KR20000077235A - Thermoplastic polyester stack including foamed layer and product thereof - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention aims to provide a thermoplastic polyester laminate and a product thereof, wherein the thermoplastic polyester laminate has excellent thermal insulation, sound absorption, light weight, heat resistance, chemical resistance and excellent moldability of the foamed thermoplastic polyester layer. It can further exhibit excellent mechanical strength while maintaining. The thermoplastic polyester laminate according to the present invention includes a laminated structure AB including a thermoplastic polyester fiber reinforcement layer A and a thermoplastic polyester foam layer B, wherein the fiber reinforcement layer A and the foam layer B are laminated to each other. It is characterized by. In addition, the product according to the invention is characterized in that it comprises the thermoplastic polyester laminate of the present invention.

Description

Thermoplastic polyester stack including foamed layer and product thereof {Thermoplastic polyester stack including foamed layer and product about}

The present invention relates to a thermoplastic polyester laminate comprising, for example, a foam layer for use in interior materials, fillers, thermal insulation materials and shock absorbers.

The thermoplastic polyester foam sheet is excellent in heat insulation and sound absorption, is light in weight, and further shows heat resistance and chemical resistance (these resistances are characteristics of the thermoplastic polyester) and excellent moldability. Therefore, it is very popular. For example, Japanese Patent No. 2847723 proposes a technique for connecting a surface material made of a fabric such as a nonwoven fabric with a thermoplastic polyester foam layer in order to take advantage of these advantages for interior materials of automobile trunk compartments.

Thermoplastic polyester foam sheets have the above advantages, but also have the drawbacks specific to foam materials. Therefore, improvement of the above disadvantage is required.

For example, JP-A-170999 / 1994 discloses a polyester resin layer on at least one side of a thermoplastic polyester foam sheet in consideration of the fact that unevenness on the surface of the thermoplastic polyester foam sheet causes pinholes during thermoforming of the foam sheet. We propose technique to form. JP-A-300585 / 1996 proposes a technique of forming a non-foamed polyester resin on a thermoplastic polyester foam sheet in order to improve the surface printability of the thermoplastic polyester foam sheet. JP-A-156005 / 1997 discloses a polyester resin non-foamed layer on one side of a thermoplastic polyester foam sheet to improve the appearance design with heat resistance used for a thermocooking container utilizing the heat resistance of the thermoplastic polyester foam sheet. Proposing a technology to form. JP-A-180952 / 1998 discloses a thermoplastic polyester non-foamed film, an ethylene-vinyl alcohol copolymer resin film and another thermoplastic polyester non-foamed film in order to improve gas barrier properties. The technique of laminating | stacking on one side of ester foam sheet is proposed.

However, one of the disadvantages of thermoplastic polyester foam sheets is their low mechanical strength. JP-A-180952 / 1998 discloses that the multilayer structure can provide adequate strength. However, this multilayer structure is complicated and the improvement of mechanical strength is also not enough.

When these problems of mechanical strength are solved, the thermoplastic polyester foam sheet is used in automobile interior materials and food heating containers by making good use of the thermoplastic polyester foam sheet having excellent moldability, heat insulation and sound absorption, and furthermore, excellent heat resistance and chemical resistance. It can be effectively used in various products such as fillers, shock absorbers, house interior materials (for example, floor mats), and laminates for electronic components. Thermoplastic polyester foam sheet is excellent in light weight and is particularly suitable for large scale products.

An object of the present invention is to increase the mechanical strength of the thermoplastic polyester foam layer so that the thermoplastic polyester foam layer can be used for various purposes.

The present inventors earnestly examined to solve the said problem. As a result, when the fiber-reinforced thermoplastic polyester layer containing the reinforcing fibers is laminated on the thermoplastic polyester foam layer, the obtained thermoplastic polyester laminate has excellent thermal insulation, sound absorption, light weight, heat resistance, chemical resistance and It can also exhibit excellent mechanical strength while maintaining formability. In addition, since the present inventors have a foam layer and a fiber-reinforced layer in such a laminate, the same material, that is, a thermoplastic polyester, has good adhesion between the layers in the mutual lamination of these layers, and furthermore the same material composition, It is also excellent in recyclability since the sorting is unnecessary at the time of disposal.

Therefore, the thermoplastic polyester laminate according to the present invention is characterized in that it comprises a laminated structure AB comprising a thermoplastic polyester fiber reinforcement layer A and a thermoplastic polyester foam layer B, wherein the fiber reinforcement layer A and the foam layer B is Are stacked on each other.

In addition, the product according to the invention is characterized in that it comprises the thermoplastic polyester laminate of the invention.

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

BRIEF DESCRIPTION OF THE DRAWINGS The perspective view of the automotive ceiling material which is the molded article of Example 3. FIG.

2 is a perspective view of an L channel structure which is a molded product of Example 4. FIG.

Hereinafter, the configuration of the present invention will be described in detail.

(Thermoplastic Polyester):

The thermoplastic polyesters used in the present invention are mainly products polycondensed from acid and glycol components. Examples of the acid component include dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and diphenyl ether dicarboxylic acid; And dicarboxylic acid derivatives such as dimethyl terephthalate. These may each be used alone or in combination with each other. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol. These may each be used alone or in combination with each other.

Considering the high industrial value, polyethylene terephthalate and polybutylene terephthalate are preferred among the polycondensation products, and polyethylene terephthalate is most preferred.

In addition, the thermoplastic polyester may be used after adjusting by various high-moleculization methods. Examples of the polymerization method include a solid phase polycondensation method and a method related to the polymerization reaction with various chain extenders in the molten or solid phase. The polymerization method may be suitably applied to a thermoplastic polyester resin to produce a laminate structure according to the present invention. For example, the fiber reinforcement layer and the foam layer may be formed from a thermoplastic polyester polymerized with a chain extender in the molten phase, or the fiber reinforcement layer and the foam layer may be formed from a thermoplastic polyester polymerized with a chain extender in the solid phase. These layers can also be formed by combining their respective polymerisation methods. The polymerization method is not particularly limited, but considering the stability of the quality, a thermoplastic polyester polymerized by adding a polycarboxylic anhydride (used as a chain extender) is preferred. Furthermore, in consideration of the pole number problem such as gelation, thermoplastic polyester which is polymerized by adding polycarboxylic anhydride by solid state addition reaction is more preferable. By using the thermoplastic polyester polymerized by the above method, the rigidity of the fiber-reinforced thermoplastic polyester layer is further improved, and the foam moldability of the thermoplastic polyester foam layer is improved. The recycled thermoplastic polyester resin which recycled the waste drinking water bottle can also be used preferably after adjusting by the said polymerization method.

