JP2008110651A - Automobile interior trim material and automobile interior part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an automobile interior trim material and an automobile interior part using a foamed sheet making a modified PPE based resin as a base material, not including a glass fiber or the like, also having extremely lightweight, inexpensive and stable quality and environment fitting property and excellent in deodorant and antibacterial action. <P>SOLUTION: In the base material for the automobile interior trim material, a surface material is laminated on an indoor side surface of a non-foamed layer of a thermoplastic resin foamed laminated sheet formed with the non-foamed layer through a latex adhesive relative to the base material for the automobile interior trim material in which the non-foamed layers comprising a thermoplastic resin are laminated on both surfaces of the foamed layer obtained by extrusion-foaming-molding a thermoplastic resin. By incorporating a photocatalyst in the latex adhesive, the automobile interior trim material and the automobile interior part are obtained, which are excellent in deodorant and antibacterial action, do not contain the glass fiber, are light weight and inexpensive, prevent deterioration of the surface material and are provided with the stable quality and the environment fitting property. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an automobile interior material and an automobile interior part. More specifically, the present invention relates to an automotive interior material and an automotive interior component that have a deodorizing function, are lightweight and have environmental compatibility.

Conventionally, as an automobile interior material such as an automobile ceiling material, a sheet in which glass fibers are laminated on urethane foam and a laminated sheet in which glass fibers are mixed or laminated on polypropylene resin are widely used. These interior materials are characterized by excellent molding processability, heat resistance characteristics and sound absorption characteristics. On the other hand, these interior materials use glass fiber as a constituent material, so they are inferior in recyclability, particularly material recyclability, cannot be reduced in weight, and increase in fuel efficiency of automobiles increases CO ₂ amount. Therefore, it is inferior in environmental compatibility. On the other hand, as a substitute for glass fibers, laminated sheets in which sisal fibers / jute fibers are mixed or laminated as carbon fibers or natural fibers have also appeared. However, in order to ensure price stability and quality stability, these laminated sheets have to increase the amount of constituent fibers used. As a result, the weight cannot be reduced and the fuel consumption of the automobile increases. Since the amount of CO ₂ increases, the environmental compatibility is still not fully satisfied.

  In recent years, a further reduction in weight of automobile interior materials has been demanded in response to further demands for improving fuel consumption of automobiles. Furthermore, the comfort with respect to the temperature in the passenger compartment such as heat and cold in the passenger compartment of the automobile is affected by the heat insulating performance of the automobile interior material, and the conventional automobile interior material is inferior to this characteristic.

  In order to solve the above problems, a non-foamed layer made of a thermoplastic resin is laminated on both sides or one side of a foamed sheet using a modified polyphenylene ether resin (hereinafter referred to as “modified PPE resin”) as a base resin. An automobile interior material composed of the foamed laminated sheet, and an automobile interior material provided with a skin layer on its surface via an adhesive have been proposed (see Patent Documents 1 and 2, etc.).

  On the other hand, in recent years, for automobile interior materials, in order to improve comfort against odors in vehicle interiors, there has been a demand for lower VOC (so-called new car odor) of automobile interior materials and the appearance of components with a deodorizing function. ing. Various components using techniques related to functions such as deodorization, antibacterial function, and antifouling are known as constituent materials having a deodorizing function. For example, a deodorant that uses the excellent adsorption action of activated carbon is well known, but it has a function of adsorbing malodorous components and reducing the odor concentration around the activated carbon deodorant in the short term. Although it is excellent, it does not reduce the amount of malodorous components and is a deodorizing method with a limited expiration date. In addition, some deodorizing sprays are directly sprayed on odor-causing substances to deodorize, but in this method, a temporary deodorizing effect is manifested by the action of the fragrance, Odor is generated, and it has not become a radical odor elimination method. Furthermore, phthalocyanine is known as a method for deodorizing by decomposing malodorous components, but it is not effective against all malodors, and it is not effective against all offensive odors and is an odor generated by decomposition of tobacco odor and human sweat. It is not an effective deodorization method for bad odors such as herbic acid. As a deodorizing method other than phthalocyanine, a method using a titanium oxide photocatalyst is well known. When the titanium oxide photocatalyst is irradiated with light such as sunlight or black light, the organic matter is decomposed into carbon dioxide gas and water, etc., and the odor of isovaleric acid etc. that emits malodor due to decomposition of tobacco odor and human sweat is deodorized. It is known to do. This titanium oxide photocatalyst has been confirmed to have a bactericidal function that kills E. coli also due to its strong oxidizing power, and its antibacterial effect is also known.

  While photocatalysts such as titanium oxide photocatalyst have the above-mentioned beneficial functions, when the photocatalyst is directly supported on a fiber structure such as a non-woven skin or knitted skin of an automobile interior material by a binder resin, the skin Because the binder resin and fiber structure that make up the material are hydrocarbon resins that are organic substances, problems such as decomposition, discoloration, and generation of a strange odor due to the strong oxidative decomposition power of the photocatalyst occur, so the use is limited It was often done.

  In view of this, a fiber fabric having an excellent deodorizing, antibacterial, and antifouling function has been proposed that prevents discoloration and deterioration of the fiber by fixing the titanium oxide photocatalyst to the fiber structure with a silicone cross-linking resin. (See Patent Document 3). In addition, after forming a corrosion-resistant resin film made of a fluororesin on the surface of a cloth made of synthetic fiber, a photocatalytic film is formed on the film, thereby preventing the fiber structure from being discolored or deteriorated. Has been proposed (see Patent Document 4). Furthermore, a technique for manufacturing a porous photocatalyst by coating titanium oxide on the porous surface of silica gel inorganic material fine particles is disclosed (see Patent Document 5). In addition, water-absorbing inorganic porous material and photocatalyst are fixed to the fiber structure with an acrylic silicone binder resin to prevent discoloration and deterioration of the fiber structure, and have excellent deodorizing, antibacterial, and antifouling properties. A fiber fabric having a function has also been proposed (see Patent Document 6).

  In this way, environmentally friendly (environmental characteristics), inexpensive (price) and lightweight (lightweight characteristics) automotive interior materials, and the fabric fabric can be discolored and deteriorated while exhibiting a continuous deodorizing function. Various methods and materials for the prevention have been investigated. However, although the above-mentioned characteristics can be satisfied individually, automotive interior materials that have an excellent deodorizing function, are comprehensively satisfied with environmental characteristics, price, and light weight, and are easy to manufacture. There is still a demand for the emergence of materials that satisfy these characteristics.

JP-A-9-29875 JP-A-9-174729 Japanese Patent Laid-Open No. 10-1879 JP-A-10-216210 JP-A-8-196903 JP-A-2005-194652

  An object of the present invention is to provide an automobile interior material and an automobile interior part that have an excellent deodorizing function, are lightweight, and have both stable quality and environmental compatibility.

  In producing an automobile interior material in which a skin material is laminated on a room-side non-foamed layer of a thermoplastic resin foamed laminated sheet via a latex adhesive, the present inventors include a photocatalyst in the latex adhesive. The present inventors have found that automotive interior materials and automotive interior parts that have an excellent deodorizing function and suppress discoloration and deterioration of the skin material due to a photocatalyst can be obtained at low cost. Further, the thermoplastic resin is a mixed resin of a heat-resistant resin, in particular, a polyphenylene ether resin (hereinafter referred to as “PPE resin”) and a polystyrene resin (hereinafter referred to as “PS resin”). A non-foamed layer made of a modified PPE resin, which is a mixed resin of a PPE resin and a polystyrene resin, or a heat-resistant PS resin is formed on the surface of a foamed layer obtained by extrusion foam molding of a certain modified PPE resin. If it is an automobile interior material in which a skin material is laminated with a latex adhesive containing the photocatalyst on the non-foamed layer on the indoor side surface of the thermoplastic resin foam laminated sheet, it has an excellent deodorizing function and does not contain a glass component, It was found that automobile interior materials and automotive interior parts that are lightweight, prevent deterioration of the skin material, and have stable quality and environmental compatibility can be obtained at low cost.

