JP2005240031A - Modified polyphenylene ether-based resin foam sheet, substrate for car interior material and car interior material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified polyphenylene ether-based resin foam sheet excellent in environmental sanitation, especially, suitably usable in applications of car interior materials. <P>SOLUTION: The modified polyphenylene ether-based resin foam sheet is obtained by supplying modified polyphenylene ether-based resin to an extruder, melt-kneading and extruding from the extruder to foam, wherein toluene content in the modified polyphenylene ether-based resin foam sheet is ≤100 ppm based on the total weight of the modified polyphenylene ether-based resin foam sheet. The resin foam sheet can keep the environment good in curing, storage or use. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a modified polyphenylene ether-based resin foam sheet excellent in environmental hygiene, and a vehicle interior material and an automotive interior material using the modified polyphenylene ether-based resin foam sheet.

  Conventionally, various automobile interior materials have been proposed. As a sheet applied to such an automobile interior material, for example, Patent Document 1 discloses modified polyphenylene ether resin films on both sides of a modified polyphenylene ether resin foam sheet. A laminated sheet for automobile interior materials suitable for thermoforming formed by lamination has been proposed.

  On the other hand, environmental hygiene problems such as sick house problems in living spaces have recently occurred, which are said to be caused by volatile organic compounds contained in building materials, etc. Is required. And since the inside of a motor vehicle is also a closed space like a living space, reduction of the volatile organic compound contained in a motor vehicle interior material is also calculated | required.

Japanese Patent No. 2905037

  The present invention is excellent in environmental hygiene, and in particular, a modified polyphenylene ether-based resin foam sheet suitably used for automotive interior materials, and a base material for automotive interior materials using the modified polyphenylene ether-based resin foam sheet and Providing automotive interior materials.

  The modified polyphenylene ether-based resin constituting the modified polyphenylene ether-based resin foam sheet of the present invention is not particularly limited, and is a mixture of polyphenylene ether and polystyrene resin represented by the following chemical formula 1; Modified polyphenylene ether obtained by graft copolymerization, a mixture of this modified polyphenylene ether and polystyrene resin, and the presence of a catalyst such as an amine complex of copper (II) with a phenol monomer and a styrene monomer represented by the following chemical formula 2 Examples thereof include a block copolymer obtained by oxidative polymerization under the above, a mixture of this block copolymer and a polystyrene resin, and the like. The modified polyphenylene ether resin may be used alone or in combination.

（Ｒ₁ 、Ｒ₂ は炭素数が１〜４のアルキル基又はハロゲン原子を示し、ｎは重合度を示す。）

(R ₁ and R ₂ represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n represents the degree of polymerization.)

  Examples of the polyphenylene ether represented by the above chemical formula 1 include poly (2,6-dimethylphenylene-1,4-ether), poly (2,6-diethylphenylene-1,4-ether), poly (2, 6-dichlorophenylene-1,4-ether), poly (2,6-dibromophenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-1,4-ether), poly (2- Chloro-6-methylphenylene-1,4-ether), poly (2-methyl-6-isopropylphenylene-1,4-ether), poly (2,6-di-n-propylphenylene-1,4-ether) ), Poly (2-bromo-6-methylphenylene-1,4-ether), poly (2-chloro-6-bromophenylene-1,4-ether), poly (2-chloro-6-ether) Rufeniren 1,4 ether) and the like, which may be used in combination be used alone, also the degree of polymerization n is usually that of 10 to 5000 is used.

（Ｒ₃ 、Ｒ₄ は炭素数が１〜４のアルキル基又はハロゲン原子を示す。）

(R ₃ and R ₄ represent an alkyl group having 1 to 4 carbon atoms or a halogen atom.)

  Examples of the phenolic monomer represented by the above chemical formula 2 include 2,6-dimethylphenol, 2,6-diethylpheninol, 2,6-dichlorophenol, 2,6-dibromophenol, 2-methyl-6- Ethylphenol, 2-chloro-6-methylphenol, 2-methyl-6-isopropylphenol, 2,6-di-n-propylphenol, 2-bromo-6-methylphenol, 2-chloro-6-bromophenol, Examples thereof include 2-chloro-6-ethylphenol, and these may be used alone or in combination.

  Examples of the polystyrene resin mixed with the polyphenylene ether, the modified polyphenylene ether, or the block copolymer include polystyrene, a copolymer of styrene and a vinyl monomer copolymerizable therewith, and high impact polystyrene. And polystyrene is preferred. In addition, the polystyrene-based resin may be used alone or in combination.

  Examples of the vinyl monomer include methyl methacrylate, acrylonitrile, methacrylonitrile, and butyl acrylate. Moreover, as high impact polystyrene, rubber components such as styrene-butadiene copolymer and styrene-butadiene-styrene block copolymer are added to polystyrene or a copolymer of styrene and a vinyl monomer copolymerizable therewith. The thing formed by adding 1 to 20 weight% is mentioned.

  Examples of the styrene monomer that is graft copolymerized with polyphenylene ether or block copolymerized with a phenol monomer include styrene; α-methylstyrene, 2,4-dimethylstyrene, p-methylstyrene, ethylstyrene, p- Examples thereof include alkylated styrene such as t-butylstyrene; halogenated styrene such as monochlorostyrene and dichlorostyrene.

  The modified polyphenylene ether resin is preferably a modified polyphenylene ether resin in which the phenylene ether component is 15 to 60% by weight and the styrene component is 85 to 40% by weight, and the phenylene ether component is 20 to 60% by weight. A modified polyphenylene ether resin having a styrene component of 80 to 40% by weight is more preferable, and a modified polyphenylene ether resin having a phenylene ether component of 25 to 50% by weight and a styrene component of 75 to 50% by weight is particularly preferable.

  This is because if the amount of the phenylene ether component in the modified polyphenylene ether-based resin is small, the heat resistance of the foamed sheet may be lowered, while if it is large, a good-quality foamed sheet may not be obtained.