In consideration of moldability and recyclability, the acid component or glycol component in which the thermoplastic polyester fiber reinforcement layer and the foaming layer manufactured to form a repeating unit of the thermoplastic polyester of the fiber reinforcement layer is usually 50 mol% or more, preferably Is the same as the acid component or glycol component which forms the repeating unit of the thermoplastic polyester of the foamed layer at a ratio of 70 mol% or more, more preferably 80 mol% or more, or the melting point difference of the thermoplastic polyester is within 30 ° C. It is desirable to match. In consideration of recyclability, the thermoplastic polyester fiber reinforcement layer and the foam layer are more preferably the same at a ratio of 100 mol%, and the two layers include polyethylene terephthalate (PET) at a ratio of 100 mol% as the thermoplastic polyester. Most preferred.

Although not limited, the thermoplastic polyester used in the present invention is preferably used because the melt kneading of the thermoplastic polyester with the polycarboxylic anhydride to effect the chain extension reaction increases the molecular weight of the thermoplastic polyester more reliably. Is a thermoplastic polyester whose molecular weight is increased by a process comprising melt kneading or melt mixing a mixture comprising a thermoplastic polyester and a polycarboxylic anhydride for carrying out the chain extension reaction.

In the polycarboxylic anhydride which can be used in the present invention, aromatic tetracarboxylic dianhydride, particularly pyromellitic dianhydride is preferable. Examples of other useful dianhydrides are 3,3 ', 4,4'-diphenyltetracarboxylic acid, (perylene-3,4,9,10) tetracarboxylic acid, 3,3', 4,4'- Benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) ether, bis (3,4-dicarboxyphenyl) sulfone, 1,2 , 3,4-cyclobutanetetracarboxylic acid and 2,3,4,5-tetracarboxyhydrofuran. The amount of polycarboxylic anhydride used is usually in the range of 0.05 to 2 parts by weight per 100 parts by weight of the thermoplastic polyester.

In carrying out the melt kneading, other materials may be added if necessary. Examples of these other materials include: polyolefins such as polyethylene, polypropylene, and polybutylene; And other thermoplastic resins such as vinyl chloride resins, polyvinyl acetals, polyvinyl alcohols, polystyrenes, AS resins, ABS resins, polyamides, polycarbonates, and thermoplastic elastomers; Fillers such as calcium carbonate and talc; And crystal nucleating agents, crystallization promoters, plasticizers, antioxidants, stabilizers, pigments, flame retardants and release agents.

Although not limited, the thermoplastic polyester used in the present invention is preferably a thermoplastic polyester having an increased molecular weight by a process comprising melt kneading or melt mixing a mixture comprising thermoplastic polyester and polycarboxylic anhydride. Do.

The melt kneading is preferably carried out by melt dispersing kneading with a twin screw extruder. This twin screw extruder is not particularly limited, but examples thereof include a co-rotating interlocking twin-screw extruder with an exhaust port, a co-rotating non-engaging twin-screw extruder with an exhaust port, and a reverse rotary interlocking 2 with an exhaust port. Axial screw extruder, reverse rotation non-engaged biaxial screw extruder with exhaust port, co-rotating interlocking twin screw extruder without exhaust port, coaxial rotation non-engaged biaxial screw extruder without exhaust port, no exhaust port Non-rotating non-engagement twin screw extruder, and non-rotating non-engagement twin screw extruder without vent. Among these, the reverse rotation non-engagement twin screw extruder provided with an exhaust port is especially preferable. The melt kneading temperature also depends on the melting point of the polymer or copolymer used, but is preferably in the range of 240 to 340 ° C. The extruder residence time is also preferably in the range of 20 to 100 seconds.

The mixture obtained by the melt-dough is preferably fed to a solid state polyaddition treatment described later to have a pellet shape. When using a twin screw extruder for the melt dough, the mixture is extruded from the extruder in the form of strands (diameter = preferably 1 to 10 mm, more preferably 3 to 5 mm) and then with a pelletizer. Cutting (preferably between 1 and 20 mm in length, more preferably between 2 and 10 mm) gives solid-chip-shaped pellets.

Although not limited, since the solid state polyaddition further increases the molecular weight, the thermoplastic polyester used in the present invention preferably performs the solid state addition of the melt kneaded mixture after the melt kneading step and the melt kneading step. Thermoplastic polyester obtained by a process comprising a step.

In carrying out the solid state addition reaction, it is preferable to mold the melt-kneaded mixture into pellet shape and then use it for the reaction. The use of pellet shaped mixtures has the economic advantage of not having to make the reaction space large. The mixture is heated in an inert gas stream under atmospheric pressure or under reduced pressure, in which the solid phase addition is heated in the reactor in the range of 180 to 230 ° C. to carry out the solid phase addition reaction. Under the inert gas flow or reduced pressure, volatile components or water are effectively removed from the mixture.

The thermoplastic polyester used in the present invention is preferably a thermoplastic polyester obtained by solid state polyaddition reaction on a pellet. The reason for this is as follows. It is also possible to carry out a melt kneading reaction of a mixture comprising a thermoplastic polyester and a polycarboxylic anhydride, but since the reaction is carried out at a temperature higher than the melting point of the thermoplastic polyester, the reaction proceeds excessively to cause three-dimensionalization. Can be. As a result, the die expansion effect during the extruder or during the extrusion provides a very non-uniform molded article, so crushing or local stretching occurs. Also, for example, the intrinsic viscosity (IV) distribution of the polymerized PET resin may be nonuniform. However, solid state polyaddition can polymerize thermoplastic polyesters and have a sufficiently high intrinsic viscosity without causing these problems. Therefore, the preferred polymerization method that can be used in the present invention is a solid state polyaddition reaction, more preferably a pelletized polyaddition reaction. The thermoplastic polyester obtained by the solid state polyaddition reaction has such a high molecular weight that the thermoplastic polyester can measure the intrinsic viscosity (IV), and the thermoplastic polyester is non-dimensionalized, and thus formability is obtained. Since it has surely, it has a preferable form as a molding material. As a result, this molding material has little disadvantage and can provide a molded article having good moldability and appearance in extrusion molding.