That is, the present invention
(1) The non-foamed layer is formed on a surface of a foamed layer obtained by extrusion foam molding of a thermoplastic resin and a non-foamed layer made of a thermoplastic resin is laminated on the surface of the thermoplastic resin foamed laminate sheet via a latex adhesive. A vehicle interior material having a deodorizing function, wherein the latex adhesive contains a photocatalyst,
(2) The automobile interior material according to (1), wherein the photocatalyst is one or more photocatalysts selected from titanium oxide and zinc oxide, and has a particle diameter of 5 nm to 20 μm.
(3) The automobile interior material according to (1) or (2), wherein the photocatalyst is contained in an amount of 3 to 30 parts by weight with respect to 100 parts by weight of the latex adhesive.
(4) The automobile interior material according to any one of (1) to (3), wherein the latex adhesive is a latex having a polystyrene resin as a constituent resin.
(5) The automobile according to any one of (1) to (3), wherein the latex adhesive is a latex comprising a styrene / butadiene copolymer resin or a carboxylated modified styrene / butadiene copolymer resin as a constituent resin. Interior materials,
(6) A latex mixture in which the latex adhesive comprises a binder latex having a carboxylated modified styrene / butadiene copolymer resin as a constituent resin and a resin latex having a carboxylated modified acrylonitrile / styrene copolymer resin as a constituent resin. The automobile interior material according to any one of (1) to (3),
(7) The thermoplastic resin constituting the foam layer of the thermoplastic resin foam laminated sheet is a modified polyphenylene ether resin composed of 25 to 70% by weight of a polyphenylene ether resin and 75 to 30% by weight of a polystyrene resin ( 1)-(6) automobile interior material,
(8) The automobile interior material according to any one of (1) to (7), wherein the foamed layer of the thermoplastic resin foamed laminated sheet is obtained by extrusion foam molding using a hydrocarbon-based foaming agent.
(9) Any of (1) to (8) above, wherein the thickness of the foamed layer of the thermoplastic resin foamed laminated sheet is 1 to 5 mm, the expansion ratio is 3 to 20 times, and the basis weight is 100 to 300 g / m ² . Automotive interior materials,
(10) A modified polyphenylene ether resin comprising 5 to 70% by weight of a polyphenylene ether resin and 95 to 30% by weight of a polystyrene resin, and a heat-resistant thermoplastic resin constituting the non-foamed layer of the thermoplastic resin foamed laminated sheet The automobile interior material according to any one of (1) to (9), which is at least one of polystyrene resins,
(11) The automobile interior material according to any one of (1) to (10), wherein the basis weight of the non-foamed layer of the thermoplastic resin foamed laminated sheet is 50 to 300 g / m ² .
(12)
The automobile interior material according to any one of (1) to (11), wherein the skin material is made using a nonwoven fabric.
(13) The automobile interior material according to (12), wherein the nonwoven fabric includes a synthetic fiber,
(14) The automobile interior material according to (12) or (13), wherein the basis weight of the nonwoven fabric is 100 to 300 g / m ² .
(15) An automobile interior part formed by molding the automobile interior material of any one of (1) to (14) so that the skin layer is on the indoor side,
It is.

The present invention relates to a non-foamed layer on the interior side of a thermoplastic resin foam laminated sheet in which a non-foamed layer made of a thermoplastic resin is laminated on the surface of a foamed layer obtained by extrusion foam molding of a thermoplastic resin. It is a base material for automotive interior materials with a skin material laminated via an adhesive, and it is made entirely of plastic material, so it does not contain glass fiber, etc., it is very lightweight and has excellent environmental compatibility, and latex adhesion Because it contains a photocatalyst in the agent, it has a deodorizing function, and the addition of the deodorizing function is only to use a material containing a photocatalyst as an adhesive in the production process of a conventional automobile interior material. Since it can be manufactured by an extremely simple method, an automobile interior material satisfying various characteristics such as a deodorizing function and other lightweight properties required for the automobile interior material can be obtained at low cost.
In addition, the photocatalyst is contained in the latex adhesive that adheres the skin material to the thermoplastic resin foam laminated sheet, and is contained in the adhesive layer located on the inner side of the skin material, so that light directly contacts the photocatalyst. Therefore, the excessive oxidative decomposition force by the photocatalyst can be suppressed, and the decomposition, discoloration, generation of off-flavor, etc. of the hydrocarbon resin in the binder resin and the fiber structure constituting the skin can be suppressed.

  The automotive interior material according to the present invention is a thermoplastic resin in which a non-foamed layer made of a thermoplastic resin is laminated on the surface of a foamed layer obtained by extrusion foam molding of a thermoplastic resin, preferably on both surfaces of the foamed layer. An automotive interior material in which a skin material is laminated on a foamed laminated sheet via a latex adhesive, wherein the latex adhesive contains a photocatalyst and has a deodorizing function by the photocatalyst.

  Hereinafter, although the automobile interior material and the automobile interior part of the present invention will be described in more detail based on the drawings, the present invention is not limited thereto.

  FIG. 1 shows a cross-sectional configuration of an automobile interior material 1 according to an embodiment of the present invention. In addition, since the vehicle interior component which shape | molded this also has the same cross-sectional structure, hereafter, the structure of the vehicle interior material 1 is demonstrated. In the automobile interior material 1, the noise prevention layer 20 is laminated on the outdoor side of the thermoplastic resin foam laminated sheet 50, and the skin material 30 is laminated on the indoor side. The thermoplastic resin foam laminate sheet 50 has non-foamed layers 11 (inside the room) and 13 (inside the interior) and thermoplastic resin as the base resin on both surfaces of the foamed layer 10 which is an extruded foam sheet using the thermoplastic resin as the base resin. Outdoor side) is formed. The noise prevention layer 20 is laminated on the surface of the outdoor non-foamed layer 13 of the thermoplastic resin foam laminated sheet 50, and the skin material 30 is an adhesive containing the photocatalyst 40 on the surface of the indoor non-foamed layer 11. They are stacked via the layer 18.

As the thermoplastic resin used as the base resin of the foam layer 10 which is a foam sheet, for example,
Heat-resistant polystyrene resins such as styrene-acrylic acid copolymer, styrene-maleic anhydride copolymer, styrene-itaconic acid copolymer;
Modified PPE resins such as polystyrene or heat-resistant polystyrene and polyphenylene ether (PPE) blends, styrene / phenylene ether copolymers such as styrene graft polymers on PPE;
Polycarbonate resin;
Polyester resins such as polybutylene terephthalate and polyethylene terephthalate;
Etc.
These resins can be used alone or in combination of two or more. Among these, a modified PPE resin is preferable in that it has excellent quality such as heat resistance and rigidity, and is easy to process and manufacture. Furthermore, the modified PPE resin is preferably a mixed resin of a PPE resin and a PS resin.

  Specific examples of the PPE resin in the modified PPE resin include, for example, poly (2,6-dimethylphenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-4-ether), Poly (2,6-diethylphenylene-1,4-ether), poly (2,6-diethylphenylene-1,4-ether), poly (2-methyl-6-n-propylphenylene-1,4-ether) ), Poly (2-methyl-6-n-butylphenylene-1,4-ether), poly (2-methyl-6-chlorophenylene-1,4-ether), poly (2-methyl-6-bromophenylene) -1,4-ether), poly (2-ethyl-6-chlorophenylene-1,4-ether) and the like, and these can be used alone or in combination of two or more.

  Specific examples of the styrene monomer that is polymerized, preferably graft-polymerized, on the PPE resin include, for example, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, dichlorostyrene, and p-methylstyrene. And ethyl styrene. These may be used alone or in combination of two or more. Among these, styrene is preferable in terms of versatility and cost.

  PS resins that form mixed resins with PPE resins in modified PPE resins include styrene or derivatives thereof, such as α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, dichlorostyrene, p-methylstyrene. And a resin mainly composed of ethylstyrene or the like. Therefore, the PS-based resin is not limited to a homopolymer composed of only styrene or a styrene derivative, but may be a copolymer obtained by copolymerizing with another monomer.

  When a modified PPE resin is used as the base resin used for the foamed layer 10, it is usually preferably 25 to 70% by weight of PPE resin and 75 to 30% by weight of PS resin. It is more preferably 35 to 60% by weight and PS resin 65 to 40% by weight, and further preferably 38 to 58% by weight PPE resin and 62 to 42% by weight PS resin. If the PPE resin in the modified PPE resin is less than 25% by weight, the heat resistance tends to be inferior. If the PPE resin exceeds 70% by weight, the viscosity at the time of heat flow increases and foam molding becomes difficult. Tend to be.

  In addition, the foam sheet as the foam layer 10 is preferably obtained by extrusion foam molding using a hydrocarbon-based foaming agent as a foaming agent in terms of compatibility with the base resin. The hydrocarbon foaming agent used is preferably a volatile foaming agent from the viewpoint of foamability of the base resin, and specific examples include ethane, propane, butane, pentane and the like. Among them, the hydrocarbon-based foaming agent having a Kauri-butanol value (KB value) indicating the solubility of the foaming agent of 20 to 50 is compatible with the base resin and has good foamability and small change over time in foamability. preferable. When the KB value is less than 20, the compatibility with the base resin is insufficient, and the content of the foaming agent in the base resin tends to decrease. On the other hand, when the KB value exceeds 50, the dissipation of the foaming agent included in the base resin tends to increase. In addition, it is also possible to use those having the above range by appropriately mixing two or more types having a KB value higher and lower than this range. Furthermore, among the specific examples of the foaming agent, isobutane or isobutane is suitable in that the moderate solubility of the foaming agent and the dissipation of the foaming agent are small, and the change in foamability with the aging of the foamed layer is small. And a mixture of normal butane having a high isobutane ratio, and further preferably having an isobutane content of 50% by weight or more. When the isobutane content in the mixture is less than 50% by weight, the dissipating property of the foaming agent is large, and the change in foamability accompanying the change with time of the foamed layer tends to be large.

