JP2005161789A - Laminated sheet for interior part of automobile - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated sheet for interior parts of an automobile capable of precisely compressing a desired part to reduce the thickness as well as forming the part to a complicated shape. <P>SOLUTION: This laminated sheet for interior parts of the automobile is characterized in that modified polyphenylene ether-based resin sheets 2 and 2 are integrally laminated on both surfaces of a modified polyphenylene ether-based resin foamed sheet 1 with open cell ratio of 40-90%, where the modified polyphenylene ether-based resin foamed sheet has a high open cell ratio. Thereby the laminated sheet for interior parts of the automobile can be precisely formed into the desired shape by smoothly deforming the cells while smoothly drawing the gas in the cell of the foamed sheet to outside thereof in the forming. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminated sheet for automobile interior materials used for automobile interior materials such as automobile ceiling materials and door members.

  Conventionally, various automobile interior materials have been proposed. As such an automobile interior material, for example, Patent Document 1 discloses a base material in which a PPO resin skin layer is adhered to the front and back surfaces of a PPO resin foam layer. There is provided an automobile interior part in which a skin material is coated on the surface side of the interior part, and an interior part for an automobile in which a compression part is formed on the outer peripheral edge and the opening peripheral part of the interior part.

  However, the PPO resin foam layer of the above automotive interior parts is formed from closed cells, so the outer peripheral edge and the peripheral edge of the mounting opening such as the room mirror should be thinned by pressing. However, there is a problem that the bubbles cannot be crushed just by compressing the air in the bubbles, and it is not possible to reduce the thickness to the desired thickness. There is a problem that an automobile interior material having a desired shape cannot be obtained, and this tendency is particularly remarkable when the PPO resin foam layer has a low density (high foaming ratio).

  Furthermore, in Patent Document 2, in a laminated interior material in which a foam layer and a surface material are laminated, an inorganic filler is contained in the foam, and there are minute amounts on the walls of many bubbles in the foam layer. There has been proposed a laminated interior material in which openings are formed and a portion in which a large number of bubbles are made into continuous cells and the thickness of the foam is reduced is formed in the laminated interior material.

  This laminated interior material is heated until the foam layer is softened and cooled while compressing the portion where the thickness is to be reduced, thereby destroying the bubbles in the foam layer of the compressed portion and making them into continuous cells. The gas inside is diffused to the outside, and the bubbles are plastically deformed to reduce the thickness of the compressed portion.

  However, since the laminated interior material contains a large amount of an inorganic filler in the foam layer, it is difficult to increase the foaming ratio of the foam layer, lacking in lightness, and further compression in the foam layer. The bubbles in the parts other than the part that has been made are closed cells, and if the laminated interior material is left at a high temperature, the gas in the closed cells expands and deforms, resulting in a lack of dimensional stability. It was.

No. 8-1943 Japanese Patent No. 2525429

  The present invention can compress and thin the thickness of desired locations such as the outer peripheral edge and the peripheral edge of the mounting opening of the rearview mirror, etc., and can be formed into a complicated shape, with dimensional stability and lightness. The laminated sheet for automobile interior materials excellent in

  In the laminated sheet A for automobile interior materials of the present invention, the modified polyphenylene ether resin sheets 2 and 2 are laminated and integrated on both surfaces of the modified polyphenylene ether resin foamed sheet 1 having an open cell ratio of 40 to 90%. It is characterized by.

  The modified polyphenylene ether resin constituting the foamed sheet 1 is not particularly limited, and is a mixture of polyphenylene ether and polystyrene resin represented by the following chemical formula 1, graft copolymerization of styrene monomer to the polyphenylene ether. A modified polyphenylene ether, a mixture of the modified polyphenylene ether and a polystyrene resin, and a phenolic monomer and a styrene monomer represented by the following chemical formula 2 in the presence of a catalyst such as an amine complex of copper (II). Examples thereof include a block copolymer to be obtained and a mixture of this block copolymer and a polystyrene resin. 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 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 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 having a phenylene ether component (polyphenylene ether component) of 15 to 60% by weight and a styrene component (polystyrene resin component) of 85 to 40% by weight. More preferable is a modified polyphenylene ether resin having a phenylene ether component (polyphenylene ether component) of 20 to 60% by weight and a styrene component (polystyrene resin component) of 80 to 40% by weight, and a phenylene ether component (polyphenylene ether component). Is particularly preferably a modified polyphenylene ether resin having a styrene component (polystyrene resin component) of 75 to 50% by weight.

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

  And if the open cell ratio of the whole modified polyphenylene ether-based resin foam sheet 1 is low, it may be difficult to compress a portion of the laminated sheet for automobile interior material to a desired thickness. If it is high, the mechanical strength of the laminated sheet for automobile interior materials may be lowered, so it is limited to 40 to 90%, and preferably 50 to 85%.

  In addition, the open cell rate of the modified polyphenylene ether-based resin foam sheet 1 refers to that measured in accordance with ASTM D2856-87. Specifically, a plurality of planar square sheet-like test pieces having a side of 25 mm are cut out from the modified polyphenylene ether-based resin foam sheet 1 over the entire length in the thickness direction of the foam sheet 1, and the plurality of tests are performed. Laminates are formed by stacking the pieces in the thickness direction so that the total thickness is 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

  Moreover, when the average cell diameter of the modified polyphenylene ether resin foamed sheet 1 is small, the foamed sheet 1 may become soft and the mechanical strength may be lowered. On the other hand, when the average cell diameter is large, the surface smoothness of the foamed sheet 1 is degraded. The thickness is preferably 0.2 to 0.9 mm, and more preferably 0.3 to 0.8 mm. In addition, the average cell diameter of the modified polyphenylene ether-based resin foam sheet 1 is a value measured in accordance with a test method of ASTM D2842-69.

