JPH09309183A - Molded object for car interior material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded object for a car interior material having excellent heat resistance, low in cost and capable of being produced easily. SOLUTION: A primary foamed laminated sheet obtained by laminating a non-foamed layer composed of a modified polyphenylene ether resin (II) on at least the single surface of a foamed sheet composed of a modified polyphenylene ether resin (I) is heated for 30-120sec in an oven to heat the surface thereof to the thermal deformation temp. of the base material resin of the foamed layer and the heated sheet is molded in a mold in such a state that a closed-cell ratio is held to 70% or more to produce a molded object for a car interior material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention belongs to the technical field of producing and using molded articles for automobile interior materials. More specifically, it belongs to the technical field of producing and using molded articles for automobile interior materials, which are excellent in dimensional stability, heat resistance and heat insulation.

[0002]

2. Description of the Related Art Conventionally, as an automobile interior material, urethane foam is laminated on a base material mainly composed of thermoplastic resin foam, and styrene-maleic anhydride is formed on both sides of a foam sheet of styrene-maleic anhydride copolymer. A laminate sheet formed by laminating a non-foamed layer of an acid copolymer into a desired shape is widely used. These automobile interior materials are characterized by being lightweight, having high heat insulating properties, and having excellent moldability.

However, when the conventional automobile interior materials are used for applications such as automobile ceiling materials that are exposed to high temperatures for a long time, their heat resistance is insufficient, and they may sag under their own weight. However, problems such as deformation may occur, and it is desired to solve the problem.

In recent years, the demand for heat resistance of foam laminated sheets for automobile ceiling materials has become more severe. For example, when a car is exported overseas, it may be transported just below the hot equator, and there is a demand for further improvement in heat resistance in order to eliminate the concern about deformation of the ceiling material during transport. is there. In addition, the price competition of automobiles is becoming fierce, and the price and quality of automobile components are being reviewed. Under these circumstances, the quality requirements for automobile ceiling materials are also changing. For example, ceiling material holders have been simplified and omitted to reduce costs such as labor saving. As a result, the number of holding portions of the automobile ceiling material is reduced, so that the automobile ceiling material tends to be required to have high heat resistance.

In order to satisfy the above requirements for heat resistance, an automobile ceiling material using a material having high heat resistance,
That is, an automobile ceiling material using a foam laminated sheet in which a modified PPE resin film is laminated on both surfaces of a modified polyphenylene ether (PPE) resin foam sheet has been proposed (Japanese Utility Model Publication No. 4-11162). The modified PPE
A modified PPE resin foam laminated sheet in which a modified PPE resin film is laminated
Since a PE resin is used, it is said that it is possible to improve deformation at high temperatures and sag due to its own weight.

The modified PPE resin has a small dimensional change, which is a characteristic of an amorphous resin, and has excellent rigidity at high temperatures. Furthermore, it is a resin that not only has quality, but also has cost competitiveness.

[0007]

[Problems to be Solved by the Invention] However, the above-mentioned modified PP
Even in the case of an automobile ceiling material using a modified PPE resin foam laminated sheet in which an E resin film is laminated, it is a fact that the demand for heat resistance in the market is not sufficiently satisfied.

[0008]

When manufacturing a molded article for an automobile interior material, since it has good moldability and can be molded by conventional equipment, molding by a conventional technique has been carried out. However, the inventors of the present invention have found that in the conventional molding, even if a material having good heat resistance is used, if the residual strain during molding is large, the molded article will be relaxed when exposed to high temperature. Therefore, it was thought that it would be impossible to obtain a molded product that satisfies the recent demand for improved heat resistance because of the deformation.

Therefore, the present inventor has conducted various studies to develop a modified PPE resin molded article for automobile interior materials, which has high heat resistance, good dimensional stability, and heat insulation, and as a result, has found that The heating time has a great influence on the heat resistance of the molded product. By adjusting the mold temperature within a predetermined range, the mold is well determined and the heat resistance is improved.
It has been found that when the molded body has a low closed cell rate, although the heat resistance is improved, the rigidity and heat insulating properties are deteriorated, and a molded body for an automobile interior material cannot be obtained. That is, when a base material having high heat resistance such as a modified PPE-based resin foam laminated sheet is used, heating is sufficiently performed while maintaining a high closed cell ratio to sufficiently heat the inside to form a molded product. Suppresses residual strain,
By molding with a temperature-controlled mold, the mold is well determined,
It was found that it is possible to obtain a molded article for automobile interior materials which has excellent heat resistance and good rigidity and heat insulating properties.

The present invention has been made on the basis of the above findings, and is a modified polyphenylene ether resin (I).
The primary foamed laminated sheet obtained by laminating the non-foamed layer of modified polyphenylene ether resin (II) on at least one side of the foamed sheet is heated in an oven for 30 to 120 seconds to adjust the surface temperature to the base resin of the foamed layer. Molding was performed using a mold whose temperature was controlled to a temperature not higher than the heat distortion temperature of the base material resin of the foam layer at 60 ° C. or higher while keeping the closed cell ratio at 70% or higher while maintaining the heat distortion temperature or higher. A molded body for an automobile interior material (Claim 1), a molded body for an automobile interior material (Claim 2) according to claim 1 formed by laminating a skin material, and a modified polyphenylene ether resin (I) foamed sheet on at least one surface. The primary foamed laminated sheet obtained by laminating the non-foamed layer of modified polyphenylene ether resin (II) is heated in an oven for 30 to 120 seconds so that the surface temperature becomes equal to or higher than the heat deformation temperature of the base resin of the foamed layer, And closed bubbles For an automobile interior material, characterized by being molded using a mold whose temperature is maintained at 70% or higher and at a temperature not higher than the heat deformation temperature of the base resin of the foam layer at 60 ° C or higher. The present invention relates to a method for producing a molded article (Claim 3) and a method for producing a molded article for automobile interior materials (Claim 4) according to claim 3, which comprises laminating a skin material.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION A molded article for an automobile interior material according to the present invention comprises a modified polyphenylene ether (PPE) resin (I) foamed sheet (primary foamed sheet) and a modified PPE resin (II) -free resin. 2 obtained by molding a primary foam laminated sheet obtained by laminating foam layers under specific conditions
The next foamed laminated sheet molded body (molded body for automobile interior material).

