JP3351138B2 - Thermoplastic resin composition for interior materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition for interior materials, and more particularly, to a thermoplastic resin composition having excellent fluidity at the time of molding, and having a color tone and flame retardancy. The present invention relates to a thermoplastic resin composition for interior materials having excellent heat resistance.

[0002]

2. Description of the Related Art In recent years, with the remarkable progress of petrochemistry and organic polymer chemistry, polymer materials have become very familiar in our living space. For example, polyethylene,
BACKGROUND ART Thermoplastic resins such as polypropylene and vinyl chloride are also used for interior materials such as carpets and wallpapers in cars and homes. However, on the other hand, since these polymer materials have the property of burning high heat due to their composition, once a fire occurs, not only the fire spreads but also smoke, toxic gas, corrosive gas, etc. may be generated. Therefore, from the viewpoints of better safety and disaster prevention, flame retardancy and non-combustibility are required.

[0003] From this point, various measures for flame retardancy have been taken for polymer materials used in such applications. However, recent trends in flame retardant regulations are not only in terms of the property of being difficult to burn, but also toxic gas. It is also required that they are hardly generated and that they have low smoke emission.

[0004] Conventionally, the flame retardancy of polymer materials has been Br-based,
It has been developed mainly with halogen-based flame retardants such as Cl-based, but gradually became tired from the aspect of fuming and toxic gas generation, and instead replaced with low fuming, low-toxic metal hydroxide, tin oxide,
The development of inorganic flame retardants such as antimony oxide, borates, phosphorus compounds and the like is currently being actively conducted.

[0005] Among them, aluminum hydroxide, which is a metal hydroxide, is an excellent flame retardant without generating toxic gas since it exhibits a flame retardant effect by endothermic and dehydration reactions accompanying heating, and is widely used. . However, in order to impart sufficient flame retardancy, it is necessary to add a large amount, and in this case, there is a possibility that the excellent original moldability of the resin, the mechanical strength of the molded article, the color tone, etc. may be impaired.

In view of the above, as a means for ensuring flame retardancy without impairing the excellent molding processability inherent in resin, mechanical strength, color tone, etc. of a molded article, a technique of performing a surface treatment on an inorganic filler has been developed. I have. For example, a method in which EVA is filled with an inorganic hydrate or the like surface-treated with a silane coupling agent (Japanese Patent Application Laid-Open No. Sho 61-264034), M is obtained by surface-treating a polyolefin resin with a silicone derivative or a fatty acid or a fatty acid metal salt.
g (OH) ₂ (JP-A-62-18135)
3) has been proposed.

[0007] Further, there is also known a method of increasing the mechanical strength by adding a flame-retardant aid to enhance the flame-retardant effect, thereby reducing the filling amount of metal hydroxide. For example, a method of blending fine phosphorus and red phosphorus which has been subjected to surface treatment with a fatty acid or a fatty acid metal salt to ethylene propylene rubber or ethylene butene-1 rubber (Japanese Patent Laid-Open No. 62-218432), Mg (OH) ₂ or Al ₂ (OH) ₃ 50 ~
A method of filling 100 parts, 3 to 50 parts by weight of any of red phosphorus, zinc borate and titanium dioxide (JP-A-61-130)
370). Further, the mechanical strength is improved by making the metal hydroxide finer [JET (JET
I @ Japan Energy and Technology Intelligence
) Vol 39, No. 3, 1991, p. 71] is also already known.

[0008]

However, in the above-mentioned conventional method, the inorganic hydrate is converted into a silane coupling agent, a fatty acid,
In the method of surface treatment with a fatty acid metal salt, although the mechanical strength of the obtained resin composition is improved, the fluidity of the resin composition under heating is insufficient, and not only the improvement of the moldability is not obtained. In addition, there has been a problem that heat generated during a kneading process or the like in which a high torque is applied deteriorates the resin and the added chemicals and causes the molded product to be colored. When a phosphorus-based compound such as red phosphorus is used as a flame retardant, a strict work environment is required because compounding may cause dust and harm the health of workers. Increase. In addition, although the method of using aluminum hydroxide in the form of fine particles also improves mechanical strength, it does not satisfy the demands of the industry. On the other hand, when magnesium hydroxide is used, the flame retardancy and kneading properties can be solved, but the cost is high, the chemical resistance is poor and the color tone of the molded body changes over time, so it is not suitable for use as an interior material. Had a problem.

[0009] An object of the present invention is to provide a flame-retardant thermoplastic resin composition for interior materials which has excellent fluidity during molding and has excellent flame retardancy and color tone, and in which the color tone does not change with time. It provides things.

