethylene sheet with an expansion ratio of 5 times and a thickness of 2 min (hereinafter referred to as expanded PE) were layered in the same way as in example 1 with the exception of fact that the preheating temperature was 100 ° C. As a result, a layered product with a reinforced PET / expanded PE structure was obtained. This layered product was evaluated in the same way in Example 1. The results of this are shown in Table 1.

COMPARATIVE EXAMPLE 2

The reinforced PET and the foamed PET, which were used in Example 1, and further a vinyl chloride resin film with a thickness of 0.5 mm as an ornamental layer (hereinafter referred to as PVC film) were layered in the same way as in Example 1. As a result, a stratified product with a reinforced PET / expanded PET / PVC film structure was obtained. This stratified product was evaluated in the same way as in Example 1. The relative results are shown in Table 1.

In the following an example of molding for producing an automobile roof material is presented in the following example, such as an example of automobile interior decoration materials which are examples of articles including the layered product of the present invention. Furthermore, a molded article of L-channel structure is presented in Example 4 below as an example of various interior decoration materials, such as wall materials, which are other examples of articles including the layered product of the present invention.

EXAMPLE 3

A layered product of reinforced PET / expanded PET / reinforced PET structure was produced in the same way as in Example 1 except that the thickness of the reinforced PET was changed to 1 mm. This layered product was heated with far infrared rays until the actual temperature of each layer of the layered product rose to 180 ° C or more. Then the heated layered product was molded into the form of an automobile roof material by a vacuum molding process. The resulting molded article had great stiffness and good adiabatic properties. The shape of this printed article is shown in Figure 1.

EXAMPLE 4

The layered product of reinforced PET / expanded PET / reinforced PET structure, as used in Example 3, was molded by compression molding with a mold heated to 180 ° in the form of an L-shaped channel with curved surfaces that do not need to be joining components in the wall corner parts. Due to the fact that the resulting molded article had no joining parts on its curved surfaces, this molded item facilitated the joining work in assembling the wall materials. The shape of this printed article is shown in Figure 2.

From the results of the molding in Examples 3 and 4 above, it could be understood that, if the layered product according to the present invention is suitable for various molding or molding conditions, this layered product is readily moldable into desired molded products of various shapes, for example also in the form of boxes or bathtubs, such as heat-insulating containers. Various details of the invention can be modified without departing from its spirit or scope. Furthermore, the foregoing description of the preferred embodiments according to the present invention is provided for illustrative purposes only and not for the purpose of limiting the invention as defined by the following claims and their equivalents.

Claims (8)

CLAIMS 1. A layered product of thermoplastic polyester, comprising a layered structure AB which includes a layer A of a fiber-reinforced thermoplastic polyester and an expanded layer B of a thermoplastic polyester, in which the fiber-reinforced layer A and the expanded layer B are layered on each other. 2. The thermoplastic polyester laminate product according to claim 1, wherein only a laminate structure AB is included in the thermoplastic polyester laminate product, and wherein another layer A of a fiber-reinforced thermoplastic polyester is laminated on the opposite side of the layer B expanded. 3. Thermoplastic polyester layered product according to claim 1 or 2, wherein the thermoplastic polyester has a molecular weight increased by a process including the step of mixing in the melt state of a mixture including a thermoplastic polyester and a polycarboxylic anhydride to effect a reaction of chain elongation. The thermoplastic polyester laminate product according to claim 3, wherein the thermoplastic polyether is obtained by a process including the melt mixing step and further the step of carrying out a solid state polyaddition reaction of the melt mixed mixture after the mixing step in the molten state, thus further continuing the chain elongation reaction. The thermoplastic polyester laminate product according to any one of claims 1 to 4, wherein the fiber in the fiber-reinforced layer A is glass fiber. 6. Thermoplastic polyester layered product according to any one of the claims 1 to 5, wherein 50 mol% or more of the acid components as used to produce the thermoplastic polyester of the fiber-reinforced layer A is the same 50% molar or more of the acid components as used to produce the thermoplastic polyester of the expanded layer B, and in which 50% molar or more of the glycol components as used to produce the thermoplastic polyester of the fiber reinforced layer A is the same 50 mol% or more of the glycol components as used to produce the thermoplastic polyester of the expanded B layer. 7. Thermoplastic polyester laminate product according to any one of claims 1 to 6, wherein the thermoplastic polyester is polyethylene terephthalate (PET). An article comprising the thermoplastic polyester layered product as indicated in any one of claims 1 to 7.