The modified PPE resin (I) foamed sheet constituting the molded article for automobile interior materials serves as a base of the molded article for automobile interior materials, and this modified PPE is used.
Since it is formed of the resin (I), it has good heat resistance and moldability, and a secondary foamed laminated sheet having good heat resistance can be easily molded, and this is a foamed sheet. Low density, light weight, and small amount of resin used,
It is possible to obtain molded products for automobile interior materials that have cost competitiveness and excellent sound insulation and heat insulation.

Modified PPE resin (I) Modified PPE resin (II) formed on at least one side of a foamed sheet
The non-foamed layer is a layer laminated to improve rigidity, strength, and dimensional stability. Since this layer is formed of the modified PPE resin (II), heat resistance and dimensional stability are improved. Become. Further, since the same type of resin as that used for the foamed sheet is used, the adhesiveness is good, and since this layer is a non-foamed layer, the rigidity, strength, and dimensional stability are good.

As the modified PPE resin (I) for forming the modified PPE resin (I) foamed sheet, a mixed resin of a PPE resin and a polystyrene resin (PS resin),
Copolymers such as grafts and blocks obtained by polymerizing a styrene monomer on a PPE resin are exemplified. Among these, a mixed resin of a PPE-based resin and a PS-based resin is preferred from the viewpoint of easy production.

Examples of the PPE resin include poly (2,6-dimethylphenylene-1,4-ether),
Poly (2-methyl-6-ethylphenylene-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) and poly (2-ethyl-6-chlorophenylene-1,4-ether). These may be used alone or in combination of two or more. Among them, poly (2,6-dimethylphenylene-1,4-ether) is preferable from the viewpoint of versatility of raw materials and cost. Also, if you want to impart flame retardancy,
Poly (2-methyl-6-chlorophenylene-1,4-ether), poly (2-methyl-6-bromophenylene-1,4-ether), poly (2-ethyl-6-) containing a halogen element Chlophenylene-1,4-ether) is preferred.

P forming a mixed resin with the PPE resin
The S-based resin is a resin containing styrene or a derivative thereof, for example, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, dichlorostyrene, p-methylstyrene, ethylstyrene or the like as a main component (60% or more). . Therefore, the PS resin is not limited to a homopolymer or a copolymer consisting only of styrene or a styrene derivative, and may be a copolymer produced by copolymerizing with another monomer. Further, for example, when polymerizing styrene or a styrene derivative, such as high impact polystyrene, a polymer obtained by adding synthetic rubber or rubber latex may be used.

Examples of the other monomer copolymerizable with styrene or its derivative which can be used in the production of the PS resin include acrylonitrile, methacrylonitrile,
Examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and maleic anhydride. These may be used alone or in combination of two or more.

Specific examples of the PS-based resin include polystyrene, styrene-α-methylstyrene copolymer, styrene-butadiene copolymer represented by high-impact polystyrene, and styrene-acrylonitrile copolymer. . Among these, polystyrene is preferable in terms of versatility and cost.

Specific examples of the styrene monomer to be polymerized, preferably graft-polymerized to the PPE resin include, for example, styrene, α-methylstyrene, 2,4-
Examples include dimethylstyrene, monochlorostyrene, dichlorostyrene, p-methylstyrene, ethylstyrene and the like. These may be used alone or in combination of two or more. Of these, styrene is preferred in terms of versatility and cost.

When the styrene-based monomer is polymerized with the PPE-based resin, the styrene-based monomer is used as the main component (60% (wt%, the same applies hereinafter) or more) together with the styrene-based monomer. A polymerizable monomer, for example, one or more kinds of acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like may be contained.

As a method for producing a graft copolymer obtained by polymerizing a PS-based monomer with the PPE-based resin, a conventionally known method may be used, for example, JP-B-52-30991 and JP-B-52-38596. A radical polymerization initiator and a styrene-based monomer are added to a PPE-based resin disclosed in, for example, the publication, and the mixture is stirred in an anhydrous state in the presence or absence of an organic solvent in a temperature range of 130 to 200 ° C. However, a method of polymerizing a styrene-based monomer may be used.

The PPE resin and the PS resin or PP
The proportion of the styrene monomer (which may contain a monomer copolymerizable with the styrene monomer) to be polymerized in the E resin is 25 to 75% of the PPE resin, and further 35.
~ 60%, especially 38 to 58%, styrene monomer 75 to polymerize PS resin or PPE resin
25%, further 65-40%, especially 62-42%
Is preferred. If the proportion of the PPE-based resin is too small, the heat resistance tends to be inferior. If the proportion of the PPE-based resin is too large, the viscosity at the time of heating and flowing may increase, making foam molding difficult.

The thickness of the modified PPE resin (I) foamed sheet (primary foamed sheet) containing the modified PPE resin as the base resin is 1 to 5 mm, and more preferably 1.5 to 5.
3.5 mm, foaming ratio 3 to 20 times, further 5
˜15 times, the cell diameter is 0.05 to 0.3 mm, more preferably 0.1 to 0.7 mm, and the closed cell ratio is 70% or more, further preferably 80% or more. In addition, the amount of volatile components remaining in the primary foam sheet is 1 with respect to the total weight of the foam sheet.
It is preferably -5%, more preferably 2-4%. Note that the amount of residual volatile components can be determined, for example, by modifying the foamed sheet sample with
It is measured by the difference in weight before and after heating by heating the resin (I) above the decomposition temperature and below the decomposition temperature to volatilize the volatile components sufficiently, or by gas chromatography.