  The amount of the hydrocarbon-based foaming agent added when the foamed sheet of the foamed layer 10 is subjected to extrusion foam molding is preferably 2.0 to 5.0 parts by weight with respect to 100 parts by weight of the heat resistant resin. More preferably, it is -4.5 weight part. When the addition amount of the hydrocarbon-based foaming agent is less than 2.0 parts by weight, the secondary foaming ratio at the time of molding heating may be too low, which tends to have an adverse effect on obtaining good moldability. If it exceeds 0.0 parts by weight, extrusion foaming tends to be unstable, or the surface of the foamed sheet tends to be rough.

  When the automobile interior material 1 of the present invention is molded to produce an automotive interior part, heat is applied during molding, and the foamed layer 10 (primary foamed sheet) is further foamed (secondary foamed). As thickness of the foam layer 10 (primary foam sheet), 1.0-5.0 mm is preferable and 1.5-3.5 mm is more preferable. If the thickness of the foamed layer 10 (primary foamed sheet) is smaller than 1.0 mm, the strength and heat insulating properties are inferior and may not be suitable as an automobile interior material. On the other hand, when the thickness exceeds 5.0 mm, heat is hardly transmitted to the central portion in the thickness direction of the foamed layer 10 when the foamed layer 10 (primary foamed sheet) is further foamed (secondary foamed) due to heat applied during molding. Therefore, sufficient heating cannot be performed, and the moldability tends to decrease. In addition, if the heating time is increased to perform sufficient heating, bubbles may be generated in the cells on the surface of the foam layer 10, and it may be difficult to obtain an acceptable product.

  The expansion ratio of the foam layer 10 (primary foam sheet) is preferably 3 to 20 times, and more preferably 5 to 15 times. When the foaming ratio of the foamed layer 10 (primary foamed sheet) is lower than 3 times, the flexibility is inferior, breakage due to bending or the like tends to occur, and the effect of weight reduction tends to be reduced. When the foaming ratio of the foamed layer 10 (primary foamed sheet) exceeds 20 times, the strength is lowered, and heat is not easily transmitted during molding, and it is difficult to heat up to the center part, and thus formability tends to be lowered. .

  The cell diameter, which is the size in the thickness direction of the primary foamed sheet, of the cells of the primary foamed layer forming the foamed layer 10 (primary foamed sheet) is preferably 0.05 to 0.9 mm, preferably 0.1 to 0. 7 mm is more preferable. If the cell diameter is smaller than 0.05 mm, sufficient strength tends to be difficult to obtain, and if it exceeds 0.9 mm, the heat insulation tends to be poor.

Basis weight is preferably from 100 to 300 g / m ² of the foam layer 10 (primary foamed sheet), 120~200g / m ² is more preferable. When the basis weight is lower than 100 g / m ² , the rigidity as the interior material tends to be insufficient, and when the basis weight exceeds 300 g / m ² , the effect of lightness tends to decrease due to an increase in weight.

  The amount of residual volatile components in the foamed layer 10 (primary foamed sheet) is preferably 1.0 to 5.0% by weight, more preferably 2.0 to 4.0% by weight based on the total weight of the foamed layer 10. preferable. If the residual volatile component is less than 1.0% by weight, the secondary foaming ratio when molding an interior product may be too low, and this tends to affect obtaining good moldability. On the other hand, if the residual volatile component exceeds 5.0% by weight, air retention may occur between the non-foamed layers 11 and 13, and the dimensional stability over time tends to decrease. The amount of residual volatile components in the foamed layer 10 may be measured by gas chromatography, but usually the temperature range above the temperature at which the heat resistant resin begins to soften the test piece of the foamed layer 10 and below the decomposition temperature. It can be measured by the difference in weight before and after heating to sufficiently volatilize volatile components by heating.

  In general, in the foam layer 10 (primary foam sheet), a cell that has been flattened during extrusion foam molding changes its shape in a direction that eliminates the flatness ratio during molding heating, thereby causing heat shrinkage. To do. The heat shrinkage results in thermal deformation of the automobile interior material (hereinafter referred to as “heat-resistant deformation”).

  The heat-resistant deformation means that, when a car interior material is subjected to a heat test, a dimensional change of the car interior material occurs due to a shape deformation due to heat shrinkage of the foamed cell before and after heating. For example, in the case of a car ceiling material In the bent part of the ceiling molded body after the heating test, it means a phenomenon in which deformation occurs in the heating test and the end portions of the front and rear parts are deformed.

  Shape change such as heat-resistant deformation can be suppressed by making the density of cells in the front and back surface layer portions of the foamed layer 10 (primary foamed sheet) larger than the density of cells in the central layer portion of the foamed layer. Specifically, the surface layer portion of the foam layer is formed by forming the surface layer portion on the front and back surfaces of the foam layer as a hard skin layer by uniformly cooling both the front and back surface layer portions of the foam layer 10 during extrusion foam molding. The amount of heat shrinkage can be suppressed by stiffening the part.

  Furthermore, the amount of heat shrinkage can be reduced by making the change in the cell internal pressure of the foamed layer 10 as small as possible. For example, by securing a time (curing time) of 30 days or more after the foamed layer 10 is formed into an extruded foam sheet until the non-foamed layers 11 and 13 are laminated, the change in the cell internal pressure can be made as small as possible.

  In addition, the amount of heat-resistant deformation due to heat shrinkage is controlled even when the non-foamed layer 11 or 13 is not laminated, by controlling the heating temperature at the time of secondary heat molding to a range of 135 to 155 ° C. It can also be reduced by molding under conditions that do not give any distortion.

  In addition, the base resin of the foam layer 10 which is a foam sheet includes, as necessary, an air conditioner, an impact resistance improver, a lubricant, an antioxidant, an antistatic agent, a pigment, a stabilizer, an odor reducing agent, Talc or the like may be added.

Next, the non-foamed layers 11 and 13 will be described.
The non-foamed layers 11 and 13 are laminated on the foamed layer 10 so that the movement of the foamed layer 10 due to heat deformation due to heating is controlled by the non-foamed layers 11 and 13, and the heat-deformed control of the foamed laminated sheet at a high temperature. Further, the stability of the molded body shape at the time of molding is achieved, and the bending rigidity is further improved. It should be noted that an improvement in bending rigidity is required because the interior material does not bend or bend when the automobile interior material is moved or assembled to the vehicle body, thereby causing a problem in handling (handling properties).
Specific examples of the thermoplastic resin used for the non-foamed layer 11 or 13 include, for example, a PS resin, a heat resistant PS resin, a modified PPE resin, a polyethylene terephthalate (PET) resin, and a polyamide (nylon) resin. These can be used alone or in combination of two or more. Among these, a modified PPE resin and a heat-resistant PS resin are preferably used from the viewpoint of adhesiveness with the foamed layer 10.

  When the modified PPE resin is used as the non-foamed layer 11 or 13, the modified PPE resin used as the non-foamed layer 11 or 13 is styrene based on the PPE resin as in the case of the foamed layer 10 described above. It has been modified by polymerization with a monomer mainly composed of a compound or by mixing with a styrene polymer. For example, a mixed resin of a PPE resin and a PS resin, a styrene monomer in a PPE resin PPE-styrene copolymer obtained by polymerizing styrene, a mixture of this copolymer and PS resin or PPE resin, a mixture of the copolymer, PPE resin and PS resin, and the like. Among these, a mixed resin of a PPE resin and a PS resin is preferable from the viewpoint of easy production.