  In addition, if the expansion ratio of the modified polyphenylene ether resin foam sheet is small, the heat insulating property of the modified polyphenylene ether resin foam sheet may be lowered. On the other hand, if the expansion ratio is large, the mechanical strength of the modified polyphenylene ether resin foam sheet is reduced. And since moldability may fall, 5 to 25 times is preferable and 7 to 20 times is more preferable. The expansion ratio of the modified polyphenylene ether-based resin foam sheet refers to a value obtained by dividing the specific gravity of the synthetic resin constituting the modified polyphenylene ether-based resin foam sheet by the specific gravity of the modified polyphenylene ether-based resin foam sheet.

  And if the open cell ratio of the whole modified polyphenylene ether-based resin foamed sheet is large, the moldability of the modified polyphenylene ether-based resin foamed sheet may be lowered, so 25% or less is preferable. The open cell ratio of the modified polyphenylene ether-based resin foam sheet refers to that measured in accordance with ASTM D2856-87. Specifically, a plurality of planar square sheet-like test pieces each having a side of 25 mm are cut out from the modified polyphenylene ether-based resin foam sheet over the entire length in the thickness direction of the foam sheet. The laminated body is formed by superposing the whole thickness in the thickness direction so as to be about 25 mm.

Next, after accurately measuring the apparent volume of the laminate using a caliper, the volume is measured by the 1-1 / 2-1 atmospheric pressure method using an air-comparing hydrometer, and the open cell ratio is calculated by the following formula: Is calculated. In addition, the volume of the laminated body by the 1-1 / 2-1 atmospheric pressure method is measured using the air comparison type hydrometer which is marketed with the brand name "air comparison type hydrometer 1000 type | mold" from Tokyo Science, for example. be able to.
Open cell ratio (%) = 100 × (apparent volume−volume of laminate by air comparison type hydrometer) / apparent volume

  Further, if the average cell diameter of the modified polyphenylene ether-based resin foam sheet is small, the foam sheet may become soft and the mechanical strength may be reduced. On the other hand, if the average cell diameter is large, the surface smoothness of the foam sheet may be reduced or brittle. Therefore, 0.2 to 0.9 mm is preferable, and 0.3 to 0.8 mm is more preferable. The average cell diameter of the modified polyphenylene ether-based resin foam sheet refers to that measured according to the test method of ASTM D2842-69.

If the density of the modified polyphenylene ether-based resin foam sheet is small, the mechanical strength of the modified polyphenylene ether-based resin foam sheet may decrease. On the other hand, if the density is large, the flexibility of the modified polyphenylene ether-based resin foam sheet decreases. Therefore, 0.03 to 0.30 g / cm ³ is preferable, and 0.04 to 0.20 g / cm ³ is more preferable. The density of the modified polyphenylene ether-based resin foam sheet is a density measured in accordance with the method described in JIS K7222: 1999 “Measurement of foamed plastic and rubber-apparent density”.

  In addition, if the thickness of the modified polyphenylene ether resin foam sheet is small, the thickness of the automobile interior material obtained using the modified polyphenylene ether resin foam sheet may be reduced, and the mechanical strength of the automobile interior material may be reduced. On the other hand, if it is thick, the moldability of the modified polyphenylene ether-based resin foamed sheet may be lowered, so 2 to 10 mm is preferable, and 2 to 8 mm is more preferable.

  The modified polyphenylene ether-based resin foam sheet includes a heat stabilizer, an inorganic filler such as talc as a foam regulator, and a metal salt of a fatty acid such as a metal salt of stearic acid as long as the physical properties of the foam sheet are not impaired. Further, flame retardants, lubricants, impact resistance improvers, pigments and the like may be added.

  The heat stabilizer is not particularly limited. For example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-) Phenol-based heat stabilizers such as tert-butyl-4-hydroxyphenyl) propionate, phosphorus-based heat stabilizers such as tris (2,4-di-tert-butylphenyl) phosphite, 3-hydroxy-5,7-di -Lactone heat stabilizers such as a reaction product of tert-butyl-furan-2-one and o-xylene, sulfur heat stabilizers such as didodecyl-3,3'-thiodipropionate, and the like Thermal stabilizers, phosphorus-based heat stabilizers, and lactone-based heat stabilizers are preferred. Lactone-based heat stabilizers are effective for radical scavenging in the early stage of radical generation. It is more preferable to contain a lactone heat stabilizer because it effectively suppresses the generation of toluene, and the lactone heat stabilizer is used in combination with a lactone heat stabilizer and a phenol heat stabilizer. It is particularly preferred to use a phosphorus heat stabilizer in combination.

  If the content of the thermal stabilizer in the modified polyphenylene ether-based resin foam sheet is small, the modified polyphenylene ether-based resin is thermally decomposed during the production process of the modified polyphenylene ether-based resin foam sheet, and toluene, styrene monomer, ethylbenzene On the other hand, since the mechanical strength of the resulting modified polyphenylene ether-based resin foamed sheet may decrease, the modified polyphenylene ether-based resin foamed sheet has a weight of 0.1 to 3%. % Is preferred.

  Furthermore, when a lactone heat stabilizer and a phenol heat stabilizer are used in combination as a heat stabilizer, the weight ratio of the lactone heat stabilizer to the phenol heat stabilizer (lactone heat stabilizer / phenolic heat stabilizer). Heat stabilizer) is preferably adjusted to be 0.10 to 0.55. Similarly, when a lactone heat stabilizer and a phenol heat stabilizer are used in combination, a lactone heat stabilizer and It is preferable to adjust the weight ratio of the phosphorus-based heat stabilizer (lactone-based heat stabilizer / phosphorus-based heat stabilizer) to be 0.05 to 0.45.