The solid state polyaddition reaction of the present invention can also be carried out on moldings comprising a mixture of thermoplastic polyester and glass fibers, for example pelleted thermoplastic polyester moldings containing glass fibers.

The solid state polyaddition reaction provides a polymer thermoplastic polyester having an increased intrinsic viscosity, and the intrinsic viscosity of the thermoplastic polyester is preferably 0.5 dl / g or more, more preferably 0.5 to 1.8 dl / g, more preferably 0.6 To 1.8 dl / g.

(Foam layer)

Various processes conventionally can be used as a process for forming a thermoplastic polyester foam layer, and therefore this process is not specifically limited. Hereinafter, the example is demonstrated concretely.

The thermoplastic polyester foam layer used in the present invention can be obtained, for example, by a process comprising the following steps: melt kneading an additive such as thermoplastic polyester and a thickener whose amount is adjusted in an extruder; Mixing the obtained melt kneaded mixture with a blowing agent under high pressure; Extruding the resulting mixture into a low pressure region such as air to foam the mixture into a sheet;

Examples of the extruder include an extruder such as a single screw extruder, a multi screw extruder, and a tandem extruder. When using these extruders, the melt kneaded mixture is extruded from the die into the low pressure region.

Examples of such blowing agents include physical blowing agents having the property of gasifying or expanding upon heating.

Typical examples of such blowing agents; Inert gases such as carbon dioxide and nitrogen gas; Methane, ethane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane and 3,3-dimethylbutane Saturated aliphatic hydrocarbons; Saturated alicyclic hydrocarbons such as methylcyclopropane, cyclopentane, ethylcyclobutane and 1,1,2-trimethylcyclopropane; Aromatic hydrocarbons such as benzene; Hydrocarbon halides such as trichloromonofluoromethane, dichlorofluoromethane, monochlorodifluoromethane, trichlorotrifluoroethane and dichlorotetrafluoroethane; Ethers such as dimethyl ether and 2-ethoxyethanol; Ketones such as acetone, methylethyl ketone and acetylacetone. These can be used individually or in combination with each other, respectively.

The amount of the blowing agent 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 kneaded mixture obtained by melt kneading a mixture comprising thermoplastic polyester to obtain a thermoplastic polyester foam layer. The ester foam layer can have a preferred expansion ratio. Also, the amount of blowing agent is preferably 10 parts by weight or less, particularly preferably 7.5 parts by weight or less per 100 parts by weight of the melt-kneaded mixture so that the size stability of the thermoplastic polyester foam layer does not deteriorate during extrusion.

The thickness of the thermoplastic polyester foam layer obtained by the above method can be appropriately adjusted according to the purpose of use of the thermoplastic polyester laminate, but is usually preferably in the range of about 0.5 to about 5 mm. In addition, the expansion ratio of the thermoplastic polyester foam layer can be appropriately adjusted according to the purpose of use of the thermoplastic polyester laminate, for example, in the range of 1.5 to 20 times.

The foam layer used in the present invention may further include additives such as stabilizers, pigments, fillers, flame retardants and antistatic agents, depending on the purpose.

In addition, the amount of the blowing agent is preferably 0.5 to 10 parts by weight, more preferably 1 to 10 parts by weight per 100 parts by weight of the thermoplastic polyester. If the amount of foaming agent is too large, foaming occurs excessively during molding, thereby degrading the size stability of the resulting laminate or foam layer.

It is also possible to add conventional foaming-nucleating agents such as talc and various metal salts in order to finely foam the foaming layer. The amount of foam-nucleating agent added is preferably in the range of 0.01 to 5 parts by weight per 100 parts by weight of thermoplastic polyester. In addition, when performing extrusion foaming, conventional reaction promoters may be used to improve extrusion moldability. Examples of the reaction accelerators include Group I, II and III metal compounds such as sodium carbonate; Organometallic compounds such as aluminum stearate. The addition amount of the reaction accelerator is preferably in the range of 0.01 to 5 parts by weight per 100 parts by weight of the thermoplastic polyester.

(Fiber Reinforcement Layer):

The reinforcing fibers may be, for example, inorganic fibers such as glass fibers, carbon fibers or metal fibers, or organic fibers that do not melt at the molding temperature of matrix resins such as thermoplastic polyester fibers or polyamide fibers. Among them, glass fibers are excellent in cost, strength and rigidity, and there is no particular problem even if they are recycled into the same fiber reinforced thermoplastic polyester. In addition, thermoplastic polyester fibers are excellent in recyclability because their materials are the same as matrix fibers.

Although not limited, the fiber length is preferably in the range of 0.1 to 5 mm, more preferably 0.2 to 1.0 mm.

Although not limited, the amount of fibers is preferably in the range of 1 to 45% by weight, more preferably 5 to 45% by weight.

The above-mentioned thermoplastic polyester and the fiber are mixed, and if necessary, further mixed with the other materials mentioned in the description of the foam layer, and the resulting mixture is used, for example, using a sheet extruder at a thickness of 0.3 to 20 mm at 240 to 280 ° C., Preferably, the fiber reinforced layer is obtained by molding into a sheet shape of 0.3 to 10 mm. In addition, the thickness is not particularly limited because the thickness can be freely changed depending on the purpose for which the laminate is used.