When the thickness of the primary foamed sheet is less than 1 mm, the strength and heat insulation properties are insufficient, and the primary foamed sheet for automobile interior materials may not be suitable. On the other hand, if it exceeds 5 mm, it is difficult for heat to be transferred to the central portion in the thickness direction of the modified PPE-based resin foam layer during molding heating, so that sufficient heating cannot be performed and moldability may deteriorate. In addition, if the heating time is extended to perform sufficient heating, cells on the surface of the foam layer may be broken, which may make it difficult to obtain an acceptable product. In addition, when the expansion ratio of the primary foam sheet is less than 3 times, it is inferior in flexibility, is likely to be damaged by bending or the like, and it is difficult to obtain a lightweight one. 20
If the ratio is more than twice, the strength and the moldability tend to decrease due to difficulty in heating to the center. further,
When the cell diameter is less than 0.05 mm, it is difficult to obtain sufficient strength, and when it exceeds 0.3 mm, the heat insulating property tends to be poor. Further, when the closed cell ratio is less than 70%, the heat insulating property and rigidity are poor, and the target secondary expansion ratio becomes difficult to obtain even by molding heating, and the moldability tends to be poor. In addition, if the residual volatile component is less than 1%, the secondary expansion ratio may be too low for good molding, and if it exceeds 5%, air pockets may form between the non-foamed layer. In some cases, the dimensional stability with time may deteriorate.

The base resin for producing the modified PPE-based resin (I) foamed sheet used in the present invention contains, as necessary, a cell regulator, an impact resistance improver, a lubricant, an antioxidant, and a static agent. You may add an antistatic agent, a pigment, etc.

A non-foamed layer of modified PPE resin (II) is formed on at least one surface of the primary foamed sheet as described above.
When the modified PPE-based resin (II) non-foamed layer is formed only on one side of the primary foamed sheet, the weight is reduced, the process for manufacturing the primary foamed laminated sheet is short and simple, and the material cost is low. This is preferable because the production cost is reduced as a whole. On the other hand, when the non-foamed layer of the modified PPE resin (II) is formed on both sides, it is preferable because it has high rigidity and can be used for a large interior member such as a wagon car.

As the modified PPE resin (II) for forming the non-foamed layer, the modified PPE resin (II) includes the PPE resin and the polystyrene resin (PS resin) as in the case of the primary foam sheet. ) And a copolymer such as a graft or a block obtained by polymerizing a styrene monomer in a PPE resin. Of these, PPE
A mixed resin of a system resin and a PS resin is preferable from the viewpoint of easy production.

Specific examples and preferred examples of the PPE-based resin, specific examples and preferred examples of the PS-based resin, specific examples and preferred examples of the styrene-based monomer, and further, those contained in the PS-based resin or a styrene-based monomer. Specific examples of the monomer that can be polymerized with the body are the same as in the case of the primary foam sheet, and thus the description thereof will be omitted. However, as a preferred specific example of the PS resin, a styrene-butadiene copolymer represented by high impact polystyrene is added because the effect of improving the impact resistance of the non-foamed layer is large.

The proportion of the PPE resin in the non-foamed layer of the modified PPE resin (II) to the PS resin or the styrene monomer polymerized into the PPE resin is 25 to 75% of the PPE resin, and Is 27-73% against P
75 to 25%, more preferably 73 to 27%, of a styrene-based monomer polymerized with an S-based resin or a PPE-based resin is preferable.
If the proportion of the PPE-based resin is too small, the heat resistance of the molded article tends to be inferior. If the proportion of the PPE-based resin is too large, the viscosity at the time of heating and flowing increases, which may make extrusion molding difficult. .

The thickness of the non-foamed layer is 50 to 300 μm,
Furthermore, 75 to 200 μm is preferable. When the thickness of the non-foamed layer is less than 50 μm, strength, rigidity, heat resistance and the like tend to be inferior, and when the thickness is more than 300 μm, moldability tends to be inferior.

When forming the modified PPE resin (II) non-foamed layer, the base resin forming the modified PPE resin (II) non-foamed layer may be filled with an impact resistance improver, if necessary. The agents, lubricants, antioxidants, antistatic agents, pigments and the like may be added alone or in combination of two or more.

The impact resistance improver is formed by laminating a modified PPE-based resin (II) non-foamed layer on a modified PPE-based resin (I) foamed sheet and then secondary-foaming the molded product (for example, for automobile interior materials). It is a component used to prevent cracking of the non-foamed layer during transportation of the molded article for automobile ceiling material) or when further punching is performed on the molded article for automobile interior material. As a result of the study, the effectiveness was found.

The impact resistance improver may be used without particular limitation as long as it exhibits its effect when mixed with the base resin. In this case, it may be reacted with the modified PPE resin (II) or the like by mixing.

Examples of the impact resistance improver include rubber such as natural rubber and synthetic rubber, and graft polymerization of a monomer having a carbon-carbon double bond such as styrene and methyl methacrylate around rubber particles. Those that have been used are preferably used.

Specific examples of the rubber include, for example, styrene-butadiene type thermoplastic elastomer, natural crepe rubber, GR-N type rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, ethylene-propylene copolymer, ethylene. -Propylene-diene copolymer, acrylonitrile-butadiene copolymer, chloroprene rubber, butyl rubber, urethane rubber, silicone rubber, polysulfide rubber, hydrogenated nitrile rubber, polyether special rubber, fluororubber, tetrafluoroethylene-propylene Rubber, acrylic rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, propylene oxide rubber, ethylene-acrylic rubber, liquid rubber, norbornene rubber, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer Chromatography, urethane-based thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, 1,2-polybutadiene type thermoplastic elastomer, vinyl chloride thermoplastic elastomer, fluorine-based thermoplastic elastomer, MBS resin, ethylene -
Examples thereof include vinyl acetate copolymer. These may be used alone or in combination of two or more. Among these, good compatibility with the modified PPE resin,
Styrene-butadiene rubber is preferable in terms of versatility.

The amount of impact modifier added is preferably 2 to 25%, more preferably 4 to 20%, based on the modified PPE resin (II). If the impact resistance improver is less than 2%, the effect of improving the flexibility and impact resistance of the non-foamed layer will not be sufficiently exhibited, and breakage due to bending or impact will not be sufficiently prevented. Also, the amount of impact resistance improver used is 25%.
If it exceeds, the heat resistance and rigidity will be poor.

The filler is a component used for improving strength, rigidity, dimensional stability and the like, and the filler used is not particularly limited. Specific examples of the filler include talc (magnesium silicate), calcium carbonate (heavy, light, colloid, etc.), mica, magnesium oxide, magnesium carbonate, barium sulfate, calcium sulfate, calcium sulfite, silica, clay, kaolin , White carbon, magnesium hydroxide, carbon black, zeolite, molybdenum and the like. Of these, talc, calcium carbonate and mica are particularly preferred.