The density of the modified polyphenylene ether-based resin foam sheet 1 is preferably 0.030~0.175g / cm ^3, more preferably ^{0.035~0.105g / cm 3, 0.040~0.075g / cm} 3 Is particularly preferred. This is due to the following reasons. That is, by adjusting the density of the modified polyphenylene ether-based resin in the laminated sheet for automobile interior materials within the above range, the bubbles of the foamed sheet 1 are configured while satisfying both the lightness and mechanical strength of the foamed sheet 1. The bubble film is made to have an appropriate thickness, and the bubble film can be easily plastically deformed by an appropriate bending force. The density of the modified polyphenylene ether-based resin foam sheet 1 is a density measured in accordance with the method described in JIS K7222: 1999 “Measurement of foamed plastic and rubber-apparent density”.

  Therefore, in the laminated sheet portion (compressed portion) for automobile interior material that has been compressed by pressing or the like to be thinned when being molded into the automobile interior material, the bubble film constituting the bubbles is the foam sheet 1. The plastic film is surely plastically deformed in the compression direction, and it is not necessary for the bubble film to be restored to the original state because a large gas pressure may be required to restore the plastically deformed bubble film to the original state. Therefore, the compressed portion of the laminated sheet for automobile interior material does not cause a springback phenomenon, and its thickness is not restored over time, and the thickness after compression is maintained.

  Thus, the laminated sheet for automobile interior material is accurately molded into a desired shape and formed into an automotive interior material with high dimensional accuracy, and the shape thereof is reliably maintained. It also has excellent performance in terms of attachment to the vehicle body and in-vehicle equipment such as a rearview mirror to automobile interior materials.

  On the other hand, if the thickness of the modified polyphenylene ether-based resin foam sheet 1 is small, the thickness of the automobile interior material obtained by molding the laminated sheet A for automobile interior material may be reduced, and the mechanical strength may be lowered. If it is thick, the moldability of the laminated sheet A for automobile interior materials may be lowered, so 2 to 10 mm is preferable, and 3 to 8 mm is more preferable.

  The modified polyphenylene ether-based resin foamed sheet 1 preferably has a foamed layer mainly composed of open cells. As such a modified polyphenylene ether-based resin foamed sheet 1, (1) mainly continuous A foam sheet consisting only of a foam layer composed of bubbles and having an overall open cell ratio of 40 to 90%; and (2) composed mainly of closed cells on both sides of the central foam layer 11 composed mainly of open cells. In other words, the surface foamed layers 12 and 12 are formed, and the total open cell ratio is 40 to 90%.

  The above-mentioned foamed sheet (1), that is, the modified polyphenylene ether resin foamed sheet 1 consisting mainly of a foamed layer mainly composed of open cells and having an overall open cell ratio of 40 to 90% is mainly composed of closed cells. The formed foam layer does not exist, and is entirely composed of a foam layer composed mainly of open cells. A non-foamed layer, so-called skin layer, may be formed on the entire surface of both surfaces of the modified polyphenylene ether resin foam sheet (1).

  Since this modified polyphenylene ether-based resin foamed sheet is entirely composed of open cells, the modified polyphenylene ether-based resin foamed sheet is generally homogeneous throughout.

  Therefore, even when the laminated sheet for automobile interior material is subjected to compression molding when being molded into the automobile interior material, the modified polyphenylene ether-based resin foam sheet 1 is molded into a desired shape while being compressed substantially uniformly in the thickness direction. Therefore, the strength of the modified polyphenylene ether-based resin foam sheet 1 is not partially reduced, and the predetermined strength is maintained.

  Further, the foamed layer of the modified polyphenylene ether-based resin foamed sheet 1 only needs to be mainly composed of open cells, and not all the cells need to be open cells, but 70 of the bubbles contained in the foamed layer. % Or more of bubbles are preferably continuous cells. In addition, the open cell rate of a foamed layer says what was measured by the measuring method of the above-mentioned open cell rate.

  Next, the modified polyphenylene ether-based resin foam sheet of (2) above, that is, having a central foam layer 11 mainly composed of open cells at the center, and closed cells on both sides of the center foam layer 11 is provided. A modified polyphenylene ether-based resin foam sheet in which the skin foam layers 12 and 12 mainly constituted from the above are formed continuously and integrally and the total open cell ratio is 40 to 90% will be described. The central foamed layer 11 and the skin foamed layer 12 do not have a clear boundary at the interface, but the central foamed layer 11 and the skin foamed layer 12 are mixed. Non-foamed layers 13, 13, so-called skin layers, may be formed on the entire surface of the skin foam layers 12, 12.

  Further, the central foamed layer 11 of the modified polyphenylene ether resin foamed sheet 1 only needs to be mainly composed of open cells, and not all the cells need to be open cells, but the bubbles contained in the central foamed layer 11 80% or more of the bubbles are preferably open cells. The open cell ratio of the central foam layer 11 refers to that measured by the above-described method for measuring open cell ratio.

  Similarly, the skin foam layer 12 of the modified polyphenylene ether resin 1 only needs to be mainly composed of closed cells, and not all the bubbles need to be closed cells. It is preferable that 60% or more of the bubbles are closed cells. In addition, the closed cell rate of the skin foam layer 12 refers to a value obtained by subtracting the open cell rate measured by the above-mentioned open cell rate measuring method and the ratio of the resin from 100 (%).