(Laminated body):

The thermoplastic polyester laminate according to the invention is characterized in that it comprises a laminate structure comprising a fiber reinforced layer of thermoplastic polyester and a thermoplastic polyester foam layer, wherein the fiber reinforced layer and the foam layer are laminated to each other, i.e. fibers The reinforcement layer is laminated on the foam layer or the foam layer is laminated on the fiber reinforcement layer. For reference, "laminate" herein refers to a product in which two or more layers stacked on each other are integrated. Specifically, when the fiber reinforcement layer is denoted by A and the foamed layer is denoted by B, the thermoplastic polyester laminate includes at least one laminate structure AB in the entire laminate structure, such as laminate structure AB, laminate structure ABA, laminate structure ABAB. do.

In view of strength, the thermoplastic polyester laminate according to the invention comprises said three-layer ABA or a series of said laminated structures AB. However, the thermoplastic polyester laminate is not limited to this.

The thermoplastic polyester laminate according to the present invention comprises a laminate of the foam layer and the fiber reinforcement layer. If necessary, a design layer or thermoplastic polyester non-foaming film to be described later may be further laminated on at least one side of the thermoplastic polyester laminate.

The design layer or thermoplastic polyester non-foamed film is used as the outermost layer of the thermoplastic polyester laminate according to the present invention as needed. The design layer comprises a fabric such as a nonwoven fabric, a woven fabric or a baffle blanket, and the thermoplastic polyester laminate according to the present invention improves appearance quality when used, for example, for interior use. The thickness of the design layer is not particularly limited. For example, a thermoplastic polyester non-foamed film is provided to enhance properties, moldability, printability and adhesion to the body of the laminate, for example, and to enhance surface protection such as waterproofing. In the thermoplastic polyester non-foamed film, there is no restriction on transparency, extension or absence, crystallinity, surface hardness and thickness.

Examples of the method of laminating the layer or the film such as the foamed or fiber reinforced layer in the present invention include a method by heat-sealing and a method by adhesion. When the method by adhesion is used, the adhesive layer is not treated as any layer in the thermoplastic polyester laminate according to the invention.

For reference, the laminate according to the invention may also be referred to as a multilayer article, a multilayer article or a laminate, for example.

(product):

As long as the product includes the thermoplastic polyester laminate according to the present invention, the kind of the product according to the present invention is not limited.

The thermoplastic polyester laminate used in the product according to the invention has sufficient strength by the fiber reinforcement layer with light weight, heat insulation and sound absorption by the foam layer. Thus, products containing this laminate are suitable for, for example, automotive interiors, home interiors and various box-type thermal insulated containers, but the use of the products is not limited thereto. In particular, since the laminate has sufficient strength, the product containing the laminate can also be applied to large-scale molded articles.

Examples of such products include:

(Automotive Parts):

Automotive Interior, Automobile Exterior, Bumper, Exterior Wall, Instrument Panel, Chassis, Seat, Ceiling, Trunk Mat, Cowl, Wheelhouse Cover, Seat Back, Seat Frame, Floor Mat, Sun Visor, Molded Doors, Pillar Pillar trims, door trims, quarter trims, wiring protectors, automotive cooler thermal insulation, trunk side, headrests, armrests, toolboxes in the trunk, side impact absorbing pads, center pillar trim (center pillar garnishes), air filters, acoustic sheets, gaskets, dust covers, shock absorbing pads, helmets, saddles, roof side, trunk lids, drips, door frames.

(Members for cars, airplanes or ships)

Automobile interior materials, automobile exterior materials, chassis, exterior walls, core materials, seats, partition walls, metering holes, floor acoustic barrier materials, mattresses for subways, refrigerators and refrigerators, longerons of aircraft fuselage, decks, airplane bodies, containers, ships Galleys, various packing materials, pipe heat insulators, cowlings for aircraft.

(Household appliances):

Housings, electric pots, color TVs, refrigerators, thermos, internal and external units of air conditioners, vacuum cleaners, washing machines, electronic component trays and thermal insulators for power saving instruments.

(OA Appliance Supply):

Housing, personal computer, word processor, speaker grille.

(Public buildings and building materials):

Building thermal insulators, residential thermal insulators, thermal insulators for non-housing buildings, building materials for homes, building materials for homes, building materials for public buildings and buildings, furniture, wallpaper, cushion flooring, underfloor container boxes, bricks, wet verandas verandas), flooring, floor coverings, moisture proof and waterproof thermal insulation, long roof insulation and condensation prevention materials, roof insulation and waterproofing, joints, carpet coverings, folded face roofing materials, thermal insulation for water and hot water pipes , Thermal insulation for bathtubs, anti-condensation for sinks, joints for chassis, back-up materials, tunnel materials, floor-heat mats, thermal insulation for septic tanks, veneer-coupled products, general joists , Kitchen cabinets, container boxes, formwork functional heat-insulating panels, thermal insulation panels, pipe panels, acoustic panels, partition walls, edges or decorations of furniture and building materials, Plinths, round porches, parting verandas, stair railings, bathroom door frames, chassis frames, opening frames, bay window frames, face pediment boards, face fire screens , Eaves, top rails, warehouses, roof, ceiling, wall and floor fittings, door panels, wall panels, artificial wood, fire doors, side and protection walls of highways, electromagnetic wave absorbers, drying ovens, heating stoves, Ducts, unit baths, box culverts, prefabricated houses, housing panels, waterproof fans and panels.

(Industrial Goods):

Pipe covers, packing materials, cushioning materials, heat-insulating instruments, plant equipment, heat insulators for air conditioning equipment, freeze protection, thermostats, heat insulators for refrigerated air conditioning equipment, parting strips, partition walls, reaction wood wood, dew condensation, storage tanks, pipes, formworks, clean rooms, roentgen.

(Vessel):

Table utensils, food trays, bows, design vessels, folding boxes, packing materials, fish boxes, packaging materials, buckets for business use, pallets, containers, pesticide boxes, frozen foods Thermal insulators, ice boxes, cooler boxes, core materials in bags, medical instrument containers, tool boxes, production line trays, display utensils, transport boxes, delivery boxes, tanks.