  And the amount of toluene remaining in the modified polyphenylene ether-based resin foamed sheet is limited to less than 100 ppm with respect to the total weight of the modified polyphenylene ether-based resin foamed sheet, preferably 60 ppm or less, and excellent in environmental hygiene. Thus, even when used as an automobile interior material in a closed space inside a car, the car space can be kept good in terms of hygiene.

  Furthermore, the amount of the styrene monomer remaining in the modified polyphenylene ether-based resin foam sheet is preferably less than 700 ppm with respect to the total weight of the modified polyphenylene ether-based resin foam sheet, thus suppressing the amount of residual styrene monomer. Therefore, it can be excellent in terms of environmental hygiene, and even when used as an automobile interior material in a closed space inside a car, the car interior space can be kept better in terms of hygiene.

  Here, the amount of toluene or the amount of styrene monomer remaining in the modified polyphenylene ether-based resin foam sheet refers to that measured in the following manner. A 0.2 g sample piece is cut out from the modified polyphenylene ether resin foam sheet. Then, after storing the sample piece in a 20 ml bottomed cylindrical container, 1 ml of dimethylformamide containing 50 ppm of diethylbenzene is supplied into the container, and the sample piece is dissolved in this solvent. The opening of the container is hermetically closed by a lid member so as to be opened and closed.

  After that, after heating the container to (90 ± 1) ° C. for 1 hour, the container lid member is removed so that the gas in the container does not leak to the outside, and 2 ml of gas in the container is collected. The amount of toluene or the amount of styrene monomer is measured by an internal standard method after being supplied to a gas chromatograph.

  The amount of toluene remaining in the modified polyphenylene ether-based resin foam sheet was specifically measured under the following measurement conditions using a gas chromatograph commercially available from Shimadzu Corporation under the trade name “GC-18A”. Can be measured.

Column: DB-WAX (0.25 μm × 30 m × 0.25 mm)
Column temperature: Hold at 100 ° C. for 5 minutes, then heat at a heating rate of 40 ° C./min and hold at 220 ° C. for 2 minutes.
Inlet temperature: 150 ° C
Detector: 250 ° C
Carrier gas: helium (pressure: 122 kPa) with a moving flow rate of 1.6 ml / min
Split ratio: 70: 1

  The modified polyphenylene ether resin sheet may be laminated and integrated on both surfaces of the modified polyphenylene ether resin foam sheet. The polyphenylene ether resin constituting the modified polyphenylene ether resin sheet is the same as the modified polyphenylene ether resin constituting the modified polyphenylene ether resin foamed sheet, but the phenylene ether component is 10 to 50% by weight. And a modified polyphenylene ether-based resin having a styrene component of 90 to 50% by weight, more preferably a modified polyphenylene ether-based resin having a phenylene ether component of 10 to 40% by weight and a styrene component of 90 to 60% by weight, A modified polyphenylene ether-based resin having a phenylene ether component of 15 to 40% by weight and a styrene component of 85 to 60% by weight is particularly preferable. When a polystyrene resin is mixed with the modified polyphenylene ether resin, the content of the polyphenylene ether component and the styrene component refers to the content including the polystyrene resin.

  This is because if the amount of the phenylene ether component in the modified polyphenylene ether-based resin sheet is small, the heat resistance and rigidity of the modified polyphenylene ether-based resin sheet may be reduced. This is because it may become non-uniform.

  The amount of toluene remaining in the modified polyphenylene ether resin sheet is preferably adjusted to be less than 100 ppm with respect to the total weight of the modified polyphenylene ether resin sheet, and adjusted to be 60 ppm or less. More preferably. Thereby, even when it is used as a base material for automobile interior materials and used in a closed space inside an automobile, the interior space of the vehicle can be kept good in terms of hygiene.

  Furthermore, the amount of the styrene monomer remaining in the modified polyphenylene ether resin sheet is preferably less than 400 ppm with respect to the total weight of the modified polyphenylene ether resin sheet. In addition, it can be excellent, and even when used as an automobile interior material in a closed space inside a car, the car interior space can be kept better in terms of hygiene.

  The amount of toluene or styrene monomer remaining in the modified polyphenylene ether-based resin sheet can be measured in the same manner as the procedure for measuring the amount of toluene remaining in the modified polyphenylene ether-based resin foamed sheet.

  The modified polyphenylene ether-based resin sheet includes a modified polyphenylene ether-based resin constituting the modified polyphenylene ether-based resin foam sheet and a modified polyphenylene directly on both sides of the modified polyphenylene ether-based resin foamed sheet without interposing an adhesive layer. It is preferably laminated and integrated by thermal fusion with the modified polyphenylene ether resin constituting the ether resin sheet.

  In this way, the modified polyphenylene ether resin foam sheet and the modified polyphenylene ether resin sheet are firmly integrated by thermal fusion between the modified polyphenylene ether resins constituting the modified polyphenylene ether resin sheet. The modified polyphenylene ether-based resin sheet can be accurately and reliably formed into a complicated shape without peeling from the surface of the foamed sheet.

  Furthermore, if the thickness of the modified polyphenylene ether-based resin sheet is thin, irregularities are conspicuous on the surface of the modified polyphenylene ether-based resin foam sheet, or the appearance may be reduced, or the mechanical strength of the modified polyphenylene ether-based resin foam sheet may be decreased. In addition, if it is thick, the moldability and light weight of the modified polyphenylene ether-based resin foam sheet may be deteriorated, so 50 to 300 μm is preferable, and 70 to 200 μm is more preferable.

  Next, a method for producing the modified polyphenylene ether resin foam sheet will be described. First, a reduction treatment of toluene contained in a modified polyphenylene ether resin used as a raw material of a modified polyphenylene ether resin foamed sheet or a polyphenylene ether before modification is performed. At this time, it is preferable to perform the reduction treatment so that the amount of toluene remaining in the modified polyphenylene ether resin or polyphenylene ether is less than 60 ppm based on the total weight of the modified polyphenylene ether resin or polyphenylene ether.