The amount of the filler added is 1 to 50 with respect to 100 parts (parts by weight, the same applies hereinafter) of the modified PPE resin (II).
Parts, preferably 5 to 40 parts. If the addition amount is less than 1 part, the clear effect of filling the filler (inorganic substance) cannot be obtained, and if the addition amount exceeds 50 parts, the viscosity of the resin composition increases and a large load is applied to the extruder. For this reason, it is not preferable, and the impact strength of the non-foamed layer is significantly reduced.

A preferred specific example of the primary foam laminated sheet in which the modified PPE resin (II) non-foamed layer is formed on at least one surface of the modified PPE resin (I) foam sheet as described above is the modified PPE resin described above. A preferable example of the foamed sheet (I) and a preferable example of the modified PPE resin (II) non-foamed layer may be combined.

The molded article for an automobile interior material of the present invention is obtained by using the above-mentioned primary foam laminated sheet in an oven for 30 to 12
Heating for 0 seconds to bring the surface temperature to the heat distortion temperature of the base resin of the foam layer or higher, and the closed cell ratio maintained at 70% or higher, the heat distortion temperature of the base resin of the foam layer at 60 ° C or higher. It is a molded product obtained by molding using a mold whose temperature is controlled to the following temperature.

The surface temperature of the primary foam laminated sheet when heated in an oven is equal to or higher than the heat deformation temperature of the base resin of the foam layer. Since the thermal deformation temperature changes depending on the resin component forming the primary foam laminated sheet, it is difficult to specify a specific thermal deformation temperature. However, for example, when the base resin of the foam layer is P
PE-based resin component 40-55%, PS-based resin component 60-4
In the case of 5%, the heat distortion temperature is about 125 to 137 ° C. If the surface temperature during heating is lower than the heat deformation temperature, the foamed laminated sheet will not be sufficiently stretched during molding, resulting in tearing of the foamed laminated sheet, whitening of the non-foamed layer, and poor moldability, and good molding. I can't get any body. Also,
It is preferable to mold the foamed laminated sheet in a state before the keloid state is generated on the surface of the foamed laminated sheet due to heating in the molding.
As a result of research conducted by the present inventors, it has been found that when molding is carried out in a state where a keloid state is generated on the surface during molding heating, the closed cell rate is lowered and the rigidity is lowered. The keloid state is caused by the foam breaking of the foamed layer, and therefore, the closed cell rate is reduced. Therefore,
The surface temperature during heating is the temperature at which no keloid state occurs,
Higher than the heat distortion temperature of the base resin of the foam layer,
It is preferably 30 ° C or lower, and more preferably 15 to 27 ° C higher than the heat distortion temperature. As a result, it can be molded in a state with a high closed cell rate, and a foamed molded product as a result can have a closed cell rate of 70% or more, and further 80% or more.

The surface temperature is a temperature measured by a method in which a thermo label (Thermo Label 5E, NOF Giken Co., Ltd.) is attached to the surface of the foam laminated sheet, the foam laminated sheet is heated in an oven, and the thermo label indicated temperature is obtained. Is.

Further, the heating time is 30 to 120 seconds, further 48 to 100 seconds, and in the case of heating for less than 30 seconds, the heat resistance of the obtained molded product is inferior, and if it exceeds 120 seconds, it is produced. Sex decreases.

Further, the time after the heating in the oven until it is led out of the oven and molded in the mold is preferably within 15 seconds, more preferably within 10 seconds, and especially within 6 seconds. If it is longer than 15 seconds, cooling of the sheet will proceed, the laminated foam sheet will not be sufficiently stretched during die molding, tearing or whitening of the non-foamed layer will occur, and mold determination will become difficult, and acceptable molding It becomes difficult to get a body.

According to the research conducted by the present inventor, when the heating is performed for less than 30 seconds, the surface temperature of the laminated foamed sheet is rapidly lowered. Therefore, the time from taking out from the oven to molding with a mold is within 6 seconds. It has been confirmed that it must be done. It has also been confirmed that a molded product having good heat resistance cannot be obtained. The reason for this is that in the case of a material with high heat resistance such as a modified PPE-based resin foamed laminated sheet, heating inside the primary foamed laminated sheet will not be sufficiently heated by heating for a short time, so that molding strain during molding remains. It is considered that the residual strain is relieved when it is exposed to high temperature for a long time as a strain, and the molded body is deformed. On the other hand, if heating for 30 seconds or more, 30
It has been also confirmed that the surface temperature decreases more slowly than in the case of heating for less than a second, the time required for molding the mold can be extended, and the range of molding conditions can be widened. It has also been confirmed that a molded product having good heat resistance can be obtained.

Further, the closed cell ratio of the primary foam laminated sheet when heated in the oven is 70% or more, and further 80%.
It is preferable to maintain the above-mentioned value from the viewpoint of improving the rigidity and heat insulating property of the obtained molded body.

The oven used for heating the primary foam laminated sheet is not particularly limited, and for example, an oven such as a heating furnace in which far-infrared heaters whose temperatures are individually adjusted is arranged above and below is preferably used.

The operating conditions of the oven for heating the primary foam laminated sheet are as follows:
Oven heating time is 30 to 12 when conditions such as 0 to 230 ° C. and heating furnace atmosphere temperature of 160 to 200 ° C. are adopted.
It is preferable because it can be easily set to 0 seconds.

The temperature of the mold used for the molding is 60 ° C.
As described above, the temperature is preferably 70 ° C. or higher and not higher than the heat distortion temperature of the base resin of the foam layer, and preferably −20 ° C. or lower. When the temperature is lower than 60 ° C, the heat resistance of the obtained molded product is poor, and when it is higher than the heat deformation temperature of the base resin of the foam layer, the molded product is likely to be deformed immediately after releasing from the mold. .

The mold temperature is a value obtained by measuring the surface temperature of the mold using a contact type thermometer (HC-200 manufactured by Anritsu Keiki Co., Ltd.).

If necessary, a skin material may be laminated on the molded article for automobile interior material, which is the secondary foamed laminated sheet molded article.