Specific examples and preferred examples of the PPE resin, PS resin or styrene monomer, specific examples of a monomer polymerizable with the PS resin and styrene monomer, the reason for using it, This is the same as described for the foamed layer 10. However, as a preferable specific example of the PS-based resin, a styrene-butadiene copolymer represented by high impact polystyrene (HIPS) is preferable because the impact resistance improving effect of the non-foamed layers 11 and 13 is large.
By the way, according to the research by the present inventors, the dimensional change due to the thermal deformation of the automobile interior material has a residual strain in the non-foamed layers 11 and 13 during the molding process such as secondary molding, and the use conditions such as under high temperature. It is known that the residual strain is generated by relaxation.
When the foamed laminated sheet is molded by thermoforming, if the foamed laminated sheet is overheated to such an extent that the residual distortion of the non-foamed layers 11 and 13 is removed, foam breakage occurs in the foamed layer 10, resulting in surface roughness or non-foamed layer 11 and 13 are peeled off from the foamed layer 10 and the appearance is impaired. On the other hand, when heated at a temperature low enough to suppress foam breakage of the foamed layer 10, the non-foamed layers 11 and 13 are insufficiently heat-softened and cannot exhibit sufficient elongation, resulting in residual strain and thermal deformation. Cause a dimensional change.
Therefore, the glass transition temperature (hereinafter referred to as “Tg”) of the thermoplastic resin constituting the non-foamed layers 11 and 13, which is one index of the degree of thermal softening of the non-foamed layers 11 and 13, constitutes the foamed layer 10. The above problems can be solved by making the Tg or less of the thermoplastic resin to be used. Specifically, the thermoplastic resin constituting the non-foamed layer 11 or 13 is a modified polyphenylene ether resin composition composed of 5 to 70% by weight of a polyphenylene ether resin and 95 to 30% by weight of a polystyrene resin. Preferably, the PPE ratio of the polyphenylene ether resin constituting the foam layer is less than or equal to.
On the other hand, when a modified PPE resin is used as the thermoplastic resin constituting the non-foamed layer 11 or 13, a thermoplastic resin having a Vicat softening temperature equal to or higher than the heat resistance evaluation temperature is preferable. The reason is that if the non-foamed layer 11 or 13 is softened at the heat resistance evaluation temperature, it cannot function to control the cell movement of the foamed layer 10.

  When heat-resistant PS resin is used as the non-foamed layers 11 and 13, the heat-resistant PS resin used as the non-foamed layers 11 and 13 is a copolymer of styrene or a derivative thereof and another monomer. . Examples of monomers having an effect of improving heat resistance and copolymerizable with styrene or derivatives thereof include unsaturated carboxylic acids such as maleic acid, fumaric acid, acrylic acid, methacrylic acid, and itaconic acid or derivatives thereof. And nitrile compounds such as acid anhydrides, acrylonitrile, and methacrylonitrile, or derivatives thereof. These may be used alone or in combination of two or more. In addition, when polymerizing styrene or a styrene derivative, a polymer obtained by adding synthetic rubber or rubber latex, an unsaturated carboxylic acid such as maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid or the like Derivatives and acid anhydrides thereof, and copolymers with nitrile compounds such as acrylonitrile and methacrylonitrile may also be used. Among these, styrene-maleic anhydride copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, acrylonitrile-butadiene-styrene copolymer, its heat resistance improving effect, general purpose From the viewpoint of property and cost.

As the base resin for the non-foamed layer 11 or 13, the heat-resistant PS resin may be used alone or in combination of two or more. The heat-resistant PS resin may be blended with other thermoplastic resins. Examples of the thermoplastic resin to be blended include polystyrene, HIPS, polycarbonate, polyester, polyamide, and copolymers thereof. Among these, HIPS is preferable from the viewpoints of versatility, uniform dispersion, a large effect of improving the impact resistance of the non-foamed layer, and cost. A known HIPS can be used, and the content of the rubber component is usually 1 to 15% by weight.
When a heat-resistant PS resin is used as the thermoplastic resin constituting the non-foamed layer 11 or 13, a resin having a Vicat softening temperature that is equal to or higher than the heat resistance evaluation temperature is preferable, as in the case of using a modified PPE resin. .

Basis weight of the non-foamed layer 11 and 13 is preferably ^{50~300g / m 2, 75~200g / m} 2 is more preferable. When the basis weight of these non-foamed layers is lower than 50 g / m ² , the strength, rigidity, heat resistance and the like tend to decrease, and when higher than 300 g / m ² , the foamed laminated sheet tends to be inferior in moldability. There is.

  If necessary, the thermoplastic resin forming the non-foamed layers 11 and 13 may contain an impact resistance improver, a filler, a lubricant, an antioxidant, an antistatic agent, a pigment, a stabilizer, an odor reducing agent, and the like. You may add individually or in combination of 2 or more types. The impact resistance improver is formed by laminating non-foamed layers 11 and 13 on the foamed layer 10 and punching processing when molding a laminated sheet that is secondarily foamed at the time of heat molding as an automobile interior part, or an interior material (foamed laminate). This is effective for preventing cracking of the non-foamed layers 11 and 13 when transporting the sheet) and the interior parts (molded body). Any impact resistance improver may be used without particular limitation as long as it can be mixed with the base resin to exert its effect. Further, the impact resistance improver may be a component capable of exhibiting the impact resistance improving effect introduced into the thermoplastic resin by modification by polymerization, for example, containing an impact resistance improving component such as HIPS. Even when these are mixed and used for the non-foamed layer, impact resistance can be imparted to the non-foamed layer 11 or 13.

  As the noise preventing layer 20, any non-woven fabric or woven fabric fiber material can be used. The nonwoven fabric used for the noise prevention layer 20 may be of any type as long as the raw material fibers are joined by an adhesive, molten fiber, or a mechanical method. The type of the raw fiber is not particularly limited, and any of synthetic fiber, semi-synthetic fiber, or natural fiber can be used. Specifically, synthetic fibers such as polyester, polypropylene, polyamide (nylon), polyacrylonitrile, and natural fibers such as wool, cotton, and cellulose can be used. Among them, polyester fibers are preferable, and particularly high heat resistance. Polyethylene terephthalate fibers are preferred. Examples of the type of nonwoven fabric include a bonded binder-bonded fabric, a needle punched fabric, a spunbonded fabric, a spray fiber fabric, a water needle fabric, and a stitchbonded fabric, and any nonwoven fabric can be used.

  As shown in FIG. 1, an automobile interior material 1 according to the present invention has an outer skin through an adhesive layer 18 on the surface of one indoor-side non-foamed layer 11 among the non-foamed layers 11 and 13 on both sides of the foamed layer 10. The material 30 is laminated. The skin material 30 is a member that is laminated on the outermost layer on the indoor side of the automobile interior material 1 and is disposed at a portion that can be seen and touched from the interior of the automobile. Therefore, particularly, design properties, scratch resistance, touch feeling, and the like are required. .

  As the structure of the skin material 30, any nonwoven fabric, nonwoven fabric / knit laminate, nonwoven fabric / pad material / knit laminate, pad material / knit laminate, etc., can be used. can do.

  The nonwoven fabric used for the skin material 30 may be of any type as long as it is a cloth-like material obtained by bonding raw material fibers with an adhesive, a molten fiber, or a mechanical method. The type of raw fiber is not particularly limited, and any of synthetic fiber, semi-synthetic fiber, or natural fiber can be used. Specifically, synthetic fibers such as polyester, polypropylene, polyamide (nylon), polyacrylonitrile, and natural fibers such as wool, cotton, and cellulose can be used. Among them, polyester fibers are preferable, and particularly high heat resistance. Polyethylene terephthalate fibers are preferred.

  As a kind of the nonwoven fabric used for the skin material 30, a bonding binder-bonded fabric, a needle punch fabric, a spunbond fabric, a spray fiber fabric, a stitchbond fabric, or the like is used depending on the manufacturing method, and any nonwoven fabric is used. can do.

Nonwoven fabric used in the skin material 30, taking into account the quality and cost, preferably has a basis weight of 100 to 300 g / m ^2, more to have a basis weight of 120~200g / m ² preferable. When the basis weight of the nonwoven fabric is less than 100 g / m ^2, there is a tendency that sufficient feel as an interior material cannot be obtained. On the other hand, when the basis weight of the nonwoven fabric exceeds 300 g / m ² , the molding distortion of the skin material tends to affect the thermal deformation.

  The pad material used for the skin material 30 is used for the purpose of improving the tactile sensation (high-quality feeling) of the skin material, and a foam having properties as a cushioning material is used. As the type of foam used as the pad material, polyurethane foam, polyvinyl chloride foam, polypropylene foam, polyethylene foam, polybutadiene foam and the like can be used.

  Any knit can be used for the skin material 30 as long as it is used for interior materials such as tricot, double raschel, and velvet.

  Next, the adhesive 18 that bonds the skin material 30 to the thermoplastic resin foam laminated sheet will be described. In the present invention, as a resin component of the adhesive layer 18 used for laminating the skin material 30 on the indoor non-foamed layer 11, a thermoplastic resin (hereinafter referred to as a resin that is compatible with the resin constituting the non-foamed layer 11). , Sometimes referred to as “adhesive resin”). As a specific example, when the non-foamed layer 11 is a modified PPE resin or a heat resistant PS resin, a PS resin, a heat resistant PS resin, a modified PPE resin, a styrene / butadiene copolymer resin (hereinafter referred to as “SB system”). Resin ”), carboxylated modified styrene / butadiene copolymer resin (hereinafter sometimes referred to as“ carboxylated modified SB resin ”) and carboxylated modified acrylonitrile / styrene copolymer. Resin (hereinafter sometimes referred to as “carboxylated modified AS resin”). Among these, PS resin, SB resin, carboxylated modified SB resin, and carboxylated modified AS resin are particularly preferable from the viewpoint of processability, versatility, and cost.

