JPH08134281A - Flame retardant resin composition - Google Patents

Abstract

PURPOSE: To obtain a flame retardant resin composition that shows a high melt fluidity suitable for powder slush molding, is excellent in extrusion moldability, and does not release toxic materials when burnt. CONSTITUTION: This flame retardant resin composition comprises a resin mixture of an olefin resin and a flexibilizer and having a melt index in the range of 0.5 to 150 to which a filler has been added in an amount of 30wt.% or less. The filler is made up of 1 to 10wt.% metal hydroxide, 1 to 5wt.% red phosphorus, 0.5 to 3wt.% boron compound, 2 to 10wt.% metal oxide, and 1 to 3wt.% dioctyl phthalate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for resin molded articles for molding automobile interior parts,
The present invention relates to a flame-retardant polyolefin-based resin composition for obtaining a resin molded product by powder slush molding for forming automobile interior parts.

[0002]

2. Description of the Related Art Conventionally, there is a powder slush molding method as one of the molding methods for skins of, for example, console boxes and door trims in automobile interiors. However, this is mainly because of its workability (fluidity during melting). Vinyl chloride resin is used as a material. In addition, as an automobile interior component, an integrally molded product in which urethane foam is molded and foamed on the inner surface (back surface) of the skin is used in order to impart elasticity to the above skin and to maintain the overall shape and robustness. ing. The above-mentioned skin and integrally molded product are processed by powder slush molding, extrusion molding and the like. Also, the seat is mainly made of a vinyl chloride resin material, and is manufactured by a combination of a skin obtained by extrusion processing and urethane foam.

[0003]

Vinyl chloride resin is a material that is inexpensive, has excellent physical properties, and is self-extinguishing. However, when it is molded and used as an automobile interior part, when it is used only as a skin or as a foam layer. Each of the two-layer structure provided is an integrally molded product obtained by molding and foaming urethane foam with insert material.

[0004] When an automobile exceeds the useful life or is disposed of as an abandoned automobile due to an accident or the like, each component of the automobile is removed, and sorting work is performed for recycling. However, since the skin, which is an interior product, is integrally molded with urethane, it is difficult to separate it, cannot be recycled, and must be incinerated as waste. In addition, since vinyl chloride and urethane both generate a large amount of smoke containing harmful gas and cause pollution when incinerated, they cannot be completely incinerated today.

In addition, the molding process of these molded products involves a large number of processes because of the work of injecting urethane into the skin obtained by powder slush molding and fitting the core material manufactured by another process. It becomes complicated and causes a cost increase.

Particularly in the powder slush molding, after the raw material resin powder is brought into contact with a heated die by a powdering method in a state close to a natural fall, the raw material resin powder is melted and adhered to the die surface by the heat of the die, It is a method of collecting excess raw material powder, cooling the mold and demolding the molded product, and molding the skin of a certain thickness.Therefore, since the external pressure is not applied to the raw material powder, the raw material resin powder is High fluidity at the time of melting is required for the mold surface.

Conventionally, vinyl chloride resin has been generally used as a raw material for members requiring flame retardancy. As a substitute material, there are a flame-retardant method using a halogen compound and antimony trioxide in a flammable polyolefin resin, and a so-called non-halogen flame-retardant method that does not use these halogen compounds, and the latter general method is an inorganic method. The filler is mixed in an amount of 35 to 60% by weight.

Such a resin composition having a high content of an inorganic filler does not have not only the melt fluidity optimum for powder slush molding but also the thermal conductivity even if the melt fluidity is good. However, it is a material that cannot be used as an automobile interior product because it deteriorates the resin properties, causes uneven melting of the resin, local solidification, and the like, which causes uneven film thickness and pinholes.

As described above, the present invention has been made in view of various problems such as materials and molding methods for molding conventional automobile interior parts.
By making the polyolefin resin a flame-retardant material by a non-halogen flame-retardant method, it has high fluidity when melted, which is optimal for powder slush molding, excellent extrusion moldability, and does not generate harmful substances during combustion, and An object of the present invention is to provide a composition for a resin molded product, which can recycle the molded product when the vehicle is scrapped.