  The toluene reduction treatment method includes (1) a method in which a modified polyphenylene ether-based resin or polyphenylene ether is supplied to an extruder provided with a vent and the toluene is sucked and removed from the vent while melt-kneading, and (2) a modification. The polyphenylene ether resin powder or the polyphenylene ether powder is supplied to a stirrer, and the modified polyphenylene ether resin powder or the polyphenylene ether resin powder or A method in which an inert gas heated to a high temperature is continuously brought into contact with the polyphenylene ether powder.

  And when performing the reduction process of toluene by the method of said (1), since the reduction effect of the toluene of modified polyphenylene ether resin or polyphenylene ether improves, the modified polyphenylene ether resin of the molten state in an extruder is improved. It is preferable to press-fit water and alcohol therein. It does not specifically limit as said alcohol, For example, methanol, ethanol, etc. are mentioned, Ethanol is preferable.

  Further, if the amount of water injected into the modified polyphenylene ether resin or polyphenylene ether is small, the effect of reducing toluene may be low, while if it is large, the extrusion conditions may vary. The amount is preferably 0.2 to 4.0 parts by weight with respect to 100 parts by weight of the system resin or polyphenylene ether.

  Furthermore, if the amount of alcohol to be injected into the modified polyphenylene ether resin or polyphenylene ether is small, the effect of reducing toluene may be low, while if it is large, the extrusion conditions may vary. The amount is preferably 0.2 to 4.0 parts by weight based on 100 parts by weight of the base resin or polyphenylene ether.

  Examples of the inert gas used in the method (2) include nitrogen and argon. The temperature of the inert gas brought into contact with the modified polyphenylene ether resin powder or the polyphenylene ether powder is preferably lower than the glass transition temperature of the modified polyphenylene ether resin powder or polyphenylene ether. The glass transition temperature of the modified polyphenylene ether resin powder or polyphenylene ether refers to a temperature measured in accordance with JIS K7121: 1987 “Plastic Transition Temperature Measurement Method”.

  When the toluene reduction treatment is performed as described in (1) above, the modified polyphenylene ether resin or polyphenylene ether is extruded from the extruder into pellets, and the toluene reduction treatment is performed as described in (2) above. When performed, the modified polyphenylene ether resin or polyphenylene ether that has been subjected to the toluene reduction treatment is supplied to an extruder together with the polystyrene resin as necessary, melt-kneaded, extruded, and pelletized. In the case of a modified polyphenylene ether-based resin, the modified polyphenylene ether-based resin pellets are supplied to an extruder together with the polystyrene-based resin as necessary, melted and kneaded, and a foaming agent is pressed into the extruder to be extruded and foamed. A modified polyphenylene ether resin foamed sheet may be produced. In the case of polyphenylene ether, the polyphenylene ether pellets and the polystyrene resin are supplied to an extruder and melt kneaded, and a foaming agent is injected into the extruder and extruded and foamed. Thus, a modified polyphenylene ether-based resin foam sheet is produced.

  In the above description, the modified polyphenylene ether-based resin or polyphenylene ether pellets were once manufactured, and then the pellets were supplied to the extruder and extruded and foamed. However, the method for reducing toluene in the above (1) was described. In this case, without producing pellets, the modified polyphenylene ether resin is supplied to the extruder provided with the vent, melted and kneaded, and the toluene is sucked and removed from the vent. Then, the blowing agent is pressed into the extruder. Then, the modified polyphenylene ether resin may be extruded and foamed to produce a modified polyphenylene ether resin foam sheet. Further, even when the toluene reduction method (2) is used, the modified polyphenylene ether resin subjected to the toluene reduction treatment is supplied to an extruder and melt-kneaded without producing pellets. At the same time, a foaming agent is press-fitted into the extruder and extruded and foamed to produce a modified polyphenylene ether resin foam sheet, or polyphenylene ether and polystyrene resin subjected to toluene reduction treatment are supplied to the extruder and melted. A modified polyphenylene ether-based resin foam sheet may be produced by kneading and press-fitting a foaming agent into an extruder and extrusion-foaming.

  The blowing agent is not particularly limited as long as it is conventionally used, and examples thereof include ethane, propane, butane, pentane, dimethyl ether, and the like. May be.

  As described above, when the modified polyphenylene ether-based resin is extruded and foamed, if the modified polyphenylene ether-based resin is decomposed, toluene may be generated. Therefore, it is preferable to supply the thermal stabilizer described above into the extruder. The supply amount of the heat stabilizer is preferably adjusted to be 0.1 to 3% by weight in the modified polyphenylene ether-based resin foam sheet.

  Furthermore, in order to suppress the decomposition of the modified polyphenylene ether-based resin, it is preferable to adjust the maximum heating temperature of the modified polyphenylene ether-based resin in the extruder at the time of production of the modified polyphenylene ether-based resin foam sheet to 300 ° C. or less. It is more preferable to adjust to the following.

  And as a method of laminating and integrating the modified polyphenylene ether resin sheet on both surfaces of the modified polyphenylene ether resin foam sheet obtained as described above, for example, (1) on both surfaces of the modified polyphenylene ether resin foam sheet A method in which a modified polyphenylene ether-based resin sheet is overlaid, and the modified polyphenylene ether-based resin sheet is thermally fused and integrated on both sides of the modified polyphenylene ether-based resin foam sheet with a heat roll. (2) Both surfaces of the modified polyphenylene ether-based resin foamed sheet A modified polyphenylene ether-based resin sheet immediately after being extruded from an extruder, and laminating and integrating the modified polyphenylene ether-based resin sheet on the surface of the modified polyphenylene ether-based resin foam sheet (3 ) Coextrusion More specifically, a method of laminating and integrating a modified polyphenylene ether resin sheet on both surfaces of a modified polyphenylene ether resin foam sheet by heat fusion, etc. are mentioned. The method (2) and (3) are preferred, and the method (2) is more preferred. preferable.