  The PS resin as the adhesive resin is a resin mainly composed of styrene or a derivative thereof such as α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, dichlorostyrene, p-methylstyrene, ethylstyrene, and the like. . Accordingly, the PS-based resin is not limited to a homopolymer composed of only styrene or a styrene derivative, but may be a copolymer made by copolymerizing with another monomer.

  The SB resin as the adhesive resin is a copolymer of styrene or a derivative thereof (styrene monomer) and a butadiene monomer. The ratio of the styrene monomer and the butadiene monomer to be polymerized is that the ratio of the styrene monomer is high in heat resistance, and the ratio of the styrene monomer is high in compatibility with the non-foamed layer 11. The higher the ratio of the styrenic monomer, the better. The specific content of the styrenic component in the SB resin is preferably 60% by weight or more. When the content of the styrenic component in the SB resin is less than 60% by weight, peeling of the skin material may occur during use at high temperatures due to deterioration of heat resistance.

  In addition to the composition based on the monomer ratio, the physical properties of the SB resin include molecular structures based on the double structure of butadiene (1,2-addition structure, 1,4-addition structure (cis and trans), bridged structure). The rubbery nature comes from the 1,4 addition structure. For this reason, if there are too many bridge structures, the rubber-like elongation characteristics will be lost, and if there are too few, the properties such as solvent resistance will not be exhibited, so the final resin physical properties will be designed by adjusting the amount of this bridge structure and designing the molecular weight. Is done.

  The carboxylation-modified SB resin as an adhesive resin is a copolymer composed of styrene or a derivative thereof (styrene monomer), a butadiene monomer, and an unsaturated carboxylic acid monomer. As the monomer of unsaturated carboxylic acid to be used, either monobasic acid or dibasic acid can be used, for example, maleic acid, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid Etc. From the viewpoint of strength, heat and light stability, the composition ratio of the carboxyl group-containing monomer to be introduced is preferably 1 to 10% by weight when the total resin is 100% by weight. In addition, the content of the styrene component in the carboxylated SB resin is preferably 60% by weight or more for the same reason as that of the SB resin.

  As the adhesive resin for the adhesive layer 18, it is possible to use the above-mentioned PS resin latex, SB resin latex, carboxylated modified SB resin latex, carboxylated modified AS resin latex alone, In order to satisfy various required characteristics as an automobile interior material, it is preferable to use a mixture of several types of latexes. Among them, by using a mixture of binder latex with good low-temperature film formability and resin latex with high heat resistance, stable and strong initial adhesive strength that does not depend on drying processing conditions in the manufacturing process, and latex adhesion The heat resistance of the adhesive layer 18 can be compatible, and the stability of the adhesive 18 against mechanical force such as shearing force applied to the adhesive resin during application when the adhesive 18 is applied to the thermoplastic resin foamed laminated sheet. It is more preferable because improvement (hereinafter referred to as “mechanical stability”) can improve handling in the manufacturing process.

  As the binder latex, a latex having a carboxylated modified SB resin as a constituent resin is preferable from the viewpoint of good mechanical stability and compatibility with the non-foamed layer 11. Among the latexes having the carboxylated SB resin as a constituent resin, in the present invention, the minimum film forming temperature, which is the temperature at which the latex particles are fused to form a continuous layer after drying, is 20 ° C. or less. Are preferred, and those of 0 ° C. or lower are more preferred. When the minimum film forming temperature of a binder latex such as SB resin latex exceeds 20 ° C., when a drying failure occurs in the drying process, film formation does not occur due to drying at room temperature, and adhesion failure may occur. . However, the minimum film formation temperature of the carboxylation-modified SB resin latex substantially depends on the ratio of the styrene component and the butadiene component of the SB resin latex. As the minimum film formation temperature decreases, the ratio of the butadiene component increases. Since the compatibility with the non-foamed layer 11 made of a resin is deteriorated, the minimum film formation temperature is calculated as follows: [calculation formula: minimum film formation temperature (° C.) = 2.9 × (styrene component (wt%)) − 175], -30 [deg.] C. or higher is preferable, where the styrene component is 50 wt% or higher.

  Further, as the resin latex, a latex having a carboxylated modified AS copolymer resin compatible with the non-foamed layer 11 as a constituent resin has good mechanical stability and compatibility with the non-foamed layer 11. It is preferable from the point of having. The carboxylated AS resin is a copolymer of styrene or a derivative thereof (styrene monomer), an acrylonitrile monomer, and a carboxyl group-containing monomer. The composition ratio of the introduced acrylonitrile-based monomer and carboxyl group-containing monomer is preferably 1 to 10% by weight when the entire resin is 100% by weight from the viewpoint of strength, heat and light stability.

  The mixing ratio of the resin latex in the latex mixture is preferably 20 to 50% by weight, and more preferably 30 to 50% by weight. When the mixing ratio of the resin latex is less than 20% by weight, the heat resistance of the adhesive layer may be lowered and may not reach a level required as a practical characteristic of the interior material. Without forming a phase, the minimum film forming temperature of the latex mixture becomes 20 ° C. or higher, and there is a possibility that film formation does not occur due to drying at room temperature, resulting in poor adhesion.

  Further, the minimum film forming temperature of the latex adhesive such as the latex mixture is preferably 20 ° C. or less, and more preferably 0 ° C. or less. When the minimum film forming temperature of the latex adhesive exceeds 20 ° C., film formation does not occur due to drying at room temperature, and adhesion failure may occur.

As a method of bonding the non-foamed layer 11 and the skin material 30 with the adhesive layer 18 made of a latex adhesive as described above,
(1) A method in which a latex adhesive is applied to the surface of the non-foamed layer 11, dried in a state where the skin material 30 is laminated on an undried application surface, temporarily bonded, and then bonded by heating and pressing.
(2) After applying a latex adhesive to the skin material 30 in advance and drying and temporarily adhering the thermoplastic resin foam laminated sheet 50 so that the non-foamed layer 11 is in contact with the undried application surface , A method of bonding by hot pressing,
Either of these is preferable.

  By applying the latex adhesive as described above and laminating the non-foamed layer 11 and the skin material 30 in an undried state, foaming of the foamed sheet does not occur when a modified PPE resin foamed sheet or the like is used. The required adhesiveness is also stably exhibited by heat molding (pressing) at the heating temperature.

  As the latex used as an adhesive in the present invention, any latex known for carpet backing, coated paper, or nonwoven fiber treatment can be used.

  The solid content concentration in the latex stock solution is usually 40% by weight or more, but it can be used after appropriately diluted with water according to the coating amount and coating method. However, if the concentration of the solid content of the latex water diluted solution is too low, drying in the process becomes insufficient and may cause poor adhesion, so 20% by weight or more is preferable.

  The binder latex or resin latex used in the present invention is preferably a latex having good mechanical stability because it undergoes mechanical operations without interruption such as pumping in the production process, stirring during blending, shearing by a roll coater during coating, etc. . Measures to improve the mechanical stability of latex include increasing the amount of emulsifier added, adjusting the pH to the alkali side, carboxylating the latex, etc., but carboxylation modification is the most effective, The use of carboxylated modified latex is preferred.

  Examples of the method for applying the latex adhesive in the present invention include various roll coater methods, spray methods, foam spray methods, and the like, which are appropriately selected depending on the application amount and the shape of the application surface.

  In addition, the latex adhesive used in the present invention contains, as necessary, a stabilizer, an antioxidant, a vulcanization accelerator, a dispersant, a filler, a thickener, a colorant, an antifoaming agent. An agent, a gelling agent, an antifreezing agent, a softening agent, a thickening resin and the like may be contained.

The amount of the latex resin that forms the adhesive layer 18 is appropriately determined depending on the type of the thermoplastic resin used as the latex adhesive and the required adhesive strength with the skin material 30, but the constituent resin in the latex. The solid content of (adhesive resin) is preferably 5 to 50 g, more preferably 10 to 30 g per 1 m ² . If the amount of the constituent resin applied to the latex adhesive layer 18 is less than 5 g / m ² , the required adhesiveness may not be obtained. If it exceeds 50 g / m ² , the latex adhesive is applied from the skin material 30 during molding. Layer 18 can leach out and contaminate the mold.

  In the automobile interior material 1 according to the present invention, the photocatalyst 40 is contained in the latex adhesive of the adhesive layer 18 formed by bonding the non-foamed layer 11 and the skin material 30.

As the photocatalyst 40, one or more photocatalysts selected from titanium oxide and zinc oxide are used, and among these, a titanium oxide photocatalyst is preferably used. The titanium oxide photocatalyst is preferably an anatase-type titanium oxide photocatalyst, a rutile-type titanium oxide photocatalyst, or a brookite-type titanium oxide catalyst, among which an anatase-type titanium oxide photocatalyst is particularly suitable. Titanium oxide photocatalyst is excited by ultraviolet rays, and water and oxygen become “.OH” (OH radical) and “.O ₂ ⁻ ” (O ₂ radical), and decomposes organic matter into water and carbon dioxide by strong oxidation action, Deodorize. In addition, in order to increase the catalytic activity of the titanium oxide photocatalyst, one carrying a platinum group metal such as platinum, palladium or rhodium or one carrying a sterilizing metal such as silver, copper or zinc is used. You can also.