[0010]

In order to achieve the above object, the resin composition of the present invention comprises an olefin resin and an olefin resin mixed with a flexibility modifier.
In each case, two or more kinds having a melt index in the range of 0.5 to 150 (g / 10 minutes) are mixed and used, and also five kinds of fillers for flame retardation are used in combination, and this is used as a resin mixture. The compounding amount is 30% by weight or less in total.

That is, according to the present invention, an olefin resin, an olefin resin blended with a flexibility modifier, a resin mixture having a melt index of 0.5 to 150, and metal water as a filler are used. 1-10 wt% oxide, 1-5 wt% red phosphorus, 0.5-3 wt% boron compound, 2-10 wt% metal oxide and 1-3 wt% dioctyl phthalate are combined, and the filler is in total. There is provided a flame-retardant resin composition characterized by being blended in an amount of 30% by weight or less.

Further, according to the present invention, an olefin resin, a mixture of an olefin resin and a flexibility modifier, and a resin mixture having a melt index of 0.5 to 150 are added with a metal water as a filler. 1-10 wt% oxide, 1-5 wt% red phosphorus, 0.5-3 wt% boron compound, 2-10 wt% metal oxide and 1-3 wt% dioctyl phthalate are combined, and the filler is in total. There is provided a flame-retardant resin composition comprising a resin composition blended in an amount of 30% by weight or less and a foaming agent or a mixture of a foaming agent and a crosslinking agent.

In the present invention, the resin mixture having a melt index of 0.5 to 150 is polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, ethylene copolymer. And at least 2 selected from flexibility modifiers
It is composed of more than one resin. Examples of ethylene copolymers include ethylene / vinyl acetate copolymers, ethylene / acrylic acid ester copolymers, ethylene / acrylic acid copolymers and ethylene / methacrylic acid copolymers.

In the present invention, the metal hydroxide is magnesium hydroxide or aluminum hydroxide, the red phosphorus is red phosphorus surface-treated with a titanium coat, and the boron compound is zinc borate or aluminum borate. And the metal oxide is titanium oxide, iron oxide, alumina, silicon oxide, magnesium oxide, calcium oxide,
It is either zinc oxide.

With respect to the resin portion of the resin composition of the present invention, it is impossible to uniformly impart physical properties such as heat resistance, fluidity at the time of melting and flexibility with a single resin to the characteristics required for a molded product. Therefore, using two or more resins as a mixture,
When the filler was compounded, the characteristics of each resin were utilized to compensate for the fragile parts and obtain uniform physical properties. Further, when the required heat resistance cannot be obtained even with a mixture of two or more kinds of resins, an organic peracid compound is blended as a crosslinking agent to improve the heat resistance.

In the present invention, the olefin resin is a polyolefin resin composed of a homopolymer or a copolymer of olefins such as ethylene and propylene, and an ethylene resin composed of a copolymer of ethylene and another copolymerization component. It includes a copolymer (for example, a copolymer of ethylene and vinyl acetate, acrylic ester, acrylic acid or methacrylic acid).