  Further, the modified polyphenylene ether-based resin foam sheet is usually provided on one side (one modified polyphenylene ether-based resin sheet when the modified polyphenylene ether-based resin sheet is laminated and integrated) with an adhesive layer interposed therebetween. In addition, the anti-noise material is laminated and integrated on the other side (the other modified polyphenylene ether resin sheet when the modified polyphenylene ether resin sheet is laminated and integrated). The base material for automobile interior material is formed into a desired shape by thermoforming and used as an automobile interior material. Examples of the skin material include nonwoven fabric, woven fabric, and knitted fabric. Note that a flame retardant may be included in order to impart flame retardancy to the skin material.

  Examples of the fibers constituting the skin material include synthetic fibers made of polyester such as polyethylene terephthalate, polyamide, polyacrylonitrile, and the like; natural fibers made of wool, cotton, and the like. Polyester fibers are preferred, and heat resistance is excellent. Therefore, polyethylene terephthalate fiber is more preferable. In addition, the fiber which comprises the said skin material may be used independently, or may be used together.

  The adhesive layer is not particularly limited as long as the skin material and the modified polyphenylene ether-based resin foam sheet (modified polyphenylene ether-based resin sheet) can be bonded and integrated. For example, a thermoplastic adhesive, hot Melt adhesives, rubber adhesives, thermosetting adhesives, monomer reactive adhesives, inorganic adhesives, natural material adhesives, etc., but hot melt adhesives can be easily bonded Is preferred.

  Examples of the hot melt adhesive include polyolefin, modified polyolefin, polyurethane, ethylene-vinyl acetate copolymer, polyamide, polyester, thermoplastic elastomer, styrene-butadiene copolymer, styrene- The thing which uses resin, such as an isoprene copolymer system as a component, is mentioned, These may be used independently or may be used together.

  In addition, an anti-noise material is laminated and integrated on the other surface of the modified polyphenylene ether-based resin foam sheet, that is, the surface on which the skin material is not laminated and integrated. This is for reducing the frictional noise generated when the automobile interior material comes into sliding contact with the steel sheet to be formed. A polyolefin resin film or a nonwoven fabric is preferably used, and a nonwoven fabric is more preferably used.

  Examples of the polyolefin resin film include polyolefin resin films such as a polyethylene film and a polypropylene film, which are excellent in heat resistance and stably generate frictional noise over a long period of time regardless of ambient temperature changes. An unstretched polypropylene film is preferable in that it can be reduced. In addition, as for the said polyolefin resin film, the thing whose thickness is 10-100 micrometers normally 25-35 micrometers is normally used preferably.

  Furthermore, the fiber constituting the nonwoven fabric used for the above-mentioned noise prevention material is not particularly limited. For example, synthetic resin fibers such as polyester fiber, polyethylene fiber, polypropylene fiber, polyamide fiber, and polyacrylonitrile fiber; wool, cotton, Examples thereof include natural fibers such as cellulose fibers.

  The modified polyphenylene ether-based resin foam sheet of the present invention is a modified polyphenylene ether-based resin foam sheet obtained by supplying a modified polyphenylene ether-based resin to an extruder, melt-kneading with a foaming agent, and extrusion-foaming from the extruder. The amount of toluene remaining in the modified polyphenylene ether-based resin foam sheet is less than 100 ppm with respect to the total weight of the modified polyphenylene ether-based resin foam sheet, so that the environment during curing, storage or use is good Can be held in a stable state.

  Even when the modified polyphenylene ether-based resin foam sheet of the present invention is used in automobile interior materials and used in a closed space inside an automobile, the amount of toluene in the usage environment is kept low, causing problems such as sick house syndrome. Can be generally suppressed.

  In the modified polyphenylene ether resin foam sheet, the modified polyphenylene ether resin sheet is laminated and integrated on both sides, and the amount of toluene remaining in the modified polyphenylene ether resin sheet is the modified polyphenylene ether resin sheet. When it is less than 100 ppm with respect to the total weight of the resin, the modified polyphenylene ether resin foam sheet is excellent in heat resistance and mechanical strength, and keeps the environment during curing, storage or use in a good state. be able to.

  Furthermore, in the modified polyphenylene ether-based resin foam sheet, when 0.1 to 3% by weight of a heat stabilizer is contained, decomposition of the modified polyphenylene ether-based resin is suppressed and generation of toluene is effectively prevented. The modified polyphenylene ether-based resin foam sheet is more excellent in terms of environmental hygiene.

(Example 1)
70 parts by weight of poly (2,6-dimethylphenylene-1,4-ether), 30 parts by weight of polystyrene, 0.4 parts by weight of water and 0.2 parts by weight of ethanol are mixed to produce a modified polyphenylene ether resin composition. did.

  Then, the modified polyphenylene ether-based resin composition is supplied to a twin-screw extruder provided with a vent, melted and kneaded at 280 ° C., depressurized and degassed from the vent, and from a die attached to the tip of the extruder After extruding into a strand shape and continuously immersing the strand in a water bath and cooling, the strand was cut into predetermined lengths to produce cylindrical modified polyphenylene ether resin pellets having a diameter of about 2 mm. The amount of toluene contained in the pellet is 48 ppm with respect to the total weight of the pellet, the amount of styrene monomer contained in the pellet is 271 ppm with respect to the total weight of the pellet, and water and ethanol are contained in the pellet. It was not contained.

