JP2003103521A - Extruded molding and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a method for recycling a resin component by separating a foam and a nonwoven fabric or a woven fabric for a waste material of a ceiling material of an automobile including the foam of a modified polyphenylene ether resin and the nonwoven fabric or the woven fabric and/or an end material generated at the time of molding. SOLUTION: An extruded molding using the resin component as a raw material is obtained by comminuting the waste material of the ceiling material of the automobile including the foam of the modified polyphenylene ether resin and the nonwoven fabric or the woven fabric and/or the end material generated at the time of molding, and then separating the nonwoven fabric or the woven fabric by a sieve and/or a gravity separation and hence recycled.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the recycling of automobile ceiling materials, and more particularly to a market-aged automobile waste ceiling material containing a foamed polyphenylene ether resin and a nonwoven fabric or a woven fabric, or a manufacturing process. Scrap generated at
The present invention relates to a technique for reusing an extruded product that uses a resin component obtained by separating a non-woven fabric or a woven fabric from a waste ceiling material as a raw material.

[0002]

2. Description of the Related Art The conventional treatment of a ceiling material for an abandoned automobile has been incinerated or landfilled as it is or after crushing. However, incineration requires the use of a furnace that can handle dioxin in the exhaust gas and dioxin, and the incineration cost has become higher than before. Due to environmental problems, landfill sites are limited and landfill disposal costs have started to rise. From the viewpoint of environmental friendliness, material recycling of waste ceiling materials is desired.

A ceiling material using a heat-resistant modified polyphenylene ether (modified PPE) -based foam and a non-woven fabric or a woven fabric has been widely used because of its light weight, which leads to improvement of fuel efficiency of automobiles. It is required to recycle the abandoned ceiling materials of automobiles that have aged in the market, or the scrap materials and waste ceiling materials generated in the manufacturing process.

Ceiling materials using a modified polyphenylene ether foam and a nonwoven fabric are known in JP-A-5-124054, JP-A-9-029875 and JP-A-9-029877, but regarding recycling, JP-A-2001-7984.
2 is known. This Japanese Patent Application Laid-Open No. 2001-79842 describes that after crushing an automobile interior material composed of a PPE foam and a non-woven fabric, the two are pelletized without being separated from each other. However, the non-woven fabric and the PPE are not separated from each other. When a resin containing a series resin is used to form a film or a sheet, a molded product is easily broken, which results in a drawback that the strength is extremely weak.

[0005]

In view of such a situation, the present invention is a waste ceiling material for aged vehicles, or a manufacturing process, containing a modified polyphenylene ether resin foam and a non-woven fabric or a woven fabric. It is to contribute to the effective use of resources by realizing a material recycling method and its recycled products, not by incineration or landfilling, using the generated scraps and waste ceiling materials.

[0006]

That is, the present invention uses (1) as a raw material a resin component obtained by separating a non-woven fabric or a woven fabric from an automobile ceiling material including a foam of a modified polyphenylene ether resin and a non-woven fabric or a woven fabric. Extruded product. (Claim 1) (2) The extrusion molded article according to (1), wherein a resin component obtained by crushing an automobile ceiling material and then separating a non-woven fabric or a woven fabric by sieving and / or specific gravity separation is used as a raw material. (Claim 2) (3) An extruded product according to (1) or (2), which is obtained by adding a polystyrene resin or a modified polyphenylene ether resin to a resin component obtained by separating a nonwoven fabric or a woven fabric from an automobile ceiling material and extruding the resin component. . (Claim 3) (4) Automotive ceiling material market Abandoned automotive ceiling material,
Alternatively, the extruded product according to any one of (1) to (3), which is a scrap material generated in a manufacturing process or a waste ceiling material. (Claim 4) (5) The modified polyphenylene ether resin foam comprises a polyphenylene ether resin and a polystyrene resin, (1) to (4)
Extruded product described. (Claim 5) (6) The extrusion-molded article according to any one of (1) to (5), wherein the nonwoven fabric made of polyethylene terephthalate is separated. (Claim 6)

(7) After crushing an automobile ceiling material containing a modified polyphenylene ether resin foam and a non-woven fabric or a woven fabric, extrusion molding using a resin component obtained by separating the non-woven fabric or the woven fabric by sieving and / or specific gravity separation as a raw material Will be done (1) ~
(6) The method for producing an extruded product according to any one of (6).
(Claim 7)

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the polyphenylene ether resin (PPE resin) of the present invention include poly (2,2)
6-dimethylphenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-1,4-ether), poly (2,6-diethylphenylene-1,4-ether), poly (2, 6-diethylphenylene-1,
4-ether), poly (2-methyl-6-n-propylphenylene-1,4-ether), poly (2-methyl-)
6-n-butylphenylene-1,4-ether), poly (2-methyl-6-chlorophenylene-1,4-ether), poly (2-methyl-6-bromophenylene-1,
4-ether), poly (2-ethyl-6-chlorophenylene-1,4-ether) and the like.