  In the present invention, an apatite-coated titanium oxide photocatalyst can also be used as the titanium oxide photocatalyst. The apatite-coated titanium oxide photocatalyst is a composite material in which the surface of the titanium oxide photocatalyst is coated with calcium phosphate apatite. The apatite-coated titanium oxide photocatalyst has a function capable of suppressing the strong and excessive oxidative decomposition reaction of the titanium oxide photocatalyst, and can prevent significant deterioration of the resin and fiber.

  In addition, a visible light responsive titanium oxide photocatalyst that is excited in the visible light region in which a portion of titanium oxide is N-doped is also known, and these can also be used. For example, an anion doped type in which a part of O of titanium oxide is substituted with N or S, and a cation doped type in which a part of Ti is substituted with another atom.

The smaller the particle size of the titanium oxide photocatalyst, that is, the larger the specific surface area, the better the effect of oxidizing action, preferably 5 nm to 20 μm, more preferably 6 nm to 5 μm. If the particle size of the titanium oxide photocatalyst exceeds 20 μm, the malodor decomposition rate is slow, which is not preferable. It is difficult to technically produce a particle size of less than 5 nm, which is not preferable from the viewpoint of cost.
In the present invention, the particle diameter of the titanium oxide photocatalyst is generally referred to as an X-ray particle diameter. Usually, in an X-ray diffraction diagram obtained by a powder X-ray diffraction method, when the half width is β, It is calculated by the Scherrer equation.
Lc = 0.9λ / βcosθ
Here, Lc is the X-ray particle size (Å), λ is the X-ray wavelength (Å), and θ is the peak position angle.

  Moreover, it is preferable that content of the photocatalyst 40 in the latex adhesive 18 is 3-30 weight part with respect to 100 weight part of latex adhesives. When the content of the photocatalyst 40 in the latex adhesive 18 exceeds 30 parts by weight, the dispersibility in the latex adhesive is lowered, and in particular, the photocatalyst in a solid state cannot be uniformly dispersed in the solution-like latex adhesive. It settles in the liquid and it becomes difficult to maintain a uniform dispersion state. On the other hand, when the content of the photocatalyst in the latex adhesive 18 in the latex adhesive is less than 3 parts by weight, the decomposition rate of odor components such as bad odor is lowered, and the deodorizing effect becomes weak. The amount of 5 to 20 parts by weight is more preferable from the standpoint of expressing the deodorizing effect and maintaining a good dispersion state in the latex adhesive 18.

  Next, a method for manufacturing the automobile interior material 1 and the automobile interior part of the present invention will be described.

  First, the foam layer 10 (primary foam sheet) can be manufactured, for example, as follows. That is, what was blended with various additives as needed to the heat resistant resin as the base resin is melted and kneaded at a resin temperature of 150 to 400 ° C. using an extruder. Next, 2.0 to 5.0 parts by weight of a hydrocarbon-based foaming agent is pressed into 100 parts by weight of the heat-resistant resin into an extruder under high temperature and high pressure (resin temperature 150 to 400 ° C. and resin pressure 3 to 50 MPa). Further, after adjusting the resin temperature to the optimum foaming temperature range (150 to 300 ° C.), a cylindrical foam is obtained by extruding and foaming in a low pressure zone (usually in the atmosphere) using a circular die or the like. Then, for example, it can be produced by a method of contacting a mandrel (cylindrical cooling cylinder) or the like at a speed of 0.5 to 40 m / min, stretching and cooling, and then cutting and winding into a sheet.

  The method for producing the thermoplastic resin foam laminated sheet 1 by forming the non-foamed layers 11 and 13 on the foamed layer 10 and the method for laminating the noise preventing layer 20 thereon are not particularly limited. In a form in which the base resin of the molten non-foamed layers 11 and 13 supplied from the extruder is sandwiched between the foamed layer 10 and the noise-preventing layer 20 while the foamed layer 10 that has been foamed and wound up in advance is fed out. After laminating in layers, a method of pressure bonding with a cooling roller or the like is preferable. Especially, the method of laminating by carrying out extrusion foaming sheet shaping | molding of the foaming layer 10 and extrusion of the non-foaming layers 11 and 13 in-line is preferable at the point of simplification of a manufacturing process.

  As a method of adhering the non-foamed layer 13 and the noise preventing layer 20 of the thermoplastic resin foam laminated sheet 1, a method using an adhesive may be used as in the case of the skin material 30 as described below.

  As an adhesion method between the skin material 30 and the thermoplastic resin foam laminated sheet 50, after applying the adhesive layer 18 to the foam laminated sheet 50, the skin material 30 is laminated on the surface, and after pressure bonding using a roll or the like, The method of drying, after apply | coating the adhesive bond layer 18 to the skin material 30, the method of drying after crimping | bonding using the foaming laminated sheet 50, a roll, etc. is mentioned.

  As a molding method for obtaining an automotive interior part (secondary foamed laminated molded body) by molding from the automotive interior material 1 (primary foamed laminated sheet) obtained as described above, a heating furnace equipped with heaters at the top and bottom is used. After the automobile interior material 1 is clamped and guided at the center and heated to a temperature suitable for molding (for example, the surface temperature of the foamed laminated sheet is 135 to 155 ° C.), the skin material 30 becomes the indoor side. Then, press cooling with a temperature-controlled mold and shaping may be mentioned.

  Specific examples of molding methods include, for example, plug molding, free drawing molding, plug and ridge molding, ridge molding, matched mold molding, straight molding, drape molding, reverse draw molding, air slip molding, Examples include plug assist molding and plug assist reverse draw molding.

  When the foamed layer 10 (primary foamed sheet) in the automobile interior material 1 is subjected to secondary foaming by heating at the time of molding the automobile interior member, it is usually 1.2 to 4 times the primary foamed sheet. It is preferable to perform secondary foaming, and it is preferable to perform secondary foaming 1.5 to 3 times. Therefore, the expansion ratio of the foamed layer (secondary foam sheet) after the secondary foaming is preferably 3.6 to 80 times, more preferably 7.5 to 45 times, and even more preferably 10 to 40 times. If the secondary foaming ratio is less than 1.2 times, the flexibility tends to be inferior and breakage due to bending or the like tends to occur. When the secondary expansion ratio exceeds 4 times, the strength tends to decrease. Moreover, 1.2-20.0 mm is preferable, as for the thickness of the foaming layer (secondary foam sheet) after secondary foaming, 2.25-10.5 mm is more preferable, and 3.0-7.0 mm is further preferable. If the thickness of the foamed layer after secondary foaming is less than 1.2 mm, the strength and heat insulating properties are inferior and may not be suitable as an automobile interior part. If the thickness exceeds 20 mm, the shape development at the time of molding is inferior, or the vehicle interior tends to be bulky and narrower than necessary.

Total basis weight of the automobile interior material 1 is preferably 200~850g / m ^2, more preferably 240~600g / m ^2. If the overall weight of the automobile interior material 1 is less than 200 g / m ² , the strength tends to be inferior and damage due to bending or the like tends to occur. If it exceeds 850 g / m ² , the handleability (interior worker's handling property) accompanying an increase in weight is lowered, and there is a tendency to be contrary to the light weight which is one of the problems of the present invention.

  While various embodiments of the automobile interior material and the automobile interior part according to the present invention have been described above, the present invention is not limited to the above-described aspects. For example, automobile interior materials can be used as interior materials other than automobiles such as trains, airplanes, and building interiors, and should be interpreted broadly. In addition, the present invention can be carried out in a mode in which various improvements, changes, and modifications are added based on the knowledge of those skilled in the art without departing from the spirit of the present invention.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereby.
The resins used in Examples or Comparative Examples are shown in Table 1, photocatalyst materials are shown in Table 2, and adhesive layer and skin layer materials are shown in Table 3.

In addition, each abbreviation shown in Tables 1 to 3 indicates the following.
PPE: Polyphenylene ether resin PS: Polystyrene resin SMAA: Styrene-methacrylic acid copolymer (heat-resistant polystyrene resin)
HIPS: High impact polystyrene resin

Moreover, the evaluation method implemented in the Example or the comparative example is shown below.

(Thickness of foam layer and molded body)
About the obtained primary foamed sheet and a molded object (automobile ceiling material), the thickness of 20 places was measured in the width direction, and the average value of the measured value was computed.

(Foaming ratio)
The density df of the obtained primary foamed sheet was measured according to JIS K7222, and the density dp of the modified PPE resin was separately measured according to JIS K7112, and calculated according to the formula: foaming ratio = dp / df.