The resin mixture in the resin composition of the present invention is preferably selected from the following five basic blends A to E according to the use of the flame-retardant resin composition. (A) 20 to 70 parts by weight of a flexibility modifier (B) 100 parts by weight of polypropylene, based on 100 parts by weight of a polyolefin resin composed of a homopolymer of olefins such as ethylene and propylene or a copolymer thereof. Ethylene-based copolymer 100 to 250 parts by weight Linear ultra-low density polyethylene 10 to 80 parts by weight Linear low density polyethylene 0 to 50 parts by weight Low density polyethylene 0 to 50 parts by weight Flexibility modifier 20 to 60 parts by weight Parts (C) 100 parts by weight of polypropylene High density polyethylene 20 to 80 parts by weight Ethylene copolymer 100 to 250 parts by weight Linear ultra low density polyethylene 20 to 100 parts by weight Linear low density polyethylene 0 to 50 Parts by weight Low-density polyethylene 0 to 50 parts by weight (D) 100 parts by weight of high-density polyethylene, linear Density polyethylene 40 to 120 parts by weight Linear ultra-low density polyethylene 0 to 50 parts by weight Low density polyethylene 0 to 50 parts by weight Ethylene-based copolymer 100 to 200 parts by weight Flexibility modifier 30 to 120 parts by weight (E) Linear low density polyethylene 10 to 80 parts by weight, linear ultra low density polyethylene 0 to 50 parts by weight, low density polyethylene 0 to 50 parts by weight, relative to 100 parts by weight of the ethylene copolymer.

When it is necessary to form a composite material by laminating a foamed layer after molding the resin composition, an optimum one is selected from the basic blends (A) to (E) depending on the processing step and application. 100 parts by weight of a resin composition in which the resin mixture of any one of (A) to (E) and a filler for flame retardation is blended in a total amount of 30% by weight or less based on 100 parts by weight of azodicarbonamide And 2 to 10 parts by weight of a sodium bicarbonate-based foaming agent, or 2 to 10 parts by weight of a foaming agent and a crosslinking agent (for example,
Dialkyl oxides and peroxyketals) 0.
It may be added in an amount of 5 to 3 parts by weight.

In the present invention, the filler for making the resin flame-retardant is a combination of five kinds of metal hydroxide, red phosphorus, boron compound, metal oxide and dioctyl phthalate. It is blended so as to be 30% by weight or less. Specific examples of each filler will be illustrated below. It should be noted that each filler may be used in combination of two or more kinds. Metal hydroxides: magnesium hydroxide, aluminum hydroxide. Red phosphorus: Titanium coated surface treated product. Boron compound: zinc borate, aluminum borate. Metal oxides: titanium oxide, silicon oxide, zinc oxide, iron oxide, magnesium oxide, aluminum oxide. Dioctyl phthalate

The following are examples of combinations of fillers. Filler combination example (1): When compounded in a resin mixture. Magnesium hydroxide 1-10% by weight, red phosphorus 1-5% by weight, zinc borate 0.5-3% by weight, titanium oxide 2
-10 wt%, dioctyl phthalate 1-3 wt%. ++++ ≦ 30% by weight.

Filler combination example (2): When compounded in a resin mixture. Aluminum hydroxide 1-10 wt%, red phosphorus 1-5 wt%, zinc borate 0.5-1 wt% + aluminum borate 0.5-1 wt%, titanium oxide 2-10 wt% +
Iron oxide 0.5-2% by weight + calcium oxide 1-3% by weight, dioctyl phthalate 1-3% by weight. ++++ ≦ 30% by weight.

The flame-retardant resin composition according to the present invention will be described in more detail below. It is generally known that when a resin is mixed with a filler such as an inorganic compound, the physical properties of the resin are deteriorated. The amount of the filler to be blended, and particularly in the case of an inorganic compound, the particle size greatly affects the physical properties of the resin.

The following is a summary of these relationships. 1. The higher the blending amount of the filler, the lower the physical properties of the resin. 2. Of the fillers, the smaller the particle size of the inorganic compound, the better the affinity for the resin, and the larger the filler, the more hindering the physical properties. 3. Generally, the size of the inorganic compound blended in the resin is 1
It is desirable to be 0 micron or less. 50 as an exception
It is possible to use micron-sized ones, but at this time it is necessary to devise not only a single compound but also to formulate it with other small-sized inorganic compounds or to compound it in a copolymer resin with a high melt index. Becomes 4. In the non-halogen flame-retardant prescription, the filler is a fine powder and an inorganic compound of the above-mentioned size is used.Therefore, when the filler is compounded with the resin, physical and chemical bonds between the resin and the inorganic compound are different from each other. It will affect the physical properties.