Specific examples of the skin material include skin materials conventionally used as interior materials for automobiles, such as woven fabric and non-woven fabric. These may be manufactured from synthetic resins such as polyester (for example, polyethylene terephthalate), polypropylene, polyamide (for example, nylon), polyacrylonitrile, etc., and may be those using natural materials such as wool and cotton. Alternatively, a combination of them may be used. Further, when the molded article for automobile interior material of the present invention requires flame retardancy, it is preferable to use a skin material imparted with flame retardancy.

In the molded article for automobile interior of the present invention as described above, while keeping the closed cell ratio high at the time of molding, the heating time is set to 30 to 120 seconds and the surface temperature is made equal to or higher than the heat deformation temperature of the foam layer. Fully heat the inside of the foam layer,
Residual strain generated in the molded body can be suppressed, and the mounting heat resistance is excellent. Further, since the molding is performed in a mold whose temperature is controlled to be lower than the thermal deformation temperature of the foam layer base resin at 60 ° C. or higher, the dimensional stability after releasing from the mold is excellent, and there is little damage due to transportation and handling. It has excellent properties.

Next, a method for producing the molded article for automobile interior material of the present invention will be described.

The modified PPE-based resin (I) foamed sheet (primary foamed sheet) used in the present invention is a mixed resin of PPE-based resin and PS-based resin or a graft copolymer of styrene-based monomer onto PPE-based resin. If necessary, various additives are added to the polymerized copolymer, and the mixture is heated to 150 to 4 by an extruder.
Melt and knead at 00 ° C, further 200 to 350 ° C, then 150 to 400 ° C, further 200 to 350 ° C, 3
The foaming agent (1 to 15 parts, preferably 2 to 10 parts) is pressed into 100 parts of the resin under high temperature and high pressure of 0 to 500 atm, further 50 to 400 atm, and the optimum foaming temperature (150 to 300) is obtained.
C., and then 180 to 250.degree. C.) and then extruding into a low pressure range (usually in the atmosphere), and then forming it into a sheet by a mandrel or the like while taking it under the condition of 0.5 to 4.0 m / min. Can be manufactured by.

As the foaming agent used for producing the modified PPE resin (I) foamed sheet, hydrocarbon-based agents such as butane, propane, pentane, methyl chloride, dichloromethane, chlorofluoromethane, dichloroethane and dichlorodifluoroethane are used. Examples thereof include foaming agents and halogenated hydrocarbon foaming agents. These may be used alone or in combination of two or more. Among them, hydrocarbon blowing agents are preferred from the viewpoint of versatility and cost.

As a method for laminating the modified PPE resin (II) non-foamed layer on the primary foamed sheet, the resin which has been molded into a film shape in advance is foam-molded and / or supplied on the upper surface of the primary foamed sheet. Examples of the method include a method of adhering to the lower surface with a heat roll, a coextrusion laminating method using a multilayer extrusion die, and the like. A method is preferred in which the resin composition of the non-foaming layer supplied from the above is laminated in layers and the non-foaming layer in a plastic state is fixed by a cooling roller or the like. Among them, the method of laminating by extruding the non-foamed layer and the extrusion foamed sheet forming the primary foamed layer in-line is preferable because of reduced manufacturing steps.

As a method for producing a molded secondary foamed laminated sheet which is a molded article for automobile interior materials from the obtained primary foamed laminated sheet, primary foaming is performed in the center of an oven (for example, an oven having a heater above and below). The laminated sheet is clamped and guided, and heated for 30 to 120 seconds so that the surface temperature is equal to or higher than the heat deformation temperature of the base resin of the foam layer (for example, 120 to 200).
C.) and a closed cell ratio of 70% or more, and then secondary foaming, and molding with a mold whose temperature is controlled to 60 ° C. or higher and below the heat deformation temperature of the base resin of the foam layer (for example, vacuum molding or A method such as pressure molding may be used.

As examples of the above-mentioned forming (vacuum forming, pressure forming), plug forming, free drawing forming, plug
Examples of such methods include and-ridge molding, ridge molding, matched molding, straight molding, drape molding, reverse draw molding, air slip molding, plug assist molding, plug assist reverse draw molding and the like.
Among these, a method capable of changing the mold clearance such as plug molding or matched molding is preferable.

In the case of vacuum molding, secondary foaming is performed using a mold having only one mold like straight molding,
You may shape.

In this way, the molded article for automobile interior material of the present invention is manufactured.

When the molded article for automobile interior material, which is the molded secondary foamed laminated sheet, has a skin, the method for preparing the skin material to which an adhesive is previously attached is 1
A method of adhering the next foamed laminated sheet using a heat roll or the like, an adhesive is laminated on the primary foamed laminated sheet by a binder lamination method or an adhesive formed in advance in a film shape by a heat lamination method, and then the skin material is heated. A method of adhering using a roll or the like, a method of temporarily fixing a skin material to a primary foam laminated sheet, and simultaneously performing molding and adhesion during heat molding, and a method of simultaneously bonding the skin material when laminating the adhesive to the primary foam laminated sheet. Examples of such methods include bonding.

Examples of the adhesive include a thermoplastic adhesive, a hot melt adhesive, a rubber adhesive, a thermosetting adhesive, a monomer reactive adhesive, an inorganic adhesive, and a natural adhesive. From the viewpoint of easy adhesion, a hot melt adhesive is preferred.

Examples of the hot melt adhesive include polyolefin, modified polyolefin, polyurethane, and the like.
Examples thereof include those containing a resin such as ethylene-vinyl acetate copolymer resin system, polyamide system, polyester system, thermoplastic elastomer system, styrene-butadiene copolymer system and styrene-isoprene copolymer system.

When the surface temperature is measured by heating a laminated skin material in an oven, the surface temperature is the temperature of the surface portion of the non-foamed layer. When the surface material is laminated, the temperature of the surface portion of the non-foaming layer may be measured by cutting out the thermolabeled portion from the molded article after molding, peeling the surface material, and measuring the surface temperature. In the examples, molding was performed under the same conditions as the surface temperature was measured to evaluate heat resistance and the like.

[0066]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

The main components and materials used in Examples and Comparative Examples are shown in Tables 1 and 2.

[0068]

[Table 1]

[0069]

[Table 2]

Further, the heat distortion temperature, closed cell rate, moldability and mounting heat resistance of the base resin of the foam laminated sheets in Examples and Comparative Examples were measured by the following methods.