  Next, from 58 parts by weight of the modified polyphenylene ether resin pellets and 42 parts by weight of polystyrene (trade name “HRM-26” manufactured by Toyo Styrene Co., Ltd., toluene content: 0 ppm, styrene monomer content with respect to the total weight of polystyrene: 127 ppm) A modified polyphenylene ether resin (phenylene ether component: 40% by weight, styrene component: 60% by weight), 0.65 part by weight of talc, and a heat stabilizer comprising a lactone heat stabilizer and a phenol heat stabilizer (Ciba・ Product name “IRGASAB STYL66” manufactured by Specialty Chemicals Co., Ltd., Lactone heat stabilizer: reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene, phenol Thermal stabilizer: Octadecyl-3- (3,5-di-ter -Butyl-4-hydroxyphenyl) propionate) 0.6 parts by weight is supplied to the first extruder and melt-kneaded, and the first extruder contains 35% by weight of isobutane and 65% by weight of normal butane. After 9 parts by weight were injected and melted and kneaded at 280 ° C., the molten resin was continuously supplied to the second extruder connected to the tip of the first extruder to adjust the resin temperature to 184 ° C. Above, extrusion foaming was performed in a cylindrical shape from a circular mold (temperature: 155 ° C.) attached to the tip of the second extruder. This cylindrical foam was continuously cut between the inner and outer surfaces in the extrusion direction and developed to obtain a modified polyphenylene ether resin foam sheet.

The amount of toluene remaining in the obtained modified polyphenylene ether-based resin foam sheet is 59 ppm with respect to the total weight of the modified polyphenylene ether-based resin foam sheet, and the amount of styrene monomer remaining in the modified polyphenylene ether-based resin foam sheet is And 555 ppm relative to the total weight of the modified polyphenylene ether-based resin foam sheet. The resulting modified polyphenylene ether resin foam sheet has a thickness of 2.50 mm, a basis weight of 154 g / m ² , an expansion ratio of 17.0 times, a density of 0.062 g / cm ³ , and an open cell ratio of 19 .5%.

(Example 2)
35 parts by weight of modified polyphenylene ether resin pellets produced in Example 1 and high impact polystyrene (trade name “E641N” manufactured by Toyo Styrene Co., Ltd., toluene content relative to the total weight of the high impact polystyrene: 3 ppm, based on the total weight of the high impact polystyrene Styrene monomer content: 282 ppm) from 65 parts by weight modified polyphenylene ether resin (phenylene ether component: 24.5 wt%, styrene component: 75.5 wt%), lactone heat stabilizer and phenol heat stabilizer A heat stabilizer (trade name “IRGASAB STYL66” manufactured by Ciba Specialty Chemicals Co., Ltd.), a lactone-based heat stabilizer: 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene Reaction product, phenol System heat stabilizer: 0.6 part by weight of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), and carbon black masterbatch (manufactured by Dainichi Seika Co., Ltd.) as a colorant “PS-M SSC 98H822A, carbon black: 40% by weight) A mixed resin mixed with 1 part by weight was supplied to each of two extruders, and a molten sheet immediately after being extruded from one of the extruders was carried out. The modified polyphenylene ether-based resin foam sheet extruded and foamed from the extruder in the same manner as in Example 1 is laminated on one surface and heat-sealed and integrated, and the melted sheet immediately after being extruded from the other extruder is used as the modified polyphenylene ether. Laminated on the other side of the resin-based resin foam sheet and integrated by heat fusion, and blackened with carbon black entirely in the thickness direction on both sides Color has been modified polyphenylene ether-based resin sheet is directly manufactured a modified polyphenylene ether-based resin foam sheet obtained by laminating together by heat fusion.

The amount of toluene remaining in the obtained modified polyphenylene ether-based resin foam sheet is 59 ppm with respect to the total weight of the modified polyphenylene ether-based resin foam sheet, and the amount of styrene monomer remaining in the modified polyphenylene ether-based resin foam sheet is And 555 ppm relative to the total weight of the modified polyphenylene ether-based resin foam sheet. The resulting modified polyphenylene ether resin foam sheet has a thickness of 2.50 mm, a basis weight of 154 g / m ² , an expansion ratio of 17.0 times, a density of 0.062 g / cm ³ , and an open cell ratio of 19 .5%.

The amount of toluene remaining in the modified polyphenylene ether resin sheet was 20 ppm with respect to the total weight of the modified polyphenylene ether resin sheet, and the amount of styrene monomer remaining in the modified polyphenylene ether resin sheet was And 264 ppm relative to the total weight of the modified polyphenylene ether resin sheet. The modified polyphenylene ether resin sheet had a basis weight of 123 g / m ² and a thickness of 117 μm.

(Example 3)
The modified polyphenylene ether-based resin foam sheet and the modified polyphenylene ether-based resin sheet were colored black with carbon black in the thickness direction on both sides in the same manner as in Example 2 except that no heat stabilizer was contained. A modified polyphenylene ether-based resin foamed sheet was produced in which the modified polyphenylene ether-based resin sheet was directly laminated and integrated by thermal fusion.

The amount of toluene remaining in the obtained modified polyphenylene ether-based resin foam sheet is 68 ppm with respect to the total weight of the modified polyphenylene ether-based resin foam sheet, and the amount of styrene monomer remaining in the modified polyphenylene ether-based resin foam sheet is And 680 ppm relative to the total weight of the modified polyphenylene ether-based resin foam sheet. The resulting modified polyphenylene ether resin foam sheet has a thickness of 2.50 mm, a basis weight of 154 g / m ² , an expansion ratio of 17.0 times, a density of 0.062 g / cm ³ , and an open cell ratio of 19 .5%.

The amount of toluene remaining in the modified polyphenylene ether resin sheet is 32 ppm with respect to the total weight of the modified polyphenylene ether resin sheet, and the amount of styrene monomer remaining in the modified polyphenylene ether resin sheet is And 320 ppm relative to the total weight of the modified polyphenylene ether resin. The modified polyphenylene ether resin sheet had a basis weight of 123 g / m ² and a thickness of 117 μm.