Closed cell ratio (%) = 100 × [(volume of laminate by air comparison hydrometer)
-(Mass of laminate / density of resin)] / apparent volume

  Furthermore, if the thickness of each skin foam layer 12 of the modified polyphenylene ether-based resin foam sheet 1 is thin, the mechanical strength of the laminated sheet A for automobile interior materials may decrease, so the modified polyphenylene ether-based resin foam sheet On the other hand, 1% or more of the total thickness of 1 is preferable. On the other hand, if it is thick, the desired portion of the laminated sheet A for automobile interior materials cannot be compression-molded to the desired thickness, and the moldability may be lowered. 30% or less of the thickness of the entire resin-based resin foam sheet 1 is preferable, and 2 to 25% is more preferable. When the non-foamed layer (skin layer) 13 is formed on the entire surface of the skin foam layer 12, the “thickness of the skin foam layer 12” refers to the thickness including the thickness of the non-foam layer 13.

  Here, in the present invention, a closed cell refers to a bubble that is surrounded by a bubble wall and is not in communication with other bubbles. On the other hand, the term “open cell” refers to all bubbles other than closed cells. Specifically, a through-hole is formed in the bubble wall, and the bubble is in communication with other bubbles through the through-hole.

  In the modified polyphenylene ether resin foam sheet, the distinction between a foam layer mainly composed of open cells and a foam layer mainly composed of closed cells is determined in the following manner.

  First, a sheet-like test piece having a side square of 40 mm is cut out from the modified polyphenylene ether-based resin foam sheet 1 over the entire length in the thickness direction of the foam sheet 1.

On the other hand, 300 g of distilled water and 3 cm ³ of water-based red ink for fountain pens were supplied into a beaker to prepare a red aqueous solution, and a test piece was pressed into the red aqueous solution from above with a wire mesh to center the vertical direction in the red aqueous solution. It is set as the state completely immersed in the part. Examples of the water-based red ink for the fountain pen include those sold by the pilot company under the trade name “Pilot Ink Red”.

Thereafter, the beaker in which the test piece is immersed is placed in a decompressor and the pressure is reduced to 5.3 × 10 ⁴ Pa for 30 seconds. Next, after returning the inside of the pressure reducer to normal pressure, the test piece is taken out from the pressure reducer, and the red aqueous solution adhering to the surface of the test piece is removed with a water absorbent towel.

  And by excising the surface of all the cut surfaces in the test piece, that is, excising the outer periphery of the flat four sides from the test piece over the entire length in the thickness direction, that is, over the entire length in the thickness direction in the form of a square frame. By cutting, a flat square colored test piece having a side of 38 mm is cut out. Next, the colored state of each cross section of this colored test piece was observed with a video microscope at a magnification of 50 times, and the colored portion was mainly made of a foamed layer made of open cells, while the non-colored portion was made mainly of closed cells. The foam layer is as follows.

  Furthermore, the thickness of the skin foam layer 12 of the modified polyphenylene ether resin foam sheet 1 is measured as follows. That is, a colored test piece is produced from the arbitrary five places of the modified polyphenylene ether-based resin foam sheet 1 in the same manner as described above.

  Next, the cross section of each colored specimen is observed at a magnification of 50 times using a video microscope, and the maximum thickness and the minimum thickness in the skin foam layer 12 are measured for each colored specimen, and the addition of these thicknesses is measured. The average value is calculated. Then, the arithmetic average of the arithmetic mean values calculated for each colored test piece is defined as the thickness of the skin foam layer 12 of the modified polyphenylene ether resin foam sheet 1. The video microscope is commercially available, for example, from SCARA Co., Ltd. under the trade name “Video Microscope VMS-300”.

  Furthermore, as shown in FIG. 1, modified polyphenylene ether resin sheets 2 and 2 are laminated and integrated on both surfaces of the modified polyphenylene ether resin foam sheet 1. The modified polyphenylene ether resin constituting the modified polyphenylene ether resin sheet 2 is the same as the modified polyphenylene ether resin constituting the foamed sheet 1, but the phenylene ether component (polyphenylene ether component) is 10 A modified polyphenylene ether resin having a styrene component (polystyrene resin component) of 90 to 50% by weight and a styrene component (polystyrene) having a phenylene ether component (polyphenylene ether component) of 10 to 40% by weight is preferable. The modified polyphenylene ether resin is preferably 90 to 60% by weight, the phenylene ether component (polyphenylene ether component) is 10 to 35% by weight, and the styrene component (polystyrene resin component) is 0-65 modified polyphenylene ether resin by weight% is particularly preferred. When the polystyrene resin is mixed with the polyphenylene ether resin, the content of the polyphenylene ether component and the styrene component is the content after including the polystyrene resin.

  This is because if the amount of the phenylene ether component (polyphenylene ether component) in the modified polyphenylene ether-based resin is small, the heat resistance and rigidity of the modified polyphenylene ether-based resin sheet 2 may be reduced. This is because the fluidity is lowered and the extrudability is lowered.

  In addition, you may mix the collection | recovery goods of the laminated sheet A for motor vehicle interior materials in the modified polyphenylene ether resin which comprises the said modified polyphenylene ether-type resin sheet 2, In this case, 100 weight part of modified polyphenylene ether-type resin is used. On the other hand, 100 parts by weight or less of the collected product of the laminated sheet A for automobile interior materials is preferable. This is because if too much of the recovered product of the laminated sheet A for automobile interior materials is mixed in the modified polyphenylene ether-based resin sheet 2, mechanical strength such as bending strength of the modified polyphenylene ether-based resin sheet 2 may be lowered. Because.