In view of such circumstances, the present inventors have conducted intensive studies to achieve the above object. As a result, when aluminum hydroxide treated with a specific chemical is mixed with a thermoplastic resin and used, or when a specific chemical is used. It has been found that a thermoplastic resin composition that satisfies all of the above objects can be obtained by adding and present at the time of kneading aluminum hydroxide and a thermoplastic resin, thereby completing the present invention.

[0011]

That is, according to the present invention, hunter whiteness is 95 or more with respect to 100 parts by weight of a thermoplastic resin.
A relative water aluminum oxide aluminum hydroxide that
Alkyl phosphate wherein the alkyl group is linear or
Surface treatment with 0.1% by weight to 10% by weight of the metal salt
The present invention provides a thermoplastic resin composition for an interior material, comprising 10 parts by weight to 300 parts by weight of

Hereinafter, the present invention will be described in more detail. The feature of the present invention is that, when a thermoplastic resin is highly filled with aluminum hydroxide to obtain a flame retardant resin composition, an alkyl phosphate ester having a linear alkyl group or a metal salt thereof coexists in the composition. To make it happen. In the present invention,
The alkyl phosphate having such a structure, or a metal salt thereof, is not particularly limited, but usually has 6 to 30, preferably 8 to 22 carbon atoms in the alkyl group, and more specifically, octyl phosphate, decyl phosphate ester,
Lauryl phosphate, myristyl phosphate,
Examples include stearyl phosphate and cetyl phosphate and metal salts thereof. The number of substitution of the alkyl group can be from 1 to 3 but is not particularly limited. As the metal salt, an alkali metal such as sodium or potassium is applied.

[0013] The thermoplastic resin used in the present invention is:
In general, there is no particular limitation as long as the resin is subjected to heat molding. Examples include polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer,
Ethylene butene copolymer, ethylene acrylate copolymer, polypropylene, polystyrene, ABS, A
Styrene polymers or copolymers such as AS and AES,
Methacrylic acid polymer and the like can be mentioned. The amount of aluminum hydroxide to be added to the thermoplastic resin is 10 parts by weight to 30 parts by weight.
0 parts by weight is essential. If the amount is less than 10 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 300 parts by weight, the fluidity and mechanical strength of the resin composition decrease.

The alkyl phosphate ester blended in the thermoplastic resin composition of the present invention requires that the alkyl group be linear. Sufficient fluidity cannot be obtained with an alkyl phosphate having a side chain. In addition, a phosphoric acid ester having a hydrocarbon having an unsaturated bond, such as an oleyl phosphoric acid ester, which is not an alkyl phosphoric acid ester, causes thermal decomposition due to heat treatment during kneading and molding to cause discoloration. The amount of the alkyl phosphate or its metal salt to be added to the resin composition is about 0.1% by weight to about 10% by weight based on aluminum hydroxide constituting the resin composition.
% By weight, preferably from about 0.5% to about 2% by weight, is essential. If the compounding amount is less than 0.1% by weight, sufficient fluidity cannot be obtained, and even if it exceeds 10% by weight, no improvement in physical properties can be expected, and on the contrary, the cost becomes extremely high.

The method of compounding the alkyl phosphate or the metal salt thereof in the resin composition is not particularly limited.
Generally, it can be carried out by the following method. For example, when kneading a thermoplastic resin and aluminum hydroxide, there is a method in which it is added directly to the resin side in advance or simultaneously with aluminum hydroxide. It is also possible to add a surface treatment to aluminum hydroxide in advance and mix it with a resin. The method of treating the surface of the aluminum hydroxide with the alkyl phosphate ester or a metal salt thereof is not particularly limited. For example, an alkyl phosphate dissolved or dissolved in aluminum hydroxide suspended in a dispersion medium is used. A method of adding an ester or a metal salt thereof, thoroughly stirring and mixing, and then drying, or a method of uniformly dispersing or dissolving an alkyl phosphate ester or a metal salt thereof in water, an organic solvent, or the like in advance, followed by a Henschel mixer with aluminum hydroxide. , A method of mixing and drying using a wellner, a ribbon blender, or the like, or a method of pulverizing aluminum hydroxide, adding an alkyl phosphate or a metal salt thereof at the time of particle size adjustment, and applying a mechanochemical reaction to perform a surface treatment. Taken.

The thermoplastic resin composition for an interior material in the present invention is not required to be yellowed after molding and not change in color tone with time, and is usually filled with aluminum hydroxide and mixed. Has a b value of 3.0 (b value of the chromaticity index defined by the Hunter's color difference equation).
Below, preferably 2.0 or less, those exceeding 3.0 are not suitable for interior materials.