These may be used alone or in combination of two or more. Of these, poly (2,
6-Dimethylphenylene-1,4-ether) is preferable from the viewpoint of versatility of raw materials and cost. Further, when it is desired to impart flame retardancy, poly (2-methyl-6-chlorophenylene-1,4-ether) and poly (2-methyl-6-bromophenylene-1,4-ether) containing a halogen element are included. ), Poly (2-ethyl-6-chlorophenylene-
1,4-ether) and the like are exemplified.

In order to form a foam of a polyphenylene ether resin, it is preferable to use a modified polyphenylene ether resin to which a polystyrene resin (PS resin) is added in view of workability. The PS resin is styrene or a derivative thereof, such as α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, dichlorostyrene,
Main component (60 p-methylstyrene, ethylstyrene, etc.
And more than 70% by weight). Therefore, the PS resin is not limited to a homopolymer consisting of styrene or a styrene derivative, but may be a copolymer produced by copolymerizing with another monomer.

Further, for example, high-impact polystyrene such as styrene or a styrene derivative, which is obtained by adding a synthetic rubber or rubber latex, may be used.

Other monomers copolymerizable with styrene or a derivative thereof that can be used in the production of the PS resin include, for example, acrylonitrile, methacrylonitrile,
Examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, or carboxyl group-containing monomers such as maleic anhydride, itaconic acid, acrylic acid, and methacrylic acid, which may be used alone or in combination. These are used in combination.

Specific examples of the PS resin include polystyrene, styrene-α-methylstyrene copolymer, styrene / butadiene copolymer represented by high-impact polystyrene, and styrene / acrylonitrile / butadiene copolymer. And so on. Examples of PS resins having higher heat resistance include copolymers of styrene and a monomer containing a carboxyl group, such as styrene-maleic anhydride copolymer and styrene-itaconic acid copolymer.

When producing a foam of a polyphenylene ether resin (PPE resin), a modified PPE prepared by mixing a PS resin with the PPE resin is used, or P
Modified PPE resin obtained by graft-polymerizing styrene or its derivative on PE resin is used, or modified PPE obtained by graft-polymerizing styrene or its derivative on PPE resin
You may use the modified PPE which added PS type resin to PE type resin. In modified PPE, PPE resin and P
The compounding ratio with the S-based resin is 25-95 to 75-5, and the workability is
It is preferable in terms of heat resistance.

As a method for producing the modified PPE resin foam used in the present invention, a thermal decomposition type foaming agent can be used, and a copolymer resin of PPE and styrene or a PPE resin and PS. System resin and mixed resin, and resin with various additives added are melted and kneaded by an extruder,
A method is suitable in which a foaming agent is press-fitted under high temperature and high pressure, adjusted to an optimum foaming temperature, extruded into a low pressure zone (usually in the atmosphere), and then molded into a sheet by a mandrel or the like.

Examples of the foaming agent used in the production of the modified PPE resin foam sheet include hydrocarbons such as butane, propane, pentane, methyl chloride, dichloromethane, chlorofluoromethane, dichloroethane, dichlorodifluoroethane, and halogenated hydrocarbons. Etc., and may be used in combination.

As a method for producing an automobile ceiling material used in the present invention, for example, a foam laminated sheet obtained by laminating a non-foam resin layer on both sides or one side of a foam sheet using a modified PPE resin as a base resin. After hot-pressing a hot-melt adhesive film on top of it, overlay a non-woven fabric or woven fabric on it to temporarily fix it, put it in a heating furnace and heat it, then mold it with a mold to form an automobile. It is preferable to manufacture a ceiling material for use.

As the non-foamed layer base resin laminated on the modified PPE resin foam, PS resin, modified PPE resin,
Polypropylene (PP) resin, polyethylene (P
E) -based resins, polyamide (nylon) -based resins and the like may be used, and these may be used alone or in combination of two or more, and PS-based and modified PPE-based resins are preferable because of their adhesiveness to the modified PPE-based resin foam layer. is there.