  Further, the modified polyphenylene ether-based resin sheet 2 may contain a colorant, and such a colorant is not particularly limited, and examples thereof include carbon black, titanium oxide, zinc oxide, iron oxide, and aluminum oxide. Inorganic fillers, cyanine blue, cyanine green, miloli blue, selenium blue, cadmium red, cadmium yellow, cadmium orange, petals, ultramarine, phthalocyanine blue, etc. Is preferable, and carbon black is more preferable.

  Further, a rubber component may be added to the modified polyphenylene ether resin sheet 2 to prevent embrittlement. Examples of such a rubber component include high impact polystyrene and styrene-butadiene copolymer. Examples thereof include a styrene-butadiene-styrene block copolymer, and high impact polystyrene is preferable.

  If the content of the rubber component in the modified polyphenylene ether-based resin sheet 2 is small, the effect of preventing embrittlement of the modified polyphenylene ether-based resin sheet 2 may not be exhibited. Since the bending strength and rigidity of No. 2 may be lowered, 1 to 20 parts by weight is preferable with respect to 100 parts by weight of the modified polyphenylene ether resin.

  The modified polyphenylene ether resin sheets 2 and 2 are modified polyphenylene ethers constituting the modified polyphenylene ether resin foam sheet 1 directly on both sides of the modified polyphenylene ether resin foam sheet 1 without interposing an adhesive layer. Are firmly laminated and integrated by heat fusion between the resin and the modified polyphenylene ether resin constituting the modified polyphenylene ether resin sheet 2.

  That is, the modified polyphenylene ether-based resin sheet 2 and the modified polyphenylene ether-based resin foam sheet 1 are firmly integrated by the same type of resin constituting both, that is, by thermal fusion between the modified polyphenylene ether-based resins. In addition, the laminated sheet A for automobile interior materials can be accurately and reliably formed into a complicated shape without the modified polyphenylene ether resin sheet 2 being peeled off from the surface of the modified polyphenylene ether resin foam sheet 1.

  Furthermore, when the thickness of the modified polyphenylene ether-based resin sheet 2 is thin, the mechanical strength of the laminated sheet A for automobile interior materials may be reduced. On the other hand, when the thickness is thick, the moldability of the laminated sheet A for automobile interior materials is reduced. Since lightness may fall, 50-300 micrometers is preferable and 70-200 micrometers is more preferable.

  Next, the manufacturing method of the laminated sheet A for automobile interior materials will be described. First, as a manufacturing method of the modified polyphenylene ether resin foamed sheet 1, a conventionally used manufacturing method is used. The extrusion foaming temperature of the modified polyphenylene ether resin, the mold temperature attached to the extruder, or this mold The modified polyphenylene ether-based resin foam sheet 1 having a desired open cell ratio can be obtained by adjusting the surface cooling degree of the foam sheet immediately after being extruded from.

  Specifically, the method for producing the modified polyphenylene ether-based resin foam sheet 1 is, for example, (1) supplying the modified polyphenylene ether-based resin to an extruder, melt-kneading, and volatile foaming agent or / And a method for producing a foam sheet that is extruded from a mold attached to an extruder after being injected with an inorganic gas foaming agent and foamed, (2) An extruder after a modified polyphenylene ether resin is impregnated with a volatile foaming agent in advance For example, a foamed sheet manufacturing method for foaming by extrusion from a mold attached to an extruder.

  The volatile foaming agent is not particularly limited as long as it has been conventionally used, and examples thereof include ethane, propane, isobutane, normal butane, pentane, dimethyl ether, and the like. If it is conventionally used, it will not specifically limit, For example, a carbon dioxide gas, nitrogen, water etc. are mentioned, These may be used independently or may be used together.

  Moreover, it is preferable to adjust the kind and amount of the volatile foaming agent so that the amount of the residual foaming agent remaining in the modified polyphenylene ether resin foamed sheet 1 is 0.6 to 4.0% by weight. This is because if the amount of residual foaming agent in the foamed sheet 1 is small, a good quality foamed sheet 1 cannot be obtained, and if the amount is large, the foamed gas that has escaped from the foamed sheet 1 is mixed with the foamed sheet 1 and the modified polyphenylene ether. This is because the so-called air accumulation may occur at the interface with the resin sheet 2 and the heat resistance and dimensional stability of the foam sheet 1 may decrease.

  And as a method of laminating and integrating the modified polyphenylene ether resin sheets 2 and 2 on both surfaces of the modified polyphenylene ether resin foam sheet 1 obtained as described above, for example, (1) On both surfaces of the foam sheet 1 A method in which the modified polyphenylene ether resin sheets 2 and 2 are superposed and the above sheets 2 and 2 are heat-sealed and integrated on both sides of the foamed sheet 1 by a hot roll. (2) Both sides of the foamed sheet 1 are extruded from an extruder. A method of laminating the modified polyphenylene ether resin sheets 2 and 2 immediately after being formed, and laminating and integrating the sheets 2 and 2 on the surface of the foamed sheet 1 by heat fusion; (3) Both surfaces of the foamed sheet 1 by coextrusion Examples thereof include a method in which the modified polyphenylene ether resin sheets 2 and 2 are laminated and integrated.

  Further, the laminated sheet A for automobile interior materials is usually laminated and integrated on one surface of the laminated sheet A disposed inside the vehicle via an adhesive layer (not shown), and on the other surface. Then, the noise prevention layer 4 is laminated and integrated (see FIG. 2), and then molded into a desired shape by thermoforming and used as an automobile interior material.