(Cell diameter)
The cross section of the foamed layer of the obtained primary foamed sheet was observed with an optical microscope to measure 20 cell diameters, and the average value of the measured values was calculated.

(Weight)
A test piece having a size of 100 mm × 100 mm was cut out from any five locations of the used materials, and after measuring their weight, an average value was calculated and converted per square meter.

(Deodorization performance evaluation)
A test piece having a size of 100 mm × 100 mm is cut out from the obtained molded body (automobile ceiling material), placed in a 750 ml glass container, and sealed. The container is allowed to stand for 3 hours in an environment of room temperature 23 ° C. and humidity 50 RH%, and the amount of odor (particles) in the glass container is measured using an odor sensor (ODOR CONCENTRATION METER XP329; manufactured by NEW COSMOS ELECTRIC). (Measured value A).
On the other hand, a container in which tobacco odor is collected is prepared, and 300 ml of tobacco odor is put into the glass container in which the test piece of the molded body (automobile ceiling material) is inserted. The odor immediately after the tobacco odor is added is measured using an odor sensor (Measurement Value B). The glass container in which the test piece of the molded body (car ceiling material) is inserted is sealed and left in an environment of a room temperature of 23 ° C. and a humidity of 50 RH%, and odor measurement after 12 hours is performed using an odor sensor ( measured value C _12).
Formula α = (C ₁₂ −A) / (B−A) × 100
Is used to calculate the change rate α of the odor component.
When the odor measurement value immediately after the introduction of the tobacco odor is taken as 100, the difference in the change rate α determined by the above formula, that is,
Formula β = 100−α
The β value expressed by the following index was evaluated.
45% or more: ◎
30% or more and less than 45%: ○
10% or more and less than 30%: △
Less than 10%: ×

(Evaluation of adhesion to epidermis under heat history conditions)
A test piece having a size of 150 mm × 25 mm was cut out from the obtained molded body (automobile ceiling material), and adhesion between the skin material and the thermoplastic resin foam laminated sheet in a normal state under an environment of room temperature 23 ° C. and humidity 50 RH%. The strength was measured. In addition, a test piece having a size of 150 mm × 25 mm was cut out from the obtained molded body (automobile ceiling material), and each test piece that had passed 24 hours and 400 hours at a temperature of 80 ° C. was subjected to room temperature of 23 ° C. The adhesive strength between the skin material and the thermoplastic resin foam laminated sheet was measured under the conditions of humidity 50RH%.
Appropriate amounts of the skin material on which the test pieces of the acquired size are laminated are peeled off in parallel to the short side, and the peeled skin material and the thermoplastic resin foam laminated sheet are pulled by a tensile testing machine (manufactured by Shimadzu Corporation, Autograph). DSS-2000) was attached to a holding jig and peeled in the 180 ° direction at a pulling speed of 200 mm / min to determine the peel strength.

(Evaluation of skin adhesion and appearance under sunlight irradiation conditions)
A test piece having a size of 100 mm × 100 mm was cut out from the obtained molded body (automobile ceiling material), and the test piece was left in a place exposed to sunlight. Immediately after being left, 24 hours passed and 100 hours passed For each piece, the adhesive strength between the skin material and the thermoplastic resin foam laminate sheet was measured by the same method as in the above-mentioned skin adhesion evaluation, and for each test piece, the degree of discoloration of the skin surface appearance immediately after being left was measured. evaluated.

(Example 1)
With respect to 100 parts by weight of a mixed resin obtained by mixing 57.1 parts by weight of PPE resin (A) and 42.9 parts by weight of PS resin (B) so as to be 40% by weight of PPE resin component and 60% by weight of PS resin component, A hydrocarbon-based foaming agent (isobutane / normal butane = 85/15 wt%) containing isobutane as a main component and 0.32 part by weight of talc were kneaded by an extruder at a resin temperature of 270 ° C., and the resin temperature Is cooled to 196 ° C., extruded with a circular die at a pressure of 10 MPa, wound into a winding roll through a take-up roll, and has a thickness of 2.3 mm, a foaming ratio of 13.8 times, a closed cell ratio of 88%, a cell A roll of a foam sheet (primary foam sheet) having a diameter of 0.16 mm and a basis weight of 150 g / m ² was obtained.
Next, while feeding out the foamed sheet from a roll, a mixed resin in which 50.0 parts by weight of a styrene-methacrylic acid copolymer (C) and 50.0 parts by weight of HIPS (D) are mixed is obtained by using an extruder. Melted and kneaded at 250 ° C., extruded into a film using a T-die, laminated a film-like outdoor non-foamed layer in a molten state on the foamed sheet (foamed layer 10), and heat resistant with a basis weight of 150 g / m ² A PS resin non-foamed layer (13) was formed.
At the time of laminating the heat-resistant PS resin non-foamed layer (13), a water needle nonwoven fabric 20 g / m ² (Celes WAI-R8020 manufactured by Yuho Co., Ltd.) was laminated as an abnormal sound preventing layer (20).
Next, while the heat-resistant PS resin non-foamed layer (11) obtained as described above is formed and the sheet on which the noise prevention layer (20) is laminated is fed out from the roll, the PPE resin component is 20% by weight. A mixed resin in which 28.6 parts by weight of PPE resin (A), 66.4 parts by weight of PS resin (B) and 5.0 parts by weight of HIPS resin (D) are mixed so that the resin temperature becomes 250 ° C. A modified PPE-based resin chamber inner non-foamed layer (11) having a basis weight of 120 g / m ² was formed on the opposite surface of the sheet which was extruded into a film and formed with a heat-resistant PS-based resin chamber outer non-foamed layer (13).
Thereafter, the non-foamed layer (11) on the modified PPE resin interior side is composed of 60% by weight of carboxylated modified SB resin latex (G) and 40% by weight of carboxylated modified AS resin latex (H), and has a particle diameter of 30 nm. A mixed latex adhesive containing 5 parts by weight of titanium oxide photocatalyst (E) with respect to 100 parts by weight of the latex mixture was applied to a surface area of 25 g / m ² (solid content), and a polyester having a basis weight of 140 g / m ² A nonwoven fabric skin (K) mainly composed of fibers made of a resin is laminated on the surface as a skin material (30) to obtain an automotive interior material 1 (total weight of the automotive interior material: 605 g / m ² , Of these, the basis weight of the skin material: 140 g / m ² ).
The automobile interior material is clamped in two width directions and placed in a heating furnace so that the surface temperature of the automobile interior material is 170 ° C. on the surface of the skin material 30 and 145 ° C. on the surface of the noise prevention layer 20. Heated for 45 seconds. Thereafter, plug molding was performed with a mold clearance of 4.5 mm, and trimming and punching were performed to obtain a molded ceiling material for automobiles as an automobile interior part. When the appearance of the resulting molded ceiling material for automobiles was observed, no appearance abnormality such as cracking was observed.

(Example 2)
An automobile interior material was obtained in the same manner as in Example 1 except that the content of the titanium oxide photocatalyst (E) in the mixed latex adhesive was 20 parts by weight.
Using this automobile interior material, molding was performed in the same manner as in Example 1 to obtain a molded ceiling material for automobile as an automobile interior part. When the appearance of the resulting molded ceiling material for automobiles was observed, no appearance abnormality such as cracking was observed.

(Example 3)
An automobile interior material was obtained in the same manner as in Example 1 except that the content of the titanium oxide photocatalyst (E) in the mixed latex adhesive was 3 parts by weight.
Using this automobile interior material, molding was performed in the same manner as in Example 1 to obtain a molded ceiling material for automobile as an automobile interior part. When the appearance of the resulting molded ceiling material for automobiles was observed, no appearance abnormality such as cracking was observed.

Example 4
5 parts by weight of titanium oxide photocatalyst (F) having a particle diameter of 15 nm was contained in a mixed latex adhesive composed of 60% by weight of carboxylated modified SB resin latex (G) and 40% by weight of carboxylated modified AS resin latex (H). Except for the above, an automobile interior material was obtained in the same manner as in Example 1.
Using this automobile interior material, molding was performed in the same manner as in Example 1 to obtain a molded ceiling material for automobile as an automobile interior part. When the appearance of the resulting molded ceiling material for automobiles was observed, no appearance abnormality such as cracking was observed.

(Example 5)
Except for containing 5 parts by weight of titanium oxide photocatalyst (E) having a particle diameter of 30 nm in a mixed latex adhesive composed of 80% by weight of carboxylated modified SB resin latex (G) and 20% by weight of PS resin latex (I), An automobile interior material was obtained in the same manner as in Example 1.
Using this automobile interior material, molding was performed in the same manner as in Example 1 to obtain a molded ceiling material for automobile as an automobile interior part. When the appearance of the resulting molded ceiling material for automobiles was observed, no appearance abnormality such as cracking was observed.