Examples of PS resins include polystyrene, high-impact polystyrene, styrene-α-methylstyrene copolymer, α-methylstyrene-acrylonitrile copolymer, styrene-α-methylstyrene-acrylonitrile copolymer, and styrene-maleic anhydride. Examples thereof include acid copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-itaconic acid copolymers, and blends with polymers such as polycarbonates. In particular, modified PPE-based resin or PS-based resin is preferable because it is easy to manufacture. In order to further improve the brittleness of the non-foamed layer, a styrene-butadiene block copolymer, a styrene-butadiene-styrene block copolymer, a styrene-isoprene block copolymer, a styrene-isoprene-styrene block copolymer, or You may add the said hydrogenated block copolymer etc.

As the hot melt adhesive, olefin type, modified olefin type, polyurethane type, ethylene-vinyl acetate copolymer resin type, polyamide type, polyester type, thermoplastic rubber type, styrene-butane copolymer, styrene-isoprene are used. Examples thereof include those containing a copolymer resin as a component, and these may be used alone or in combination of two or more kinds.

As the non-woven fabric or woven fabric of the present invention, polyester, polypropylene, polyethylene, polyacrylonitrile, polyamide, modacrylic (Kanecaron, a product name of Kanebuchi Chemical Industry Co., Ltd.), synthetic fibers such as polyvinyl chloride, wool, cotton, etc. Can be used, and they may be used in combination. Especially cost,
A polyester non-woven fabric is preferable because of its texture.

The polyester fiber used in the nonwoven fabric or woven fabric of the present invention is a polyester fiber obtained by polycondensing a divalent or higher valent aromatic carboxylic acid component and a divalent or higher valent alcohol component by a known method. used. Specific examples of the polyester fibers include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, but especially polyethylene terephthalate fibers. Is preferred.

[0023] A non-woven fabric or a woven fabric is produced from aged ceiling materials of automobiles that contain the foamed product of the polyphenylene ether resin of the present invention and a non-woven fabric or a woven fabric, or scraps and waste ceiling materials generated in the manufacturing process. As a method for separating, it is possible to heat the waste ceiling material to, for example, 100 ° C. and immediately manually peel off the non-woven fabric or the woven cloth, but from the viewpoint of productivity, the ceiling material is crushed, especially after impact crushing, and then sieving with a sieve. Separate the fiber part,
Alternatively, it is preferable to separate the fiber portion with a specific gravity separator after impact grinding. In order to increase the separation accuracy, it is also possible to perform the sieving process by reducing the diameter of the screen of the impact crusher again after the impact crushing and reducing the mesh opening of the sieve after the crushing. Similarly, after impact crushing, it is also possible to reduce the specific gravity of the material that has been separated by specific gravity again by reducing the diameter of the screen of the impact crusher. After impact crushing, it is also possible to reduce the diameter of the screen of the impact crusher for the pass product of the sieve again, and separate the specific gravity after crushing.

The film or sheet can be directly extruded from the above-mentioned separated product, or can be produced by calendering or pressing. However, it is preferable to pelletize the separated product after extruding it because of stable quality.

When pelletizing the above-mentioned separated product, uniaxial,
It is preferable to use a twin-screw extruder, and it is preferable to remove a fiber component in the resin by inserting a screen mesh into a die of the extruder at a temperature at which the contained fiber does not melt. The pellet temperature is preferably 200 to 250 ° C.

In pelletizing the separated product, a polystyrene resin or a modified polyphenylene ether resin may be added and extruded.

It is also possible to independently pelletize the above-mentioned separated product and then extrude it to produce a film or sheet molded product. However, due to the physical properties of the molded product, the separated product is individually pelletized and then formed into pellets. , After blending polystyrene resin or modified polyphenylene ether resin,
When extruding, producing a film or sheet, or pelletizing the separated product, it is preferable to produce a film or sheet by using a pellet to which a polystyrene resin or a modified polyphenylene ether resin is added.

Further, as the extruded product of the present invention, it is preferable to form a film or a sheet, the content of polyphenylene ether in the product is 25 to 75% by weight, and the polystyrene resin is 75 to 25%. %, And it is particularly preferable to use high-impact styrene as the polystyrene resin from the physical properties of the film and sheet.