  In addition, as a point of forming the adhesive layer on one surface of the laminated sheet A for automobile interior materials, for example, (1) a method of spraying a powdery adhesive on one surface of the laminated sheet A for automobile interior materials, (2) Examples thereof include a method of applying an adhesive on one surface of the laminated sheet A for automobile interior materials, and (3) a method of laminating a film made of an adhesive on one surface of the laminated sheet A for automotive interior materials.

  Examples of the skin material 3 include nonwoven fabrics, woven fabrics, and knitted fabrics. Note that a flame retardant may be included in order to impart flame resistance to the skin material 3. The fibers constituting the skin material 3 include polyesters such as polyethylene terephthalate, synthetic fibers such as polyamide and polyacrylonitrile, polyester fibers are preferable, and polyethylene terephthalate fibers are more preferable in terms of excellent heat resistance. preferable. In addition, the fiber which comprises the said skin material 3 may be used independently, or may be used together.

  The adhesive layer is not particularly limited as long as the skin material 3 and the laminated sheet A for automobile interior materials can be bonded and integrated. For example, a thermoplastic adhesive, a hot melt adhesive, a rubber adhesive , Thermosetting adhesives, monomer-reactive adhesives, inorganic adhesives, natural material-based adhesives, and the like. Hot melt adhesives are preferred because they can be easily bonded.

  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 abnormal noise prevention layer 4 is laminated and integrated on the other surface of the laminated sheet A for automobile interior materials. The abnormal noise prevention layer 4 is laminated on a steel sheet constituting an automobile body. This is for reducing frictional noise generated when A comes into sliding contact, and a nonwoven fabric such as a polyolefin resin film, a needle punched nonwoven fabric, or a spunbonded 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 is used preferably, and the thing of 25-35 micrometers is more preferably used.

  Furthermore, the fiber constituting the nonwoven fabric used for the noise preventing layer 4 is not particularly limited, and examples thereof include synthetic resin fibers such as polyester fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, and polyacrylonitrile fibers. .

  Finally, in FIG. 1 and FIG. 2, the interface between the center foam layer 11 and the skin foam layer 12 and the interface between the skin foam layer 12 and the non-foam layer (skin layer) 13 in the modified polyphenylene ether resin foam sheet 1 are shown for convenience. The boundary lines are described for easy understanding, but the interface between the central foam layer 11 and the skin foam layer 12 and the skin foam layer 12 and the non-foam layer (skin layer) in the modified polyphenylene ether resin foam sheet 1 of the present invention. There is no clear boundary line at the interface with 13.

  Next, as described above, the laminated sheet A for an automobile interior material is laminated and integrated with the skin material 3 on one surface and the noise preventing layer 4 is laminated and integrated on the other surface, and then the desired shape is formed by thermoforming. It is formed into a car interior material.

  As the thermoforming method of the laminated sheet A for automobile interior materials, a general-purpose method has been conventionally used. For example, the laminated sheet A for automotive interior materials preferably has a double-sided temperature (constituting the foam sheet 1). Within the range of the glass transition temperature Tg of the modified polyphenylene ether resin) to (the glass transition temperature Tg of the modified polyphenylene ether resin T + 40 ° C.), the surface of the laminated sheet A for automobile interior materials is heated as high as possible to the extent that it does not burn Then, after the secondary foaming, the secondary foamed laminated sheet A for automobile interior materials may be thermoformed using a general-purpose molding method such as vacuum forming or pressure forming.

  The reason why it is preferable to adjust the heating temperature of the laminated sheet A for automobile interior materials to be within the above temperature range is that, if low, residual strain occurs during thermoforming of the laminated sheet A for automobile interior materials, and the dimensional change rate is On the other hand, if it is high, excessive heat is applied to the laminated sheet A for automobile interior materials, causing the foamed sheet 1 to shrink, resulting in a decrease in mechanical strength or a poor shape of the laminated sheet A for automobile interior materials. It is because it may produce.

  The glass transition temperature Tg of the modified polyphenylene ether resin constituting the laminated sheet A for automobile interior materials is a value measured in accordance with the method described in JIS K7121: 1987 "Method for measuring plastic transition temperature". Specifically, it can be measured under the condition of a heating rate of 10 ° C./min using a differential scanning calorimeter marketed by Seiko Electronics Industry under the trade name “DSC200 type”.

  Examples of vacuum molding and pressure molding include plug molding, free drawing molding, plug and ridge molding, matched molding, straight molding, drape molding, reverse draw molding, air slip molding, plug assist molding, and plug assist reverse. Examples include draw molding. In the molding method, it is preferable to use a mold whose temperature can be adjusted.

  The laminated sheet for automotive interior materials according to the present invention is characterized in that a modified polyphenylene ether resin sheet is laminated and integrated on both surfaces of a modified polyphenylene ether resin foam sheet having an open cell ratio of 40 to 90%. Because the polyphenylene ether resin foam sheet has a high open cell ratio, when molding, the gas is smoothly deformed while the gas inside the foam sheet is smoothly drawn out of the foam sheet. The laminated sheet can be accurately formed into a desired shape.

  Moreover, the laminated sheet for automobile interior materials can minimize the expansion of the bubbles by smoothly dissipating the gas in the bubbles to the outside even when exposed to high temperatures after molding. In addition, the foamed sheet is stably retained in the form of bubbles after molding, and the foamed sheet is effectively prevented from being deformed, and is excellent in dimensional stability at high temperatures.