(Miscellaneous goods and others):

Display materials, sporting goods, bedding, core materials for Japanese floor mats, bicycle parts, mattresses, blind sheets, recuperation sheets, cassette tape cases, bathroom mats, kitchen mats, health mats (health mats), desk mats, stepping boards for swimming pools, gym mats, toys, teaching materials, cut letters, underpads for artificial turf, joint carpets, surfboards, skis Plates, bed cores, shoe soles, road signs, signs, agricultural and horticultural heat insulators, piles, films, albums, binders, POP materials, damage-resistant sheets, patterns, promotional signs, flocculators, vending machines, showcases, panels Boards, skid materials, picture frames, tabletop frames, surface materials, mirror frames, pools, cisterns, sofas, rugs, floor chairs, legless chairs, cushions, rackets, table tops (table tops), models, Old surface material, buoys material (float materials), interior materials.

For reference, examples of the use of the products according to the present invention are only examples, and do not limit the present invention. A molded article having a laminated structure of the laminate according to the present invention having an arbitrary shape can be obtained, for example, using a predetermined mold.

Example

Hereinafter, the present invention will be described in more detail with reference to some preferred embodiments of the following, which are not in accordance with the present invention. However, the present invention is not limited to the following examples.

Example 1

<Polymerization of PET by Solid State Addition>

The fiber reinforced thermoplastic polyester used was prepared as follows. Polyethylene terephthalate (hereinafter referred to as PET) (intrinsic viscosity = 0.6dl / g) 69.05% by weight, 0.25% by weight of pyromellitic dianhydride (hereinafter referred to as PMDA), finely ground glass fiber (length: 3mm, CS-3J-941, manufactured by Nito Boseki Co., Ltd., 30% by weight and talc (trade name: LMP-100, manufactured by Fuji Talc, Inc.) (as nucleating agent) using a weight-loaded feeder To melt-dispersion-dough (temperature 270 ° C., residence time 30 seconds) with a twin screw extruder (L / D = 48), and the resulting mixture was extruded from the die in the form of strands. The extruded strands were cooled in water and then pelletized with a strand cutter to obtain pellets. The obtained pellet was charged into a tumbler type rotary reactor, and the reaction was carried out under a reactor condition of a rotational speed of 10 rpm, a temperature of 220 ° C., a pressure of 1 Torr (133 Pa), and a solid phase addition time of 6 hours to obtain an inherent viscosity of the pellet at 0.79 dl / g. Increased. The resulting pellets were dried at 160 ° C. under reduced pressure for 6 hours, then introduced into an extrusion machine (L / D = 24) and extruded (temperature 270 ° C., residence time 45 seconds) to form a flat article having a width of 1 m and a thickness of 3 mm. (Hereinafter referred to as reinforced PET).

The foamed thermoplastic polyesters used were prepared as follows. 98.52 wt% PET (intrinsic viscosity = 0.6 dl / g), 0.49 wt% PMDA and 0.99 wt% Talc (trade name: LMP-100, manufactured by Fuji Talc) using a weight-load feeder The melt-dispersion-dough (temperature 270 degreeC, residence time 27 second) was carried out with the screw screw extruder (L / D = 48), and the obtained mixture was extruded from die | dye in strand shape. The extruded strands were cooled in water and then pelletized with a strand cutter to obtain pellets. The obtained pellet was charged into a tumbler type rotary reactor, and the reaction was carried out under a reactor condition of a rotational speed of 10 rpm, a temperature of 220 ° C., a pressure of 1 Torr (133 Pa), and a solid phase addition time of 10 hours to obtain an intrinsic viscosity of the pellet at 0.95 dl / g. Increased. The obtained pellets were dried at 160 ° C. under reduced pressure for 6 hours, then introduced into a foam extrusion machine (L / D = 24) in which nitrogen gas was injected as a blowing agent, followed by foam extrusion (temperature 270 ° C., residence time 49 seconds), thereby expanding the expansion ratio. A flat molded article having a shape of 10 times, 1 m in width and 3 mm in thickness was obtained (hereinafter referred to as foam PET).

Each of the reinforced PET and foamed PET was cut to a size of 300 × 300 mm and each side was preheated on a heating plate at a surface temperature of 140 ° C. for 1 minute. The preheated sides were attached to each other and quickly pressed into the compressor at a pressure of 5 kg / cm ² (5,000 hPa). Further, by attaching the other side of the foamed PET to the other side of the reinforced PET in the same manner as above, a laminate of the reinforced PET / foamed PET / reinforced PET structure was obtained.

<Adhesive>

As for adhesiveness, the degree of adhesion between the layers of the laminate was evaluated as follows. These results are shown in Table 1.

: Adhesiveness is good and peeling of a layer is not seen.

: Adhesion is somewhat poor, and peeling of layer is partially seen.

X: Adhesiveness is bad and large peeling of a layer is seen.

〈Classification at the time of disposal〉

Different materials require classification at disposal and recycling. This work is manual and is avoided by those skilled in the art. So, whether or not classification is necessary And × Indicates that no classification is required). These results are shown in Table 1.

<Recyclability>

The laminate was pulverized without being sorted, and then introduced into an extruder for repelletization. In this repelletization, it was evaluated as follows whether recycled pellets which can be reused as starting materials for the fiber reinforced polyester resin can be obtained. These results are shown in Table 1.

: Recycled pellets can be obtained and reused without any problem.

: Separation of components other than PET is observed and not suitable for reuse.

X: The components decomposed in the extruder to obtain no pellets, which are not suitable for reuse at all.

Example 2

<PET nonwoven fabric laminate>

It was laminated in the same manner as in Example 1, further comprising a reinforced PET and a foamed PET used in Example 1, and a nonwoven fabric made of PET fibers (hereinafter referred to as a 'PET nonwoven fabric') as a design layer. As a result, a laminate of the reinforced PET / foamed PET / PET nonwoven fabric structure was obtained (the surface of the PET nonwoven fabric was the outermost layer). This laminate was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1

The reinforced PET used in Example 1 and a foamed polyethylene sheet (hereinafter referred to as 'foamed PE') having a thickness of 5 times and a thickness of 2 mm were laminated in the same manner as in Example 1 except that the preheating temperature was 100 ° C. As a result, a laminate of reinforced PET / foamed PE structure was obtained. This laminate was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2

It was laminated in the same manner as in Example 1, further comprising a reinforced PET and foamed PET used in Example 1, and a 0.5mm thick vinyl chloride resin film (hereinafter, referred to as a 'PVC film') as a design layer. As a result, a laminate of the reinforced PET / foamed PET / PVC film structure was obtained. This laminate was evaluated in the same manner as in Example 1. These results are shown in Table 1.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Laminate structure Reinforced PET / Foamed PET / Reinforced PET Reinforced PET / Foamed PET / PET Nonwoven Fabric Reinforced PET / foamed PE Reinforced PET / Foamed PET / PVC Film Adhesive × Classification at disposal × × Recyclability ×

Next, as an embodiment of an automobile interior material which is an example of a product including a laminate according to the present invention, a molding example for manufacturing an automobile ceiling material is described in Example 3 below. In addition, as an embodiment of various interior materials such as wall material, which is another example of a product including a laminate according to the present invention, a molded article having an L channel structure is described in Example 4 below.