Further, the extruded resin of the present invention may have any other thermoplasticity within the range not impairing the present invention, such as polyolefin resin, polyamide resin, polyalkyl (meth) acrylate resin, polyphenylmaleimide resin. A resin, a polyphenylene sulfide resin, a polyacetal resin, a polysulfone resin, a rubber-like elastic body, a graft-modified rubber-like elastic body, or the like may be added alone or in combination of two or more.

In order to improve the performance of the extrusion molding resin composition of the present invention, a phenolic antioxidant,
It is preferable to use antioxidants such as thioether-based antioxidants, heat stabilizers such as phosphorus-based stabilizers, etc., alone or in combination of two or more.

Furthermore, if desired, it is usually well known that
Inorganic filler, stabilizer, lubricant, release agent, plasticizer, flame retardant,
Additives such as flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes, antistatic agents, conductivity enhancers, dispersants, compatibilizers, antibacterial agents, etc., alone or in combination of two or more. You can

The extruded product is specifically used as an interior material of an automobile, such as a door panel, a door trim, a front panel, a part of an automobile ceiling material, for example, a non-foamed layer of an automobile ceiling material, or an automobile trunk room. It is possible to use it for the board etc.

[0033]

EXAMPLES Examples will be shown below, but the present invention is not limited thereto. (Manufacture of ceiling material) (A) Iso-butane as a main component with respect to 100 parts by weight of a mixed resin obtained by mixing a PPE resin and a PS resin so that the PPE resin component is 40% by weight and the PS resin component is 60% by weight. 3 parts by weight of a foaming agent (iso / n = 85/15) and 0.32 parts by weight of talc were kneaded by an extruder at 290 ° C.,
The resin temperature was cooled to 198 ° C and extruded with a circular die, thickness 2.6 mm, foaming ratio 11 times, basis weight 24
A foamed sheet of 0 g / m ² was obtained. The foamed sheet thus obtained was wound into a roll.

The foamed sheet thus obtained was fed out, and the PPE resin, the HIPS resin and the impact resistance improver (Toughprene # 125: 30% by weight of PPE resin component, 64% by weight of PS resin component and 6% by weight of rubber component) were added. A resin obtained by mixing a styrene-butadiene-styrene block copolymer (manufactured by Asahi Kasei) is melted and kneaded, and the resin temperature is 278 ° C. using a T-die.
Then, a non-foamed layer having a thickness of 120 μm was laminated on one side of the extruded foamed sheet, and the obtained laminated sheet was wound into a roll. Next, pay out a laminated sheet having a non-foamed layer laminated on one side,
In the same manner on the other side, 30% by weight of PPE resin component, P
The S resin component was changed to a resin component of 70% by weight, a non-foaming layer having a thickness of 120 μ was laminated, and a laminated sheet having non-foaming properties laminated on both sides was wound into a roll.

Next, the foamed laminated sheet obtained was fed out, and 30% by weight of the PPE resin component of the foamed laminated sheet and PS
A film of 30 μm thick acid-modified polyolefin-based hot melt adhesive (Hirodyne # 7586, manufactured by Hirodyne) is formed on the surface of 70% by weight of the resin component at 120 ° C.
It was thermocompression bonded. Next, a skin material made of a polyester non-woven fabric (240 g / m ² ) was placed on the hot melt adhesive film and temporarily fixed. Next, the laminated foam sheet with the skin material temporarily clamped is clamped on four sides and placed in a heating furnace to heat up to a surface temperature of 145 ° C, and plug molding is performed with a mold whose temperature is controlled to 60 ° C, followed by trimming and punching. Then, an automobile ceiling material was obtained.

(B) In the same manner as in (A) above, the PPE resin, the HIPS resin, and the impact resistance improver (Toughprene # 125: styrene-
Butadiene-styrene block copolymer (Asahi Kasei)
After laminating a non-foaming layer made of a resin mixed with the above, a non-foaming layer made of a HIPS resin having a butadiene rubber component of 12% by weight is laminated on the opposite side with the same thickness, and a non-foaming layer is laminated on both sides to form a laminated sheet. It was rolled up.