  And when molding the laminated sheet for automobile interior materials, the outer peripheral edge and the opening peripheral edge to which the indoor device such as the room mirror is compressed may be compressed in the thickness direction. Since the foam sheet of the laminated sheet for interior material has a high open cell ratio as described above, the foam sheet is desired while smoothly venting the gas in the bubbles in the part where the thickness is to be reduced in the foam sheet. The part can be smoothly compressed to the desired thickness and molded into a thin shape. Furthermore, the compressed part is hardly restored due to the springback phenomenon, and the thickness after compression can be stably maintained over a long period of time. Can be maintained.

  Furthermore, the continuous portion of the compressed portion (compressed portion) and the uncompressed portion (non-compressed portion) of the laminated sheet for automobile interior materials is a portion compressed from the uncompressed portion. In either case, the thickness of the compressed portion and the non-compressed portion are connected to each other in accordance with the degree of compression of the gas in the bubbles in that portion. Since the compression molding can be performed while pulling out, the compression portion can be molded in a beautiful state without causing cracks or the like in the continuous portion between the compression portion and the non-compression portion.

  In addition, when the foam sheet of the laminated sheet for automobile interior materials also has closed cells, a thick automotive interior material can be obtained by secondary foaming of the closed cells during the molding process. Automotive interior materials have excellent mechanical strength. And, as the interior temperature during use of the automobile interior material attached to the vehicle body increases, the closed cells that exist at a limited ratio in the foam sheet expand in the thickness direction so as not to impair the attachment property to the vehicle body. As a result, the vehicle is more stably attached to the vehicle body and has excellent attachment properties to the vehicle body.

  Further, when the foam sheet of the laminated sheet for automobile interior material is composed only of a foamed layer mainly composed of open cells, when the laminated sheet for automobile interior material is formed into the automobile interior material, the compressed portion of the foam sheet is used. Compression molding can be performed entirely without partial compression, and the foamed sheet can be accurately molded into a desired shape while maintaining the mechanical strength of the foam sheet.

  In the laminated sheet for automobile interior materials, when the modified polyphenylene ether-based resin foam sheet is formed by forming a skin foam layer mainly composed of closed cells on both sides of the central foam layer mainly composed of open cells. During molding, the gas inside the foamed sheet can be smoothly extracted to deform the foam into a desired shape, and the laminated sheet for automobile interior material can be smoothly molded into the desired shape. The laminated sheet for automobile interior materials has excellent formability, and an automotive interior material having an accurate shape and mechanical strength can be obtained smoothly by molding. Can do.

In the laminated sheet for automobile interior materials, when the density of the modified polyphenylene ether-based resin foamed sheet is 0.030 to 0.175 g / cm ³ , the lightweight and mechanical strength of the foamed sheet are made compatible. However, the bubble film constituting the bubbles of the foam sheet has an appropriate thickness, and the bubble film can be easily plastically deformed by an appropriate bending force. A desired portion of the laminated sheet can be smoothly compressed and molded into a compressed portion having a stable thin thickness in which the thickness does not recover over time.

  Further, in the laminated sheet for automotive interior materials, when the skin material is laminated and integrated on one side and the noise prevention layer is laminated and integrated on the other side, the laminated sheet for automotive interior materials is formed. By doing so, an automobile interior material having a complicated shape can be obtained accurately and easily.

(Example 1)
A mixture of polyphenylene ether and polystyrene resin (trade name “NORYL EFN4230” manufactured by GE Plastics, polyphenylene ether: 70% by weight, polystyrene resin: 30% by weight) and polystyrene (trade name, manufactured by Toyo Styrene Co., Ltd.) “HRM-26”) modified polyphenylene ether resin mixed with 50 parts by weight (polyphenylene ether component: 35 wt%, polystyrene resin component: 65 wt%, glass transition temperature: 132 ° C.) and talc 0.65 Part by weight is supplied to the first extruder and melt kneaded, and 3.6 parts by weight of a volatile foaming agent comprising 35% by weight of isobutane and 65% by weight of normal butane is injected into the first extruder and melted at 300 ° C. After kneading, the molten resin is continuously fed to the second extruder connected to the tip of the first extruder. Fed to it after adjusting so that the resin temperature is 202 ° C., extruded in a cylindrical shape from the circular die set to and 170 ° 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 resulting modified polyphenylene ether resin foamed sheet has a thickness of 3.3 mm, a density of 0.061 g / cm ³ (foaming ratio: 17.2 times), an open cell ratio of 54.0%, and an average cell size. The diameter was 0.44 mm and the basis weight was 200 g / m ² . The modified polyphenylene ether-based resin foam sheet 1 has a surface foam layer 12a mainly composed of closed cells and a foam layer 12a having a thickness of 0.8mm mainly formed on one surface of the center foam layer 11 composed mainly of open cells. On the other surface of the foam layer 11, a skin foam layer 12b having a thickness of 0.7 mm mainly composed of closed cells is formed, and the ratio of open cells contained in the central foam layer 11 is 88.6%. The ratio of closed cells contained in the layers 12a and 12b was 87.3%.

  Mixture of polyphenylene ether and polystyrene resin (trade name “NORYL EFN4230” manufactured by GE Plastics, polyphenylene ether: 70 wt%, polystyrene resin: 30 wt%) and polystyrene (trade name “HRM-, manufactured by Toyo Styrene Co., Ltd.”) 26 ”), high impact polystyrene (trade name“ E641N ”manufactured by Toyo Styrene Co., Ltd.), and carbon black masterbatch (trade name“ PS-M SSC 98H822A manufactured by Dainichi Seika Co., Ltd., carbon black: 40% by weight) as a colorant. Are mixed while adjusting so that the polyphenylene ether component is 20% by weight, the styrene resin component is 77.6% by weight, the rubber component is 2% by weight, and the carbon black is 0.4% by weight. Resin is supplied to each of two different extruders. The modified polyphenylene ether-based resin sheet in a molten state immediately after being extruded from one extruder is laminated on one surface of the modified polyphenylene ether-based resin foam sheet immediately after being developed and integrated by heat fusion, and the other A modified polyphenylene ether resin sheet in a molten state immediately after being extruded from the above extruder is laminated on the other surface of the foamed sheet and integrated by heat-sealing. The modified polyphenylene ether-based resin sheets 2 and 2 having a thickness of 95 μm that were colored black by the above were directly laminated and integrated by thermal fusion to obtain a laminated sheet A for automobile interior materials.