Example 3

〈Thickness Change of Reinforced PET〉

A laminate of reinforced PET / foamed PET / reinforced PET structures was prepared in the same manner as in Example 1 except that the thickness of the reinforced PET was changed to 1 mm. This laminate was heated in far infrared until the actual temperature of each layer of the laminate reached 180 ° C or higher. The heated laminate was then molded into the shape of the automobile ceiling by the vacuum molding method. The molded article obtained has high rigidity and good heat insulation. The shape of this molded article is shown in FIG.

Example 4

〈Forming into L Channel Structure〉

The laminate of the reinforced PET / foamed PET / reinforced PET structure used in Example 3 was molded by a pressure molding method into a heated mold at 180 ° C. to form an L-channel structure having a curved surface at the corner of the wall without the need for a seam. Made in shape Since the obtained molded article does not have a joint portion on the curved surface, this molded article facilitates the joint operation of assembling the wall materials. The shape of this molded article is shown in FIG.

From the molding results of the above embodiments 3 and 4, if the laminate according to the present invention is adapted to various molding or molding conditions, the laminate may be shaped in various shapes, for example, in a box or bathtub, such as a thermally insulating container. It can be easily molded into a predetermined molded article having various shapes.

Example 5

〈Polymerization of PET by Melt Dough〉

The fiber reinforced thermoplastic polyester used was prepared as follows. 68.8 wt% of PET (high viscosity = 0.6 dl / g), 0.5 wt% of PMDA, 30 wt% of finely ground glass fiber (length: 3 mm, trade name: CS-3J-941, manufactured by Nito Boseki Co., Ltd.) and talc 0.7 wt% of LMP-100, manufactured by Fuji Talc Co., Ltd. (as nucleating agent) was melt-dispersed-dough (temperature 285 ° C., residence time 240 seconds) using the same twin screw extruder as used in Example 1. The mixture was extruded from the die in strand form. The extruded strands were cooled in water and then pelletized with a strand cutter to obtain pellets. It was 0.71 dl / g when the intrinsic viscosity of the obtained pellet was measured. The obtained pellets were dried at 160 ° C. under reduced pressure for 6 hours, and then extruded in the same manner as in Example 1 to obtain reinforced PET having a width of 1 m and a thickness of 3 mm.

The foamed thermoplastic polyesters used were prepared as follows. 98.4% by weight PET (high viscosity = 0.6 dl / g), 0.6% by weight PMDA and 1% by weight of talc (trade name: LMP-100, manufactured by Fuji Talc) (as nucleating agent) Melt-dispersion-dough (temperature 285 degreeC, residence time 300 second) was carried out with the screw screw extruder, and the obtained mixture was extruded from die | dye in strand shape. The extruded strands were cooled in water and then pelletized with a strand cutter to obtain pellets. When the intrinsic viscosity of the obtained pellets was measured, it was 0.75 dl / g. The resulting pellets were dried at 160 ° C. under reduced pressure for 6 hours, and then foamed-extruded-molded in the same manner as in Example 1 to obtain expanded PET having a swelling rate of 5 times, a width of 1 m, and a thickness of 3 mm.

A laminate of the reinforced PET / foamed PET / reinforced PET structures was obtained by the same process as in Example 1, except that the reinforcement PET and the foamed PET were changed to those obtained by the above method including a melting reaction. This laminate was evaluated in the same manner as in Example 1. These results are shown in Table 2.

Example 6

<Unused polycarboxylic anhydride>

The fiber reinforced thermoplastic polyester used was prepared as follows. PET (high viscosity = 0.6dl / g) 69.3% by weight, finely ground glass fiber (length: 3mm, brand name: CS-3J-941, manufactured by Nito Boseki Co.) 30% by weight and talc (trade name: LMP-100, Fuji) 0.7 wt% of Talc Co., Ltd. (as nucleating agent) was melt-dispersed-kneaded (temperature 270 DEG C, residence time of 25 seconds) using the same twin screw extruder as used in Example 1, and the resulting mixture was stranded. Extruded from the die. The extruded strands were cooled in water and then pelletized with a strand cutter to obtain pellets. The obtained pellets were charged to the same tumbler rotary reactor as used in Example 1, and the reaction was carried out under a reactor condition of a rotational speed of 10 rpm, a temperature of 220 ° C., a pressure of 1 Torr (133 Pa), and a solid state addition of 10 hours for the pellets. Intrinsic viscosity was increased to 0.70 dl / g. The obtained pellets were dried at 160 ° C. under reduced pressure for 6 hours, and then extruded in the same manner as in Example 1 to obtain reinforced PET having a width of 1 m and a thickness of 3 mm.

The foamed thermoplastic polyesters used were prepared as follows. 99% by weight of PET (high viscosity = 0.6 dl / g) and 1% by weight of talc (trade name: LMP-100, manufactured by Fuji Talc) (as nucleating agent) were melted with the same twin screw extruder used in Example 1. Dispersion-dough (temperature 270 ° C., residence time 25 sec) and the resulting mixture was extruded from the die in the form of strands. The extruded strands were cooled in water and then pelletized with a strand cutter to obtain pellets. The obtained pellets were charged into the same tumbler rotary reactor as used in Example 1, and the reaction was carried out under a reactor condition of a rotational speed of 10 rpm, a temperature of 220 ° C., a pressure of 1 Torr (133 Pa), and a solid state addition of 12 hours for the intrinsic properties of the pellets. The viscosity was increased to 0.75 dl / g. The obtained pellets were dried at 160 ° C. under reduced pressure for 6 hours, and then foamed-extruded-molded in the same manner as in Example 1 to obtain expanded PET having a expansion ratio of 4 times, a width of 1 m, and a thickness of 3 mm.