Then, in the same manner as in (A), the obtained foamed laminated sheet was unwound, and the same acid-modified polyolefin hot melt adhesive film as in (A) was thermocompression-bonded to the modified PPE resin side. An automobile ceiling material was obtained in the same manner as in (A) by overlaying skin materials made of non-woven fabric. (Separation step) After crushing the end material of the automobile ceiling material of (A) or (B) with a shearing type crusher equipped with a 10φ screen, the non-woven fabric is removed with a 10 mm open sieve to obtain a pass product. After crushing with an impact crusher equipped with a 5φ screen, the non-woven fabric was separated with a 5 mm open sieve, and the non-woven fabric was further removed with a specific gravity separator to obtain a resin part. (Pelletization) 0.2 parts by weight of phenolic antioxidant AO-20 (manufactured by Asahi Denka Co., Ltd.) and 0.2 parts of phosphite antioxidant PEP-24G (manufactured by Asahi Denka Co., Ltd.) in 100 parts by weight of the above resin part.
Was added and extruded at 240 ° C. using a vented 40 mm extruder having a 60-mesh screen attached to the die to obtain pellets a or pellets b. (Production of Film) (Example 1) 40% by weight of high-impact polystyrene containing 12% of butadiene rubber was added to and mixed with 60% by weight of the above pellet a, and the mixture was used at 120 ° C. at 120 ° C. using a T-die.
When a μ film was extruded, a uniform film was obtained, and there was almost no polyester fiber layer. (Example 2) 40% by weight of high-impact polystyrene containing 12% of butadiene rubber was added to and mixed with 60% by weight of the pellet b, and a T film was used in the same manner as in Example 1 to form a film having a thickness of 120 μ at 260 ° C. When was extruded, a uniform film was obtained and there was almost no polyester fiber layer. (Comparative Example 1) The scrap material of the above-mentioned (A) automobile ceiling material was 5φ.
After crushing with a shearing type crusher with a screen, remove the 60 mesh screen on the die without separating and
Extruded at 240 ° C. using an m extruder and pelletized. To 60% by weight of the pellets, 40% by weight of high-impact polystyrene containing 12% of butadiene rubber was added and mixed, and the mixture was mixed with T-die at 260 ° C. in the same manner as in Example 1.
When a 20 μ film was extruded, a film having a striped pattern with a large thickness unevenness was obtained. When the thickness was adjusted, the film was partially torn and a uniform film could not be collected.

Industrial Applicability It is industrially superior to use a resin component obtained by separating a non-woven fabric or a woven fabric from an automobile ceiling material containing a modified polyphenylene ether resin foam and a non-woven fabric or a woven fabric as a raw material for extrusion molding. Since it is a recycling method and the strength of the obtained molded product is good, it can be used for various purposes such as automobile applications.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 5/00 C08J 5/00 4J002 C08L 25/04 C08L 25/04 71/12 71/12 // B29K 25:00 B29K 25:00 67:00 67:00 71:00 71:00 F-term (reference) 3D023 BA01 BB02 BD01 BE02 4D021 EA10 EB01 JA05 NA02 4F071 AA22 AA51 AD06 AH03 AH04 AH11 BA01 BB06 BC01 4F207 AA13 AA32J AA50 KA01 KA17 4A301 AB01 AD02 BD29 BF05 BF09 BF12 4J002 BC02X CH05W GN00

Claims (7)

[Claims] 1. An extruded product using as a raw material a resin component obtained by separating a non-woven fabric or a woven fabric from an automobile ceiling material containing a modified polyphenylene ether resin foam and a non-woven fabric or a woven fabric. 2. The extruded product according to claim 1, wherein a resin component obtained by crushing an automobile ceiling material and then separating a non-woven fabric or a woven fabric by sieving and / or specific gravity separation is used as a raw material. 3. A polystyrene resin or a modified polyphenylene ether resin is added to a resin component obtained by separating a non-woven fabric or a woven fabric from an automobile ceiling material and extruded.
Alternatively, the extruded product according to item 2. 4. The extrusion according to any one of claims 1 to 3, wherein the automobile ceiling material is a waste ceiling material of an aged vehicle on the market, a scrap material generated in a manufacturing process, or a waste ceiling material. Molding. 5. The extrusion-molded article according to claim 1, wherein the foamed material of the modified polyphenylene ether resin is composed of a polyphenylene ether resin and a polystyrene resin. 6. The extruded product according to claim 1, wherein the non-woven fabric made of polyethylene terephthalate is separated. 7. An automobile ceiling material containing a foam of a modified polyphenylene ether resin and a non-woven fabric or a woven fabric is crushed and then extruded using a resin component obtained by separating the non-woven fabric or the woven fabric by sieving and / or specific gravity separation as a raw material. The method for producing an extruded product according to claim 1, wherein