The obtained laminated sheet A for automobile interior materials had a thickness of 3.3 mm, a basis weight of 400 g / m ² , and an open cell ratio of 56.7%.

(Example 2)
When producing the modified polyphenylene ether-based resin foam sheet 1, a laminated sheet for automobile interior materials was obtained in the same manner as in Example 1 except that the temperature of the molten resin in the second extruder was adjusted to 206 ° C. It was.

In addition, the modified polyphenylene ether resin foamed sheet before lamination and integration of the modified polyphenylene ether resin sheet has a thickness of 3.0 mm and a density of 0.067 g / cm ³ (expanding ratio: 15.7 times), continuous. The bubble ratio was 71.1%, the average bubble diameter was 0.48 mm, and the basis weight was 200 g / m ² . The modified polyphenylene ether-based resin foam sheet 1 has a surface foam layer 12a mainly composed of closed cells on one surface of a center foam layer 11 composed of open cells and having a thickness of 2.1 mm. On the other surface of the foam layer 11, a skin foam layer 12b having a thickness of 0.4 mm mainly composed of closed cells is formed, and the ratio of open cells contained in the central foam layer 11 is 91.2%. The ratio of closed cells contained in the layers 12a and 12b was 84.1%.

Further, the obtained laminated sheet A for automobile interior materials had a thickness of 3.3 mm, a basis weight of 400 g / m ² , and an open cell ratio of 72.8%.

(Example 3)
In producing the modified polyphenylene ether-based resin foam sheet 1, 3.9 parts by weight of a volatile foaming agent composed of 35% by weight of isobutane and 65% by weight of normal butane was pressed into the first extruder, A laminated sheet for automobile interior materials was obtained in the same manner as in Example 1 except that the temperature of the molten resin was adjusted to 206 ° C.

In addition, the modified polyphenylene ether resin foam sheet before the lamination and integration of the modified polyphenylene ether resin sheet has a thickness of 4.9 mm and a density of 0.054 g / cm ³ (foaming ratio: 19.4 times), continuous. The bubble ratio was 70.0%, the average bubble diameter was 0.48 mm, and the basis weight was 265 g / m ² . The modified polyphenylene ether-based resin foam sheet 1 has a 0.8 mm thick skin foam layer 12a mainly composed of closed cells on one surface of a center foam layer 11 composed mainly of open cells and having a thickness of 3.4 mm. On the other surface of the foam layer 11, a skin foam layer 12b having a thickness of 0.7 mm mainly composed of closed cells is formed, and the ratio of open cells contained in the central foam layer 11 is 91.6%. The ratio of closed cells contained in the layers 12a and 12b was 81.8%.

Further, the obtained laminated sheet A for automobile interior materials had a thickness of 4.9 mm, a basis weight of 465 g / m ² , and an open cell ratio of 73.3%.

Example 4
In producing the modified polyphenylene ether-based resin foam sheet 1, 3.5 parts by weight of a volatile foaming agent comprising 35% by weight of isobutane and 65% by weight of normal butane is press-fitted into the first extruder, and the resin temperature in the second extruder Was adjusted to 205 ° C., and a laminated sheet for automobile interior materials was obtained in the same manner as in Example 1 except that the temperature of the circular mold was adjusted to 185 ° C.

In addition, the modified polyphenylene ether resin foamed sheet before the lamination and integration of the modified polyphenylene ether resin sheet has a thickness of 5.0 mm and a density of 0.060 g / cm ³ (expanding ratio: 17.5 times), continuous. The bubble ratio was 81.4%, the average bubble diameter was 0.57 mm, and the basis weight was 300 g / m ² .

  The modified polyphenylene ether-based resin foam sheet 1 is composed of only a foamed layer having a thickness of 4.8 mm mainly composed of open cells, and a non-foamed layer having a thickness of 0.1 mm is entirely formed on both sides of the foamed layer. Was formed.

Moreover, the obtained laminated sheet A for automobile interior materials had a thickness of 5.0 mm, a basis weight of 500 g / m ² , and an open cell ratio of 79.6%.

(Comparative Example 1)
In producing the modified polyphenylene ether-based resin foam sheet 1, the temperature of the molten resin in the second extruder was adjusted to be 182 ° C., and the first extruder was fed with 35% by weight of isobutane and 65% by weight of normal butane. A laminated sheet for automobile interior materials was obtained in the same manner as in Example 1 except that 4.0 parts by weight of the volatile foaming agent was press-fitted and the temperature of the circular mold was adjusted to 152 ° C.

In addition, the modified polyphenylene ether resin foam sheet before the lamination and integration of the modified polyphenylene ether resin sheet has a thickness of 2.7 mm and a density of 0.059 g / cm ³ (expanding ratio: 17.8 times), continuous. The bubble ratio was 10.0%, the average bubble diameter was 0.38 mm, and the basis weight was 160 g / m ² . The modified polyphenylene ether resin foam sheet did not have a foam layer mainly composed of open cells.