A laminate of the reinforced PET / foamed PET / reinforced PET structure was obtained by the same process as in Example 1 except that the reinforced PET and foamed PET were changed to those obtained by the above method. This laminate was evaluated in the same manner as in Example 1. These results are shown in Table 2.

Example 7

〈Use of Waste PET Bottle〉

The fiber reinforced thermoplastic polyester used was prepared as follows. Recycled PET flakes (high viscosity = 0.64dl / g) (obtained by crushing waste PET bottles) 69.05% by weight, 0.25% by weight PMDA, finely ground glass fiber (length: 3mm, trade name: CS-3J-941 30 wt% of Nito Boseki Co., Ltd. and 0.7 wt% of talc (trade name: LMP-100, manufactured by Fuji Talc Co., Ltd.) (as nucleating agent) were melt-dispersed with the same twin screw extruder as used in Example 1. The dough (temperature 270 DEG C, residence time 30 seconds) was extruded from the die in the form of strands. The extruded strands were cooled in water and then pelletized with a strand cutter to obtain pellets. The obtained pellets were charged into the same tumbler rotary reactor as used in Example 1, and the reaction was carried out under a reactor condition of a rotational speed of 10 rpm, a temperature of 220 ° C., a pressure of 1 Torr (133 Pa), and solid state addition of 6 hours for the pellets. Intrinsic viscosity was increased to 0.78 dl / g. The obtained pellets were dried at 160 ° C. under reduced pressure for 6 hours, and then extruded in the same manner as in Example 1 to obtain reinforced PET having a width of 1 m and a thickness of 3 mm. By the way, the recycled PET flakes mentioned above may be referred to as "post-consumer scrap PET".

The foamed thermoplastic polyesters used were prepared as follows. Recycled PET flakes (high viscosity = 0.64 dl / g) (obtained by crushing waste PET bottles), 98.52 wt% PMDA 0.49 wt% and talc (trade name: LMP-100, manufactured by Fuji Talc) (nucleating agent) 0.99% by weight was melt-dispersed-dough (temperature 270 ° C., residence time 27 seconds) using the same twin screw extruder as used in Example 1, and the resulting mixture was extruded from the die in strand form. The extruded strands were cooled in water and then pelletized with a strand cutter to obtain pellets. The obtained pellet was charged into the same tumbler rotary reactor as used in Example 1, and the reaction was carried out under a reactor condition of a rotational speed of 10 rpm, a temperature of 220 ° C., a pressure of 1 Torr (133 Pa), and a solid state addition of 10 hours for the intrinsic properties of the pellet. The viscosity was increased to 0.91 dl / g. The obtained pellets were dried at 160 ° C. under reduced pressure for 6 hours, and then foamed-extruded-molded in the same manner as in Example 1 to obtain expanded PET having an expansion ratio of 10 times, a width of 1m, and a thickness of 3mm.

A laminate of the reinforced PET / foamed PET / reinforced PET structure was obtained by the same process as in Example 1 except that the reinforced PET and foamed PET were changed to those obtained by the above method. This laminate was evaluated in the same manner as in Example 1. These results are shown in Table 2. By the way, this process involving the use of PET material such as obtained by polymerizing recycled PET (such as recycled PET flakes) is one of the more preferred embodiments of the processes for producing laminates of the present invention.

Example 5 Example 6 Example 7 Laminate structure Reinforced PET / Foamed PET / Reinforced PET Reinforced PET / Foamed PET / Reinforced PET Reinforced PET / Foamed PET / Reinforced PET Adhesive Classification at disposal Recyclability

Example 8

〈PET film laminate〉

The laminate of the reinforced PET / foamed PET / PET film structure (the surface of the PET film is the outermost layer) was obtained in the same manner as in Example 2 except that the PET nonwoven fabric was changed to a non-foamed PET film.

The obtained laminate had good adhesiveness, and also good sortability and recyclability upon disposal.

Example 9

〈Formation of Large Laminates〉

The large PET laminate was molded in the following manner.

The extrusion conditions for the reinforced PET sheet and the foamed PET sheet of Example 1 were adjusted to obtain reinforced PET having a width of 1 m and a thickness of 5 mm and foamed PET having a width of 1 m and a thickness of 4 mm and an expansion ratio of 10 times.

Each of the obtained molded articles was cut into a size of 1,000 mm x 3,000 mm, and laminated on each other using a flat mold of 1,030 mm x 3,100 mm under the same conditions as in Example 1, whereby the same structure as in the laminate of Example 1 was obtained. The flat laminated body of 1,000 mm x 3,000 mm which has is obtained.

The obtained laminate can be used as a building material for a house, that is, a thermal insulation material or a partition wall by cutting to a predetermined size. Moreover, this laminated body has the outstanding heat insulation effect.

Therefore, large laminates can also be easily produced by devising extrusion conditions and molding conditions for PET sheets. In addition, the thickness of each layer can also be adjusted with a predetermined strength.

Example 10

〈Forming of Large Laminates with Patterns〉

A laminate was obtained in the same manner as in Example 9 except that the plate mold was replaced with a plate mold heated to 180 ° C. having a wave pattern.

It has been found that the resulting laminate can be set on a floor or ground, for example, and can be used as a flooring material having effects such as an anti-slip effect.