Example 4
Polyphenylene ether powder (manufactured by GE Plastics, glass transition temperature: 220 ° C., toluene content with respect to the total weight of polyphenylene ether: 150 ppm, particle size: 40 to 900 μm) is supplied to the Nauter mixer, While maintaining at 140 ° C., nitrogen heated to 140 ° C. is supplied into the Nauta mixer at a supply rate of 2 Nm ³ / min, and the polyphenylene ether powder is kept in contact with the polyphenylene ether powder for 5 hours. Was stirred. Toluene was not contained in the obtained polyphenylene ether powder.

  Then, 70 parts by weight of the obtained polyphenylene ether powder and 30 parts by weight of polystyrene (trade name “HRM-26” manufactured by Toyo Styrene Co., Ltd., toluene content: 0 ppm, styrene monomer content with respect to the total weight of polystyrene: 127 ppm) Supply to an extruder, melt knead, extrude into a strand from a die attached to the tip of the extruder, cool the strand by continuously immersing it in a water tank, and then cut the strand into a predetermined length. A cylindrical modified polyphenylene ether resin pellet having a diameter of about 2 mm was prepared. The amount of toluene contained in the pellet was 2 ppm relative to the total weight of the pellet, and the amount of styrene monomer contained in the pellet was 225 ppm relative to the total weight of the pellet.

  Next, from 58 parts by weight of the modified polyphenylene ether resin pellets and 42 parts by weight of polystyrene (trade name “HRM-26” manufactured by Toyo Styrene Co., Ltd., toluene content: 0 ppm, styrene monomer content with respect to the total weight of polystyrene: 127 ppm) A modified polyphenylene ether-based resin (phenylene ether component: 40% by weight, styrene component: 60% by weight) and 0.65 part by weight of talc are fed to the first extruder and melt-kneaded, and isobutane 35 is added to the first extruder. 3.9 parts by weight of a foaming agent consisting of 65% by weight and normal butane was press-fitted and melt-kneaded at 280 ° C., and then the molten resin was continuously fed to the second extruder connected to the tip of the first extruder. After supplying and adjusting the resin temperature to be 184 ° C, the circular attached to the tip of the second extruder Type (Temperature: 155 ° C.) was extruded foam in a cylindrical shape from. This cylindrical foam was continuously cut between the inner and outer surfaces in the extrusion direction and developed to obtain a modified polyphenylene ether resin foam sheet.

The amount of toluene remaining in the resulting modified polyphenylene ether resin foam sheet is 5 ppm with respect to the total weight of the modified polyphenylene ether resin foam sheet, and the amount of styrene monomer remaining in the modified polyphenylene ether resin foam sheet is And 463 ppm relative to the total weight of the modified polyphenylene ether resin foam sheet. The resulting modified polyphenylene ether resin foam sheet has a thickness of 2.50 mm, a basis weight of 154 g / m ² , an expansion ratio of 17.0 times, a density of 0.062 g / cm ³ , and an open cell ratio of 19 .5%.

  35 parts by weight of the above modified polyphenylene ether resin pellets and high impact polystyrene (trade name “E641N” manufactured by Toyo Styrene Co., Ltd., toluene content with respect to the total weight of the high impact polystyrene: 3 ppm, styrene monomer content with respect to the total weight of the high impact polystyrene: 282 ppm) 65 parts by weight of modified polyphenylene ether resin (phenylene ether component: 24.5% by weight, styrene component: 75.5% by weight) and carbon black masterbatch (manufactured by Dainichi Seika Co., Ltd. as a colorant) -M SSC 98H822A, carbon black: 40% by weight) A mixed resin mixed with 1 part by weight was supplied to each of two extruders, and the molten sheet immediately after extrusion from one of the extruders was used as the modified polyphenylene. Ete Laminated on one side of the resin-based foamed sheet and integrated with heat fusion, and the sheet in the molten state immediately after being extruded from the other extruder is laminated on the other side of the modified polyphenylene ether-based resin foamed sheet and integrated with heat fusion Thus, a modified polyphenylene ether-based resin foam sheet was produced in which the modified polyphenylene ether-based resin sheet, which was entirely colored black with carbon black on both sides in the thickness direction, was directly laminated and integrated by thermal fusion.

The amount of toluene remaining in the modified polyphenylene ether resin sheet was 4 ppm relative to the total weight of the modified polyphenylene ether resin sheet, and the amount of styrene monomer remaining in the modified polyphenylene ether resin sheet was And 280 ppm relative to the total weight of the modified polyphenylene ether resin sheet. The modified polyphenylene ether resin sheet had a basis weight of 123 g / m ² and a thickness of 117 μm.

(Comparative Example 1)
Modified polyphenylene ether resin (trade name “EFN4230” manufactured by GE Plastics Co., Ltd.), polyphenylene ether: 70 wt%, polystyrene resin: 30 wt%, toluene content with respect to the total weight of the modified polyphenylene ether resin: 322 ppm, modified polyphenylene ether 58 parts by weight of styrene monomer content based on the total weight of the resin: 1178 ppm) and 42 weight parts of polystyrene (trade name “HRM-26” manufactured by Toyo Styrene Co., Ltd., toluene content: 0 ppm, styrene monomer content based on the total weight of polystyrene: 127 ppm) A modified polyphenylene ether-based resin (phenylene ether component: 40% by weight, styrene component: 60% by weight), and 0.65 parts by weight of talc are fed to the first extruder and melt-kneaded, After 3.9 parts by weight of a foaming agent comprising 35% by weight of isobutane and 65% by weight of normal butane was pressed into one extruder and melt-kneaded at 280 ° C., the second extruder connected to the tip of the first extruder was The molten resin was continuously supplied to adjust the resin temperature to 184 ° C., and then extruded and foamed in a cylindrical shape from a circular mold attached to the tip of the second extruder. This cylindrical foam was continuously cut between the inner and outer surfaces in the extrusion direction and developed to obtain a modified polyphenylene ether resin foam sheet.