(Heat Distortion Temperature (HDT)) The primary foamed sheet was heated to 200 ° C. using a hot press molding machine to control the temperature to 100%.
^2. Press at kg / cm ² -G to crush air bubbles to obtain a thickness of 3.
After molding to 0 mm, width 13 mm, length 127 mm,
A test piece was manufactured by applying an annealing treatment at 100 ° C. for 10 hours. After that, the heat distortion tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used to measure the heat distortion temperature according to ASTM 648, and the value when the load was 1820 kPa was taken as the heat distortion temperature.

(Closed cell ratio) A test piece was cut out from the molded body, and a pycnometer (Beckman-TOSHIB) was used.
A, LTD, AIR COMPARISON PYCN
The volume V ₀ and the submerged volume V ₁ were measured using OMETER Mode1 930), and then the closed cell ratio was calculated by the formula: closed cell ratio (%) = (V ₀ / V ₁ ) × 100.

(Moldability) Under each condition, a molded product having a length of 1425 mm, a width of 930 mm and a thickness of 3.5 mm was molded, and the length in the width direction of the molded product immediately after being released from the mold was measured. Then, after standing at room temperature for 2 hours, the length in the width direction at the same location was measured, the amount of deformation thereof was determined, and evaluated according to the following criteria.

◯: Deformation is less than 5 mm Δ: Deformation is 5 mm or more and less than 10 mm ×: Deformation is 10 mm or more (mounting heat resistance) As shown in FIG. 1, a molded article for an automobile ceiling material (size 930 mm × 1425 mm, front bent portion is As shown in FIG. 2, the angle is 120 °, and the center of the bent portion (the line that bisects the angle at the point where the extension line from the front portion side for obtaining the angle and the extension line from the ceiling portion intersect) is bent. 15mm from the point where it intersects with the front side
It is. It should be noted that this length is approximately equal to the length of the front part side of the molded article for automobile ceiling material from the intersection of the two extension lines, where 1 in FIG. 1 is the molded article for automobile ceiling material and 2 is the assist grip. Mounting holes, 3 is a sun visor mounting hole, 4 is a rearview mirror mounting hole, 5 is a room light mounting hole, 6 in FIG. 2 is a modified PPE resin (I) foam layer, and 7 is a modified PPE resin (II) non- Foam layer, 8 is a windshield, 9 is a roof, FIG. 3 is a sectional view taken along the line AA of FIG. 1, and FIG.
B cross-sectional explanatory view) was manufactured, and the molded body was mounted on the ceiling of a vehicle through a sun visor, a rearview mirror, a room light, a garnish pillar, and in the same manner as an actual vehicle as shown in FIG. Next, left and right, front and back 2 centered on the interior light
Twelve measuring points were marked on the molded body at regular intervals of 00 mm.
In order to measure the amount of sag of the measurement point with respect to the ceiling portion, a marked line was provided below each measuring point, and the distance between the marked line and the measured point of the molded body marked was measured. Further, six measurement points were marked on the front part, and the center line of the molded product and the object were marked at intervals of 150 mm (a to f in FIG. 1). A marked line was provided near the measurement point on the front part to measure the horizontal distance. 85 ± 1
The molded body was put into a constant temperature and constant humidity chamber set at 0 ° C and a humidity of 0% for 4 hours, and then cooled at -35 ° C for 2 hours. After repeating this operation four times, the absolute value of the vertical change amount of the measurement points marked on the ceiling of the molded product and the absolute value of the horizontal dimension change amount of the measurement points marked on the front part of the molded product. Was measured and the average value was calculated for each. The evaluation criteria are as follows.

◯: The average dimensional change amount in both the horizontal and vertical directions is 5.0 mm or less. Δ: Either the horizontal or vertical direction average dimensional change amount is larger than 5.0 mm. X: Both the horizontal and vertical average dimensional change amounts are larger than 5.0 mm.

Example 1 A mixed resin (HD) obtained by mixing the modified PPE resin (A) and PS resin (B) shown in Table 1 so that the PPE resin and the PS resin are 40% and 60%, respectively.
Foaming agent containing iso-butane as a main component (iso-butane / n-butane = 85) relative to 100 parts of T 125 ° C.
/ 15) 3 parts and 0.32 part of talc are added, and the mixture is kneaded in an extruder at 305 ° C., cooled to a resin temperature of 198 ° C., extruded from a circular die and cut open for 5 m.
It was wound into a roll on a take-up roll through a take-up roll having a speed of 1 / min.

The obtained primary foam sheet has a thickness of 2.3 m.
m, width 120 cm, primary expansion ratio 10 times, closed cell rate 8
5%, cell diameter 0.19 mm, and basis weight 240 g / m ² .

While paying out the obtained primary foamed sheet at a speed of 5 m / min, the PPE resin component, PS resin component and rubber component were adjusted to 30%, 64% and 6%, respectively, as shown in Table 1. Modified PPE resin (A), PS described in 1.
A mixed resin (HDT 117 ° C) in which the resin (B) and the impact resistance improver (C) are mixed is melted and kneaded at 310 ° C by an extruder, and extruded at a resin temperature of 278 ° C using a T die to perform primary foaming. A non-foamed layer having a thickness of 150 μm was laminated on one side of the sheet to produce a primary foamed piece area layer sheet, which was wound into a roll. Next, the obtained primary foamed piece area layer sheet was unwound in the same manner as above, and the non-foamed layer was laminated on the surface of the foamed layer on the side opposite to the side on which the non-foamed layer was provided by the same method. The foamed double-sided laminated sheet was wound into a roll.

The obtained primary foam double-sided laminated sheet was cut to obtain a sheet having a size of 120 cm × 160 cm and a thickness of 2.5 mm.

The cut primary foam double-sided laminated sheet thus obtained was clamped on all sides and placed in an oven having an oven temperature of 180 ° C. and heated for 60 seconds so that both surface temperatures were 150 ° C. At this time, no keloid state was observed on the surface. After that, the sheet was drawn out from the heating furnace, and after 5 seconds, the clearance adjusted to 80 ° C had a clearance of 3.5 mm.
After performing plug molding for 10 seconds using the mold, trimming was performed by punching to obtain a molded article for automobile ceiling material (test sample). At this time, the moldability was evaluated.