Further, the obtained laminated sheet A for automobile interior materials had a thickness of 2.7 mm, a basis weight of 360 g / m ² , and an open cell ratio of 15.5%.

  The crushability, formability, and dimensional stability of the laminated sheet for automobile interior materials obtained as described above were measured in the following manner, and the results are shown in Table 1.

(Crushability)
A skin material (made by Kurehatech Co., Ltd.) made of polyester fiber needle punched nonwoven fabric with a film (made by Kurabo Industries Co., Ltd., product name “X-2200”) made of a 30 μm thick hot melt adhesive on one surface of a laminated sheet for automobile interior materials , Basis weight: 150 g / m ² ), while the other side is made of polyester fiber spunbonded nonwoven fabric with anti-noise material (trade name “R-214” manufactured by Mitsui Chemicals, basis weight: 45 g / m ² ) A laminate was prepared by laminating via a melt adhesive.

  Next, the laminated body is supplied between a pair of polytetrafluoroethylene belts whose surface temperature is maintained at 135 to 145 ° C., and the laminated body is heated and compressed from both sides by the pair of belts, so that the vehicle interior material A skin material was laminated on one side of the laminated sheet for use, and an abnormal sound preventing material was laminated on the other side.

Subsequently, the laminate was supplied to a molding machine and heated with a far infrared heater until the surface temperature reached 150 ° C., and then the laminate was taken out from the molding machine. Then, after 11 seconds have elapsed from the removal of the laminate from the molding machine, the laminate is disposed between a pair of flat plate-like press plates, and the laminate is pressed by the press plate with a pressure of 0.31 MPa and a clearance of 0 mm. The sample was compressed in the thickness direction for 30 seconds below to produce a compression test piece. The maximum thickness in the thickness direction of this compression test piece was measured as the initial thickness T ₁ (mm).

Furthermore, after the compression test piece was supplied into a thermostat kept at 80 ° C. and left for 24 hours, the maximum thickness in the thickness direction of the compression test piece was measured as the post-restoration thickness T ₂ (mm). The restoration amount and restoration rate were calculated based on the following formula.
Restoration amount T ₃ (mm) = T ₂ −T ₁
Restoration rate (%) = 100 × T ₃ / T ₁

(Formability)
In the same manner as in the measurement of the crushability, a flat rectangular laminate of 700 mm in length and 1400 mm in width is prepared by laminating and integrating a skin material on one side and an anti-noise material on the other side. After 8 seconds have passed since the body was heated using a far infrared heater until the surface temperature reached 150 ° C., the laminate was held between the male and female molds maintained at room temperature having R parts of R2, R4 and R6. The male and female molds were clamped and the automobile interior material shown in FIG. 3 was molded.

  And the R shape of the automobile interior material corresponding to each R part of the molds R2, R4 and R6 was measured using a convex R measurement gauge. In Examples 1 to 4, the R shape of each R portion in the obtained automotive interior material was accurately formed corresponding to the R shape of the mold, but in Comparative Example 1, the obtained automotive interior material. Although the R shape of R4 and R6 was accurately molded corresponding to the R shape of R4 and R6 of the mold, the portion corresponding to the R shape of R2 of the mold is larger than R2. R4.

(Dimensional change rate)
A line having a length of 100 mm (dimension before heating) was drawn along the direction of the arrow in the part A and the part B shown in FIG. 3 in the automotive interior material stored at room temperature produced with moldability. Thereafter, the automobile interior material was left in a heating tank heated to 80 ° C. for 24 hours. Next, after taking out this automobile interior material from a heating tank, and letting it stand for 1 hour and cooling, the length of the straight line (the dimension after a heating) drawn on A part and B part was measured, and based on the following formula The dimensional change rate was measured.
Dimensional change rate (%) = 100 × (size after heating−size before heating) / size before heating

It is the schematic cross section which showed the laminated sheet for motor vehicle interior materials of this invention. It is the schematic cross section which showed another example of the laminated sheet for motor vehicle interior materials of this invention. It is the perspective view which showed the motor vehicle interior material shape | molded when measuring the moldability and dimensional change rate of the laminated sheet for motor vehicle interior materials obtained by the Example and the comparative example.

Explanation of symbols

1 Modified polyphenylene ether resin foam sheet
11 Central foam layer
12 Skin foam layer 2 Modified polyphenylene ether resin sheet 3 Skin material 4 Anti-noise material A Laminated sheet for automobile interior materials

Claims (6)

A laminated sheet for automobile interior materials, wherein a modified polyphenylene ether resin sheet is laminated and integrated on both surfaces of a modified polyphenylene ether resin foam sheet having an open cell ratio of 40 to 90%. The laminated sheet for automobile interior materials according to claim 1, wherein the modified polyphenylene ether-based resin foam sheet has a foam layer mainly composed of open cells. The laminated sheet for automobile interior materials according to claim 2, wherein the modified polyphenylene ether-based resin foam sheet is composed of only a foam layer mainly composed of open cells. The automobile interior according to claim 2, wherein the modified polyphenylene ether-based resin foam sheet is formed by forming a skin foam layer mainly composed of closed cells on both surfaces of a central foam layer mainly composed of open cells. Laminated sheet for materials. The laminated sheet for automobile interior materials according to any one of claims 1 to 4, wherein the density of the modified polyphenylene ether-based resin foam sheet is 0.030 to 0.175 g / cm ³ . 6. The automobile interior material according to claim 1, wherein a skin material is laminated and integrated on one surface and an abnormal sound prevention layer is laminated and integrated on the other surface. Laminated sheet.

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