The amount of toluene remaining in the resulting modified polyphenylene ether-based resin foam sheet is 321 ppm with respect to the total weight of the modified polyphenylene ether-based resin foam sheet, and the amount of styrene monomer remaining in the modified polyphenylene ether-based resin foam sheet is And 712 ppm relative to the total weight of the modified polyphenylene ether resin foam sheet. The resulting modified polyphenylene ether resin foam sheet has a thickness of 2.50 mm, a basis weight of 154 g / m ² , an expansion ratio of 17.0 times, a density of 0.062 g / cm ³ , and an open cell ratio of 19 .5%.

(Comparative Example 2)
35 parts by weight of modified polyphenylene ether resin (trade name “EFN4230” manufactured by GE Plastics, toluene content with respect to the total weight of the modified polyphenylene ether resin: 322 ppm, styrene monomer content with respect to the total weight of the modified polyphenylene ether resin: 1178 ppm) And modified polyphenylene ether comprising 65 parts by weight of high impact polystyrene (trade name “E641N” manufactured by Toyo Styrene Co., Ltd., toluene content with respect to the total weight of the high impact polystyrene: 3 ppm, styrene monomer content with respect to the total weight of the high impact polystyrene: 282 ppm) Resin (phenylene ether component: 24.5 wt%, styrene component: 75.5 wt%), and carbon black masterbatch (Daiichi Seika Co., Ltd.) as a colorant Product name “PS-M SSC 98H822A, carbon black: 40% by weight) A mixed resin mixed with 1 part by weight is supplied to each of two extruders, and a sheet in a molten state immediately after being extruded from one of the extruders. In addition, the modified polyphenylene ether-based resin foam sheet extruded and foamed from the extruder in the same manner as in Comparative Example 1 is laminated on one surface and heat-fused and integrated, and the molten sheet immediately after being extruded from the other extruder is modified as described above. Laminated on the other side of the polyphenylene ether-based resin foam sheet and integrated by heat fusion, and the modified polyphenylene ether-based resin sheet colored black with carbon black in the thickness direction on both sides is directly laminated by thermal fusion. An integrated modified polyphenylene ether resin foam sheet was produced.

The amount of toluene remaining in the resulting modified polyphenylene ether-based resin foam sheet is 321 ppm with respect to the total weight of the modified polyphenylene ether-based resin foam sheet, and the amount of styrene monomer remaining in the modified polyphenylene ether-based resin foam sheet is And 712 ppm relative to the total weight of the modified polyphenylene ether resin foam sheet. The resulting modified polyphenylene ether resin foam sheet has a thickness of 2.50 mm, a basis weight of 154 g / m ² , an expansion ratio of 17.0 times, a density of 0.062 g / cm ³ , and an open cell ratio of 19 .5%.

The amount of toluene remaining in the modified polyphenylene ether resin sheet was 118 ppm relative to the total weight of the modified polyphenylene ether resin sheet, and the amount of styrene monomer remaining in the modified polyphenylene ether resin sheet was And 413 ppm relative to the total weight of the modified polyphenylene ether resin sheet. The modified polyphenylene ether resin sheet had a basis weight of 123 g / m ² and a thickness of 117 μm.

  The amounts of toluene and styrene monomer emitted from the resulting modified polyphenylene ether-based resin foamed sheet were measured in the manner shown below, and the results are shown in Table 1.

(Emission amount)
A flat rectangular test piece of 8 cm in length and 10 cm in width was cut from the obtained modified polyphenylene ether-based resin foam sheet over the entire thickness of the foam sheet. Then, after leaving the test piece in a flexible container having a volume of 10 liters, the air in the container was completely removed, and then the container was sealed with 4000 ml of nitrogen.

Next, after heating the container to 65 ° C. for 2 hours, the air in the container was collected at 200 ml / min using an adsorption tube (trade name “Tenax-Ta adsorption tube” manufactured by Nihon Analytical Industries, Ltd.). 1000 milliliters were collected at a speed. The collected air was analyzed under the following conditions using a gas chromatography-mass spectrometer (trade name “QP5000” manufactured by Shimadzu Corporation), and the emission amount of toluene and styrene monomer per test piece was expressed by the following formula. Calculated based on 1.
Emission amount (μg / piece, 2 hours) = analysis value (μg) × 4000 (milliliter)
/ 1000 (milliliter) ... Formula 1

Column: J & W product name “DB-1” 1 μm × φ0.25 mm × 60 m
Column temperature: After holding at 40 ° C. for 3 minutes, heat at a rate of 15 ° C./min to 200 ° C., then heat at a rate of 25 ° C./min to 300 ° C. for 3.5 minutes Retained.
Inlet temperature: 240 ° C
Detector: 260 ° C
Carrier gas: helium with a moving flow rate of 1 ml / min Split ratio: 10: 1

Claims (5)

A modified polyphenylene ether resin foam sheet obtained by supplying a modified polyphenylene ether resin to an extruder, melt kneading with a foaming agent, and extruding and foaming from the extruder, and remains in the modified polyphenylene ether resin foam sheet. A modified polyphenylene ether resin foam sheet, wherein the amount of toluene to be added is less than 100 ppm based on the total weight of the modified polyphenylene ether resin foam sheet. The modified polyphenylene ether resin sheet is laminated and integrated on both sides, and the amount of toluene remaining in the modified polyphenylene ether resin sheet is less than 100 ppm with respect to the total weight of the modified polyphenylene ether resin sheet. The modified polyphenylene ether-based resin foam sheet according to claim 1, which is characterized by: The modified polyphenylene ether-based resin foamed sheet according to claim 1 or 2, further comprising 0.1 to 3% by weight of a heat stabilizer. An automobile interior comprising an outer skin material laminated on one surface of the modified polyphenylene ether-based resin foam sheet according to any one of claims 1 to 3 and an anti-noise material laminated on the other surface. Base material for materials. An automobile interior material, wherein the automobile interior material substrate according to claim 4 is thermoformed.