Example 11

〈Use of PET Industry Waste〉

The fiber reinforced thermoplastic polyester used was prepared as follows. Crushed product called industrial waste (high viscosity = 0.5-0.65dl / g) (including waste from PET film and / or PET moldings) 69.05% by weight, 0.25% by weight PMDA, finely ground glass fiber (length: 3mm , Trade name: CS-3J-941, manufactured by Nito Boseki Co., Ltd.) and 0.7 wt% of talc (trade name: LMP-100, manufactured by Fuji Talc Co., Ltd.) (as nucleating agent) Melt-dispersion-dough (temperature 270 degreeC, residence time 30 second) was carried out with the screw screw extruder, and the obtained mixture was extruded from die | dye in strand shape. The extruded strands were cooled in water and then pelletized with a strand cutter to obtain pellets. The obtained pellet was charged into the same tumbler rotary reactor as used in Example 1, and the reaction was carried out under a reactor condition of a rotational speed of 10 rpm, a temperature of 220 ° C., a pressure of 1 Torr (133 Pa), and a solid state addition of 10 hours for the intrinsic properties of the pellet. The viscosity was increased to 0.8-0.85 dl / g. The obtained pellets were dried at 160 ° C. under reduced pressure for 6 hours, and then extruded in the same manner as in Example 1 to obtain reinforced PET having a width of 1 m and a thickness of 3 mm.

The foamed thermoplastic polyesters used were prepared as follows. Crushed product called industrial waste (high viscosity = 0.5-0.65dl / g) (including waste of PET film and / or PET moldings) 98.52% by weight, 0.49% by weight PMDA and talc (trade name: LMP-100, Fuji) Talc Co., Ltd.) (as nucleating agent) was melt-dispersed-dough (temperature 270 DEG C, residence time 27 seconds) using the same twin screw extruder as used in Example 1, and the resulting mixture was stranded into dies. Extruded from. The extruded strands were cooled in water and then pelletized with a strand cutter to obtain pellets. The obtained pellet was charged into the same tumbler rotary reactor as used in Example 1, and the reaction was carried out under a reactor condition of a rotational speed of 10 rpm, a temperature of 220 ° C., a pressure of 1 Torr (133 Pa), and a solid state addition of 10 hours for the intrinsic properties of the pellet. The viscosity was increased to 0.8-0.85 dl / g. The obtained pellets were dried at 160 ° C. under reduced pressure for 6 hours, and then foamed-extruded-molded in the same manner as in Example 1 to obtain expanded PET having an expansion ratio of 10 times, a width of 1m, and a thickness of 3mm.

A laminate of the reinforced PET / foamed PET / reinforced PET structure was obtained by the same process as in Example 1 except that the reinforced PET and foamed PET were changed to those obtained by the above method. Thus, it has been found that good laminates can be made with the use of PET industrial waste.

Various specifications of the invention may be changed without departing from the spirit of the invention, which is not within the scope of the invention. Furthermore, the above description of more preferred embodiments according to the present invention is provided for the purpose of illustration only and is not intended to limit the invention as defined by the claims and their equivalents.

Because of the inclusion of the foam layer, the thermoplastic polyester laminate according to the present invention has excellent thermal insulation, good sound absorption and is lightweight. In addition, because of the inclusion of the fiber reinforcement layer, the thermoplastic polyester laminate according to the present invention has a high mechanical strength. In addition, the thermoplastic polyester laminate according to the present invention is excellent in heat resistance and chemical resistance. The thermoplastic polyester laminate according to the present invention is excellent in formability and can therefore be used as a component of various products. Therefore, the laminate according to the present invention has sufficient strength, heat insulation and sound absorption as well as light weight, and this laminate is particularly suitable for large-scale molded articles. Moreover, this laminate has good recyclability.

Claims (14)

A thermoplastic polyester laminate comprising a laminated structure AB comprising a thermoplastic polyester fiber reinforcement layer A and a thermoplastic polyester foam layer B, wherein the fiber reinforcement layer A and the foam layer B are laminated to each other. The thermoplastic polyester laminate according to claim 1, wherein only one laminated structure AB is included in the thermoplastic polyester laminate and another thermoplastic polyester fiber reinforcement layer A is laminated on the opposite side of the foam layer B. The thermoplastic polyester laminate of claim 1, wherein the thermoplastic polyester melt-kneaded the mixture comprising the thermoplastic polyester and the polycarboxylic anhydride to effect a chain extension reaction. . 4. The thermoplastic polyester laminate of claim 3, further comprising the step of further promoting the chain extension reaction by carrying out the solid state polyaddition reaction of the melt kneaded mixture after the melt kneading step and the kneading step. sieve. The thermoplastic polyester laminate according to claim 1, wherein the fibers in the fiber reinforcement layer A are glass fibers. The method of claim 1, wherein at least 50 mol% of the acid component used to prepare the thermoplastic polyester of the fiber reinforced layer A is equal to at least 50 mol% of the acid component used to make the thermoplastic polyester of the foam layer B. And at least 50 mol% of the glycol component used to make the thermoplastic polyester of the fiber reinforcement layer A is at least 50 mol% of the glycol component used to make the thermoplastic polyester of the foam layer B. sieve. The thermoplastic polyester laminate of claim 1, wherein the thermoplastic polyester is polyethylene terephthalate (PET). An article comprising the thermoplastic polyester laminate of claim 1. 3. The thermoplastic polyester laminate of claim 2, wherein the thermoplastic polyester comprises kneading a mixture comprising the thermoplastic polyester and the polycarboxylic anhydride to effect a chain extension reaction. . 10. The thermoplastic polyester laminate according to claim 9, wherein the thermoplastic polyester further comprises the step of carrying out a solid state addition reaction of the melt kneaded mixture after the melt kneading step and the melt kneading step to further promote the chain extension reaction. sieve. The thermoplastic polyester laminate according to claim 2, wherein the fibers in the fiber reinforcement layer A are glass fibers. The method of claim 2, wherein at least 50 mol% of the acid component used to prepare the thermoplastic polyester of the fiber reinforced layer A is equal to at least 50 mol% of the acid component used to prepare the thermoplastic polyester of the foam layer B. And at least 50 mol% of the glycol component used to make the thermoplastic polyester of the fiber reinforcement layer A is at least 50 mol% of the glycol component used to make the thermoplastic polyester of the foam layer B. sieve. The thermoplastic polyester laminate of claim 2, wherein the thermoplastic polyester is polyethylene terephthalate (PET). An article comprising the thermoplastic polyester laminate of claim 2.