That is, the dispersibility (uniformity) at the time of kneading the inorganic compound and the resin is good, and one particle of the inorganic compound,
The affinity of the surface of one grain with the resin at the interface of the so-called inorganic material affects the physical properties of the resin, and determines the various physical properties in the composition. For this reason, many inorganic compounds are surface-treated in order to deepen the bond with the resin.

From the above-mentioned relationship between the resin and the inorganic compound, in order to obtain a flame-retardant resin composition exhibiting better physical properties, it is necessary to devise a resin blend. The reason is summarized as follows from the characteristics of each polyolefin resin. 1. Since polypropylene and high-density polyethylene have high melting points and high hardness, they are effective in improving the heat resistance and scratch resistance required for molded articles. In particular, when an inorganic compound is contained in the resin, scratches on the surface of the molded product are
The more inorganic compounds, the easier it becomes to stick. 2. Linear low-density polyethylene and low-density polyethylene are excellent in chemical resistance and can impart physical strength such as tensile strength to the composition. 3. The ethylene-based copolymer has excellent flexibility, processability, and filling property with an inorganic compound. 4. Linear ultra-low density polyethylene is a heterogeneous resin, especially
It is added for the purpose of improving the compatibility with blends having different melt indexes and different melting points. This is similar to the method of coexisting a low-melting ethylene polymer and a high-melting ethylene copolymer. 5. The flexibility modifier is effective when blended when the ethylene-based copolymer alone lacks flexibility. As the flexibility modifier, for example, amorphous or low crystalline α ·
Olefin copolymer, ethylene / propylene copolymer /
Ethylene / propylene / gen terpolymer and the like can be used.

As described above, the flame-retardant resin composition for resin molded products used for molding automobile interior materials by powder slush molding or extrusion molding uses several kinds of resins as a mixture, The physical properties and the filling property of the filler must be improved. On the other hand, the flame-retardant filler must exhibit a small amount of compound so as not to impair the processability and physical properties of the resin. In the resin composition of the present invention, a synergistic effect on flame retardancy was exhibited by the combination of the fillers, and the total amount of the fillers blended could be suppressed to 30% or less. Also, at this time, it was confirmed that dioctyl phthalate, which is used as a plasticizer for ordinary vinyl chloride resins, etc., enhances flame retardancy in addition to its original function as a lubricant when combined with other fillers. Was done.

[0027]

EXAMPLES Next, examples of the powder slush molded skin and the powder slush molded foam layer according to the present invention will be described. Example 1 Flame-retardant polyolefin resin composition (for powder slush molding skin layer) Raw material weight (% ) 1. Polypropylene 20 2. Ultra low density polyethylene 15 3. Ethylene = vinyl acetate copolymer 30 4. Ethylene = ethyl acrylate copolymer 16.8 5. Flexibility modifier 5 6. Magnesium hydroxide 2 7. Red phosphorus 3 8. Zinc borate 1 9. Titanium oxide 4 10. Dioctyl phthalate 2 11. Antioxidant 0.2 12. Weathering agent 0.1 13. Pigment 0.9

The physical properties of the composition obtained by mixing the above raw materials are as follows. Test Item Test method Unit Characteristics melt index JIS K-6760 g / 10min 32 Density ^{JIS K-6760 g / cm 3} 0.988 Tensile strength at break ^{JIS K-6760 Kg / cm 2} 145 Tensile elongation at break JIS K-6760 % 600 Tear strength JIS K-6301 N / kg / mm 4.23 Flammability MVSS (JIS K-6911) cm / min 0 (non-flammable)

Example 2 Flame-retardant polyolefin resin composition (for powder slush molding foam layer) Raw material weight (% ) 1. Ethylene = vinyl acetate copolymer 40 2. Ethylene = ethyl acrylate copolymer 29.6 3. Linear ultra-low density polyethylene 5 4. Low density polyethylene 10 5. Magnesium hydroxide 26. Red phosphorus 4 7. Titanium oxide 3 8. Dioctyl phthalate 1.2 9. Aluminum borate 0.8 10. Antioxidant 0.3 11. Foaming agent 3 12. Crosslinking agent 0.6 13. Pigment 0.5