The molded article for automobile ceiling material thus obtained was attached to an automobile ceiling portion and a mounting heat resistance test was carried out. Further, a test piece was cut out from the center of the obtained molded article for automobile ceiling material, and the closed cell ratio was measured.

The results are shown in Table 3.

Example 2 A molded article for an automobile ceiling material was produced and evaluated in the same manner as in Example 1 except that the mold temperature was 100 ° C. Table 3 shows the results
Shown in

Example 3 A molded article for automobile ceiling material was produced and evaluated in the same manner as in Example 1 except that the mold temperature was set to 130 ° C. Table 3 shows the results
Shown in

Example 4 A molded article for automobile ceiling material was produced and evaluated in the same manner as in Example 1 except that the mold temperature was 30 ° C. The results are shown in Table 3.

Example 5 A molded article for automobile ceiling material was produced and evaluated in the same manner as in Example 1 except that the furnace temperature was 190 ° C. and the heating time in the oven was 40 seconds. The results are shown in Table 3.

Example 6 In the same manner as in Example 1, a primary foam double-sided laminated sheet was prepared in which a non-foamed layer was laminated on both sides of the primary foamed sheet.

Clamping the four sides of the primary foam laminated sheet having the skin material in which the skin material (E) is temporarily fixed to one surface of the obtained primary foam double-sided laminated sheet via the hot melt film (D) which is an adhesive agent. Then, it was placed in an oven having a furnace temperature of 180 ° C. and heated for 70 seconds so that the surface temperature was 145 ° C. on the surface of the non-foaming layer on the skin material side and 150 ° C. on the opposite side. At this time, no keloid state was observed on the surface. After that, pull out the sheet from the heating furnace and wait 8 seconds after 8 seconds.
Place the mold in a mold whose temperature is controlled at 0 ° C with the skin side facing the convex mold, perform plug molding for 10 seconds using a mold with a mold clearance of 4.0 mm, and then trim by punching. Then, a molded article for an automobile ceiling material (test sample) was manufactured, and the moldability, mounting heat resistance, and closed cell ratio were evaluated in the same manner as in Example 1.

Table 3 shows the results.

Example 7 In the same manner as in Example 1, a primary foamed piece area layer sheet was prepared by laminating a non-foamed layer on one surface of the primary foamed sheet, and a cut primary foam piece area layer sheet was obtained.

The obtained primary foam piece area layer sheet was clamped on all sides and placed in an oven having a furnace temperature of 175 ° C., the surface temperature of the non-foaming layer side was 150 ° C., and the surface temperature of the foaming layer side was 14 ° C.
It heated for 55 seconds so that it might become 5 degreeC. At this time, no keloid state was observed on the surface. After that, the sheet was drawn out from the heating furnace, and after 5 seconds, the mold was placed at a temperature of 80 ° C. so that the non-foaming layer side was the convex mold side, and the mold clearance was 3.5 mm. After plug molding for 10 seconds, trimming by punching,
A molded article for automobile ceiling material (test sample) was manufactured, and the moldability, mounting heat resistance, and closed cell ratio were evaluated in the same manner as in Example 1.

The results are shown in Table 3.

Example 8 In the same manner as in Example 7, a primary foam sheet area layer sheet in which a non-foam layer was laminated on one side of a primary foam sheet was produced, and a hot melt film (D ), The four sides of the primary foamed laminated sheet having the skin material in which the skin material (E) is temporarily fixed are clamped, and placed in an oven with a furnace temperature of 175 ° C. 145
C. and the surface temperature on the opposite side was 145.degree. C. for 60 seconds. At this time, no keloid state was observed on the surface. After that, the sheet was drawn out from the heating furnace, and after 5 seconds, the sheet was placed with the die temperature-controlled at 80 ° C. so that the skin material side was the convex die side, and the die clearance was 4.0 mm. After performing plug molding for 2 seconds, trimming was performed by punching to manufacture a molded article for automobile ceiling material, and the moldability, mounting heat resistance, and closed cell ratio were evaluated in the same manner as in Example 1.

The results are shown in Table 3.

Example 9 The PPE resin component and the PS resin component were each 55
% And 45% modified PPE resin (A) (HDT
137 ° C.) 100 parts, a blowing agent containing iso-butane as a main component (iso-butane / n-butane = 85 /
15) Add 3 parts and 0.32 part of talc, knead at 315 ° C. with an extruder, cool to a resin temperature of 205 ° C., extrude from a circular die and cut open.
It was wound into a roll on a take-up roll through a take-up roll having a speed of m / min.

The obtained primary foam sheet has a thickness of 2.3 m.
m, width 120 cm, foaming ratio 10 times, closed cell rate 87
%, The cell diameter was 0.17 mm, and the basis weight was 240 g / m ² .

The modified primary PPE resin was adjusted so that the PPE resin component, PS resin component and rubber component were 40%, 54% and 6%, respectively, while paying out the obtained primary foamed sheet at a speed of 5 m / min. (A), PS resin (B) and impact resistance improver (C) mixed resin (HDT
(125 ° C) is melted and kneaded at 315 ° C by an extruder, and T
A primary foam sheet was extruded at a resin temperature of 285 ° C. using a die, a non-foam layer having a thickness of 150 μm was laminated on one side of the primary foam sheet to produce a primary foam single-area layer sheet, which was wound into a roll.

The obtained primary foamed laminated sheet was unwound in the same manner as above, and the non-foamed layer was laminated in the same manner on the surface of the foamed layer opposite to the side on which the non-foamed layer was provided. The double-sided laminated sheet was wound into a roll.

The obtained primary foam double-sided laminated sheet was cut to obtain a primary foam laminated sheet having a size of 120 cm × 160 cm and a thickness of 2.5 mm.

The cut primary foamed laminated sheet thus obtained was clamped on all sides and placed in an oven having a furnace temperature of 185 ° C. so that both surface temperatures would be 155 ° C. 60
Heated for a second. At this time, no keloid state was observed on the surface. After that, the sheet was drawn out from the heating furnace, and after 5 seconds, it was plug-molded for 10 seconds by using a mold having a clearance of 3.5 mm, whose temperature was controlled at 80 ° C., and then trimming was performed by punching to obtain a molded article for automobile ceiling material ( A test sample) was produced and the moldability, mounting heat resistance, and closed cell ratio were evaluated in the same manner as above.