(Example 6)
An automobile interior material was obtained in the same manner as in Example 1 except that 5 parts by weight of the titanium oxide photocatalyst (E) having a particle diameter of 30 nm was contained in the latex adhesive made of PS resin latex (I).
Using this automobile interior material, molding was performed in the same manner as in Example 1 to obtain a molded ceiling material for automobile as an automobile interior part. When the appearance of the resulting molded ceiling material for automobiles was observed, no appearance abnormality such as cracking was observed.

(Example 7)
An automobile interior material was obtained in the same manner as in Example 1 except that 5 parts by weight of the titanium oxide photocatalyst (E) having a particle diameter of 30 nm was contained in the latex adhesive composed of SB resin latex (J).
Using this automobile interior material, molding was performed in the same manner as in Example 1 to obtain a molded ceiling material for automobile as an automobile interior part. When the appearance of the resulting molded ceiling material for automobiles was observed, no appearance abnormality such as cracking was observed.

  When test pieces were cut out from the molded ceiling materials for automobiles obtained in Examples 1 to 7 and evaluated for various evaluation items, as shown in Table 4, very good results were obtained.

(Comparative Example 1)
The same as Example 1 except that the titanium oxide photocatalyst was not added to the mixed latex adhesive composed of 60% by weight of carboxylated modified SB resin latex (G) and 40% by weight of carboxylated modified AS resin latex (H). The car interior material was obtained by a simple method.
Using this automobile interior material, molding was performed in the same manner as in Example 1 to obtain a molded ceiling material for automobile as an automobile interior part. When the appearance of the resulting molded ceiling material for automobiles was observed, no appearance abnormality such as cracking was observed.
However, when a test piece was cut out from the obtained molded ceiling material for automobiles and subjected to an evaluation test for various evaluation items, as shown in Table 4, the deodorizing function was remarkably inferior to the examples. .

(Comparative Example 2)
With respect to 100 parts by weight of a mixed resin obtained by mixing 57.1 parts by weight of PPE resin (A) and 42.9 parts by weight of PS resin (B) so as to be 40% by weight of PPE resin component and 60% by weight of PS resin component, A hydrocarbon-based foaming agent (isobutane / normal butane = 85/15 wt%) containing isobutane as a main component and 0.32 part by weight of talc were kneaded by an extruder at a resin temperature of 270 ° C., and the resin temperature Was cooled to 196 ° C., extruded with a circular die at a pressure of 10 MPa, wound up into a take-up roll through a take-up roll, and the foam layer had a thickness of 2.3 mm, an expansion ratio of 13.8 times, and a closed cell ratio of 88. %, A cell diameter of 0.16 mm, and a roll of a primary foam sheet having a basis weight of 150 g / m ² was obtained.
Next, while feeding out the primary foamed sheet from a roll, a mixed resin in which 50.0 parts by weight of a styrene-methacrylic acid copolymer (C) and 50.0 parts by weight of HIPS (D) are mixed is obtained by using an extruder. Melted and kneaded at a temperature of 250 ° C., extruded into a film using a T-die, and laminated with a film-like outdoor non-foamed layer in a molten state on the foamed sheet (foamed layer 10), having a basis weight of 150 g / m ² A heat-resistant PS resin non-foamed layer (13) was formed.
At the time of laminating the heat-resistant PS-based resin non-foamed layer (13), a water needle nonwoven fabric 20 g / m ² (Celes WAI-R8020 manufactured by Yuho Co., Ltd.) was laminated as an abnormal sound preventing layer (20).
Next, while the sheet formed with the heat-resistant PS resin non-foamed layer (13) obtained as described above is fed out from the roll, the PPE resin (A) 28.6 is adjusted so that the PPE resin component becomes 20% by weight. A mixed resin in which 66.4 parts by weight of PS resin (B) and 5.0 parts by weight of HIPS resin (D) are mixed is extruded into a film shape so that the resin temperature is 250 ° C. A non-foamed layer (11) having a basis weight of 120 g / m ² was formed on the opposite surface of the sheet on which the non-foamed layer was formed to obtain a thermoplastic resin foamed laminated sheet.
On the other hand, 20 parts by weight of a titanium oxide photocatalyst (E) having a particle size of 30 nm is added to and mixed with a solution composed of 60 parts by weight of water and 20 parts by weight of an acrylic binder resin, and then a uniform dispersion solution is obtained. It was. This dispersion solution was applied to the design surface side of the 140 g / m ² nonwoven fabric skin (K) using a roll coater so that the solid surface area was 15 g / m ² and dried at 120 ° C. The nonwoven fabric skin which apply | coated the contained binder resin was obtained.
60% by weight of carboxylated modified SB resin latex (G) and carboxylated modified AS resin latex (H) are formed on the modified PPE resin indoor side non-foamed layer (11) side of the thermoplastic resin foam laminated sheet obtained previously. ) A mixed latex adhesive consisting of 40% by weight was applied to a surface weight of 25 g / m ² (solid content), and the non-woven fabric coated with the binder resin was laminated on the surface as a skin material (30). A material (1) was obtained (overall weight of the automobile interior material: 620 g / m ² , of which the weight of the skin material: 155 g / m ² ).
Using this automobile interior material, molding was performed in the same manner as in Example 1 to obtain a molded ceiling material for automobile as an automobile interior part. When the appearance of the resulting molded ceiling material for automobiles was observed, no appearance abnormality such as cracking was observed.
However, when test pieces were cut out from the obtained molded ceiling material for automobiles and subjected to evaluation tests on various evaluation items, as shown in Table 4, the skin material was discolored by irradiation with sunlight.

It is principal part expanded sectional explanatory drawing of the motor vehicle interior material which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Automobile interior material 10 Foam layer 11 Indoor side non-foam layer 13 Outdoor non-foam layer 18 Adhesive layer 20 Anti-noise layer 30 Skin material 40 Photocatalyst 50 Thermoplastic resin foam lamination sheet

Claims (15)

  An automobile in which a skin material is laminated via a latex adhesive on a thermoplastic resin foam laminated sheet in which a non-foamed layer made of a thermoplastic resin is laminated on the surface of a foamed layer obtained by extrusion foam molding of a thermoplastic resin An automobile interior material having a deodorizing function, wherein the latex adhesive is a base material for an interior material and contains a photocatalyst.   The automobile interior material according to claim 1, wherein the photocatalyst is one or more photocatalysts selected from titanium oxide and zinc oxide, and has a particle diameter of 5 nm to 20 µm.   The automobile interior material according to claim 1 or 2, wherein the photocatalyst is contained in an amount of 3 to 30 parts by weight with respect to 100 parts by weight of the latex adhesive.   The automobile interior material according to any one of claims 1 to 3, wherein the latex adhesive is a latex having a polystyrene resin as a constituent resin.   The automobile interior material according to any one of claims 1 to 3, wherein the latex adhesive is a latex comprising a styrene / butadiene copolymer resin or a carboxylated modified styrene / butadiene copolymer resin as a constituent resin.   The latex adhesive is a latex mixture comprising a binder latex having a carboxylated modified styrene / butadiene copolymer resin as a constituent resin and a resin latex having a carboxylated modified acrylonitrile / styrene copolymer resin as a constituent resin. The automobile interior material according to any one of Items 1 to 3.   The thermoplastic resin constituting the foamed layer of the thermoplastic resin foamed laminated sheet is a modified polyphenylene ether resin comprising 25 to 70% by weight of a polyphenylene ether resin and 75 to 30% by weight of a polystyrene resin. The automobile interior material according to any one of the above.   The automobile interior material according to any one of claims 1 to 7, wherein the foamed layer of the thermoplastic resin foamed laminated sheet is obtained by extrusion foam molding using a hydrocarbon-based foaming agent. The thermoplastic resin thickness of the foamed laminate sheet of the foam layer is 1 to 5 mm, an expansion ratio of 3-20 times, car interior materials according to any of claims 1 to 8 having a basis weight is 100 to 300 g / m ² .   The thermoplastic resin constituting the non-foamed layer of the thermoplastic resin foam laminated sheet is a modified polyphenylene ether resin comprising 5 to 70% by weight of a polyphenylene ether resin and 95 to 30% by weight of a polystyrene resin, and a heat resistant polystyrene resin. The automobile interior material according to claim 1, which is at least one of the above. Automobile interior material according to any one of claims 1 to 10 having a basis weight of the thermoplastic resin foam non-foamed layer of the laminated sheet is 50 to 300 g / m ^2.   The automobile interior material according to any one of claims 1 to 11, wherein the skin material is made of a non-woven fabric.   The automobile interior material according to claim 12, wherein the nonwoven fabric includes a synthetic fiber. Claim 12 or 13 car interior materials according basis weight of the nonwoven fabric is 100 to 300 g / m ^2. An automotive interior part formed by molding the automotive interior material according to any one of claims 1 to 14 so that the skin layer is on the indoor side.

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