The physical properties of the composition obtained by mixing the above raw materials are as follows. Test Item Test method Unit Characteristics melt index (before foaming) JIS K-6760 g / 10min 85 Density (before foaming) JIS K-6760 g / cm 3 0.992 Tear strength (after foaming) Automobile Standards N / kg / mm 1.29 Density (after foaming) g / cm ³ 4.2 Flammability MVSS (JIS K-6911) cm / min 0 (nonflammable)

[0031]

The flame-retardant polyolefin resin composition obtained by the present invention described above has the following effects. (1) Since it is a non-halogen flame-retardant resin composition, it does not generate toxic or corrosive gas during thermal decomposition or combustion, and therefore is a material that is safe for human body without fear of environmental pollution. (2) Furthermore, by using a foamed product of the same resin composition, it is possible to mold the skin, the backup layer or the core material in the same process, which is suitable for multi-step molding when laminating polyurethane resin on conventional vinyl chloride resin. In comparison, it is possible to reduce production costs. (3) Since the amount of the filler contained in the resin composition is extremely small as compared with the normal non-halogen flame-retardant resin composition, the specific gravity of the resin composition is low and the weight of the molded product can be reduced. Become. (4) In the conventional interior materials for automobiles, it is almost impossible to completely burn or recycle the members when the vehicle is scrapped. However, when this flame-retardant resin composition is used, it is not necessary to separate each member when the vehicle is scrapped. Makes recycling easier.

In the above description, the case of forming a molded product by powder slush molding of the resin composition of the present invention has been described, but the present invention is not limited to this, and the resin composition of the present invention may be processed according to the processing method and application. Since it is characterized in that the optimum physical properties can be set, it can be applied to flame-retardant protective covers by injection molding or hollow molding, and flame-retardant sheets by inflation molding, T-die molding, calender molding and the like.

Claims (4)

[Claims] 1. An olefin resin, an olefin resin blended with a flexibility modifier, and a resin mixture having a melt index in the range of 0.5 to 150, and a metal hydroxide 1 as a filler. -10 wt%, red phosphorus 1-5 wt%, boron compound 0.5-3 wt%, metal oxide 2-10 wt% and dioctyl phthalate 1-3.
A flame-retardant resin composition, characterized by being combined so that the total amount of the fillers is 30% by weight or less. 2. An olefin resin and a mixture of an olefin resin and a flexibility modifier, and a resin mixture having a melt index of 0.5 to 150, and 1 to 10 parts by weight of a metal hydroxide as a filler. %, 1 to 5% by weight of red phosphorus,
A resin composition prepared by combining 0.5 to 3% by weight of a boron compound, 2 to 10% by weight of a metal oxide and 1 to 3% by weight of dioctyl phthalate, and blending so that the total amount of the fillers is 30% by weight or less is foamed. A flame-retardant resin composition comprising a mixture of an agent or a foaming agent and a crosslinking agent. 3. A resin mixture having a melt index of 0.5 to 150 is polypropylene, high density polyethylene,
It is composed of at least two kinds of resins selected from low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, ethylene-based copolymer and synthetic rubber, and the ethylene-based copolymer is ethylene / Vinyl acetate copolymer, ethylene / acrylic acid ester copolymer,
The flame-retardant resin composition according to claim 1 or 2, which is an ethylene / acrylic acid copolymer or an ethylene / methacrylic acid copolymer. 4. The metal hydroxide is magnesium hydroxide or aluminum hydroxide, the red phosphorus is red phosphorus surface-treated with a titanium coat, and the boron compound is zinc borate or aluminum borate. The flame-retardant resin composition according to any one of claims 1 to 3, wherein the oxide is any one of titanium oxide, iron oxide, alumina, silicon oxide, magnesium oxide, calcium oxide, and zinc oxide.