Table 3 shows the results.

Comparative Example 1 For automobile ceiling materials in the same manner as in Example 1 except that the furnace temperature was 220 ° C., the oven heating time was 8 seconds, and both surface temperatures of both the primary foam double-sided laminated sheet were 145 ° C. A molded body was manufactured and evaluated. The results are shown in Table 3.

Comparative Example 2 A molded article for automobile ceiling material was produced and evaluated in the same manner as in Comparative Example 1 except that the mold temperature was 30 ° C. Table 3 shows the results
Shown in

Comparative Example 3 A molded article for an automobile ceiling material was produced and evaluated in the same manner as in Comparative Example 1 except that the mold temperature was 130 ° C. The results are shown in Table 3.

Comparative Example 4 The furnace temperature was 205 ° C., the oven heating time was 20 seconds, and both surface temperatures of the primary foam double-sided laminated sheet were 150 ° C.
A molded article for an automobile ceiling material was manufactured and evaluated in the same manner as in Comparative Example 1 except that the above was used. The results are shown in Table 3.

Comparative Example 5 The furnace temperature was 210 ° C., the oven heating time was 18 seconds, and both surface temperatures of the primary foam double-sided laminated sheet were 165 ° C.
A molded article for an automobile ceiling material was manufactured and evaluated in the same manner as in Comparative Example 1 except that the above was used. In this case, a keloid state was recognized on the surface, and the closed cell ratio was as low as 23%. Further, since the rigidity of the molded product is low, there are problems that the molded product is broken during handling, the clip is not properly fixed to the automobile ceiling, and the molded product is wobbled when mounted on the ceiling. The results are shown in Table 3.

Comparative Example 6 The furnace temperature was 205 ° C., the oven heating time was 40 seconds, and both surface temperatures of the primary foam double-sided laminated sheet were 170 ° C.
A molded article for automobile interior material was produced and evaluated in the same manner as in Comparative Example 1 except that the above was used. Also in this case, a keloid state was recognized on the surface, and the closed cell ratio was as low as 18%. Also,
Since the rigidity of the molded body is low, there are problems that the molded body breaks during handling, the clip is not properly fixed to the automobile ceiling, and the molded body wobbles when mounted on the ceiling. The results are shown in Table 3.

[0108]

[Table 3]

[0109]

INDUSTRIAL APPLICABILITY The molded article for automobile interior material of the present invention is a molded article for automobile interior material having sufficient heat resistance and rigidity and excellent in lightweight and heat insulating property, and requires automobile interior material, especially heat resistance. It can be preferably used for interior materials (for example, ceiling materials, door trims, etc.).

Further, the molded article for automobile interior material having improved heat resistance of the present invention can be adjusted by adjusting the heating time and the mold temperature using the conventional equipment, without impairing the productivity.
It is possible to improve the low heat resistance of a conventional molded product of a material having high heat resistance, and obtain a molded product for an automobile interior material that retains the high heat resistance, rigidity, and heat insulation properties of the material itself.

[Brief description of drawings]

FIG. 1 is an explanatory plan view for explaining a planar shape after trimming by punching of molded articles for automobile ceiling materials molded in Examples 1 to 9 and Comparative Examples 1 to 6 of the present invention.

FIG. 2 is a cross-sectional explanatory view in the vicinity of an upper portion of an automobile windshield for explaining a state in which molded articles for automobile ceiling materials formed in Examples 1 to 9 and Comparative Examples 1 to 6 of the present invention are actually mounted, It is explanatory drawing at the time of providing a non-foaming layer on one side.

FIG. 3 is a cross-sectional view taken along the line AA in FIG. 1 showing molded articles for automobile ceiling materials molded in Examples 1 to 9 and Comparative Examples 1 to 6 of the present invention, in which a non-foamed layer is provided on one surface. FIG.

FIG. 4 is a sectional view taken along line BB of FIG. 1 showing molded articles for automobile ceiling materials molded in Examples 1 to 9 and Comparative Examples 1 to 6 of the present invention, in which a non-foaming layer is provided on one surface. FIG.

FIG. 5 is a cutaway explanatory view for explaining a state in which a molded article for an automobile ceiling material, which is one of the molded articles for an automobile interior material of the present invention, is attached to an automobile.

[Explanation of symbols]

 1 Molded product for automobile ceiling material 2 Assist grip mounting hole 3 Sun visor mounting hole 4 Room mirror mounting hole 5 Interior light mounting hole 6 Modified PPE resin (I) foam layer 7 Modified PPE resin (II) non-foam layer 8 Front Glass 9 roof

Claims (4)

[Claims] 1. A modified polyphenylene ether-based resin (I) obtained by laminating a non-foamed layer of modified polyphenylene ether-based resin (II) on at least one surface of a foamed sheet.
The next foamed laminated sheet is heated in an oven for 30 to 120 seconds so that the surface temperature becomes equal to or higher than the heat deformation temperature of the base resin of the foamed layer,
And, while maintaining the closed cell ratio at 70% or more, 60
A molded article for an automobile interior material, which is molded using a mold whose temperature is controlled to a temperature not lower than ° C and not higher than a heat deformation temperature of a base resin of a foam layer. 2. The molded article for automobile interior materials according to claim 1, which is formed by laminating a skin material. 3. A modified polyphenylene ether-based resin (I) obtained by laminating a non-foamed layer of modified polyphenylene ether-based resin (II) on at least one surface of a foamed sheet.
The next foamed laminated sheet is heated in an oven for 30 to 120 seconds so that the surface temperature becomes equal to or higher than the heat deformation temperature of the base resin of the foamed layer,
And, while maintaining the closed cell ratio at 70% or more, 60
A method for producing a molded article for automobile interior material, which comprises molding using a mold whose temperature is controlled to a temperature not lower than ° C and not higher than the heat distortion temperature of the base resin of the foam layer. 4. The method for producing a molded article for an automobile interior material according to claim 3, wherein the skin material is laminated.