Therefore, the aluminum hydroxide used as the filler is preferably white aluminum hydroxide to which no organic substance is adhered, and among the commercially available aluminum hydroxides, those having a hunter whiteness of 95 or more are used. . The average particle size of these aluminum hydroxides is desirably 0.1 μm to 10 μm as measured by a sedimentation balance method. If it is less than 0.1 μm, the fluidity of the resin composition decreases, and if it exceeds 10 μm, the mechanical strength of the molded article decreases.

[0018]

According to the present invention described in detail above, a specific phosphate ester is simply present at the time of filling aluminum hydroxide into a thermoplastic resin,
It provides a thermoplastic resin composition that has excellent fluidity during molding processing and excellent flame retardancy and color tone of the resin composition after molding, and does not change color tone over time. Its industrial utility value is extremely large.

[0019]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. The color tone and fluidity (M
FR), flame retardancy, and color stability over time were measured by the following methods. ○ Color: Resin composition is heated and pressed at 150 ° C and 150m
The surface of the sheet molded to a thickness of mx 150 mm x 2 mm is measured using a color difference meter (manufactured by Nippon Denshoku Co., Ltd., model: Z-1001DP).
Was measured. In the measurement, tristimulus values X, Y, and Z in the XYZ system were measured using the standard light C defined in JIS Z8720 and in the following method in accordance with JIS Z8722.
The b value was calculated using the value according to the formula for calculating the chromaticness index of the color difference color of the hunter. Kind of measurement method: Sa Illumination and geometrical conditions of attendance: 0-d Measurement was performed by covering the detection unit where the sample was placed with a black box. ○ Fluidity: Measured at 19 according to JIS-K7210
It was measured under the conditions of 0 ° C. and a load of 2.16 kg. As a measuring instrument, a melt indexer (manufactured by Takara Kogyo, model: L207) was used. ○ Flame retardancy: A test piece having a thickness of 30 mm x 25 mm x 0.3 mm is lit with a burner from the lower end. When the fire starts, remove the burner and measure the time until all specimens burn. ○ Temporal change of color tone: 1 sample of thermoplastic resin composition
It was molded at a temperature of 50 ° C. to a thickness of 2 mm.
−5-CH, and a standard white plate (X = 78.9)
2, Y = 81.11, Z = 93.84) and displayed as a yellow index (YI) value.

Examples 1 to 9 (Coating of aluminum hydroxide with surface treating agent) 40% by weight of water and 2% by weight of a surface treating agent were stirred by a homogenizer with respect to aluminum hydroxide (dry body) to be surface treated. After obtaining a uniform dispersion, the dispersion was poured into aluminum hydroxide (manufactured by Sumitomo Chemical Co., Ltd., trade name: high white aluminum hydroxide CL-303, Hunter whiteness 99) and a polyethylene bag. The mixture was sufficiently mixed with human power, and a surface treatment agent was coated on aluminum hydroxide. Among the used surface treatment agents, stearyl phosphate is a solid at room temperature, and was therefore dissolved by heating at 90 ° C. and dispersed in water for use. The dispersion was dried at 120 ° C. for 3 hours, and then crushed for the purpose of breaking agglomeration. (Preparation of thermoplastic resin composition) 150 parts by weight of aluminum hydroxide coated with the surface treating agent obtained by the above method and polyethylene beads (ultra low density polyethylene, MFR: 0.8
g / 10 min, density 0.90 g / cm ³ ) and 100 parts by weight of Labo Plast Mill (manufactured by Toyo Seiki Seisaku-sho, Ltd.
(Model: 30-C150, mixer type: R-100)
And mix gently.
Preheat at 60 ° C for 5 minutes.
The blade was rotated at 60 rpm for 10 minutes at 60 rpm and kneaded to obtain a thermoplastic resin composition. The color tone, fluidity (MFR), and flame retardancy of the obtained thermoplastic resin composition were measured.
Table 1 shows the results. The difference between the conditions in each example was only the surface treatment agent coated on the aluminum hydroxide surface, and the surface treatment agent used in each example was as follows. Example 1: Stearyl phosphate (mono-substituted / di-substituted = 1: 1) Example 2: potassium lauryl phosphate (same as above) Example 3: potassium stearyl phosphate (same as above) Example 4: monostearyl Potassium phosphate ester Example 5: Potassium myristyl phosphate ester Example 6: Potassium caprylate phosphate Example 7: Potassium monolauryl phosphate Example 8: Capryll phosphate ester Example 9: Lauryl phosphate ester (monosubstituted) / Di-substituted product = 1: 1)

Comparative Example 1 In Example 1, aluminum hydroxide without surface treatment (trade name: high white aluminum hydroxide CL-303, Hunter whiteness 99, manufactured by Sumitomo Chemical Co., Ltd.) was used. Otherwise, a thermoplastic resin composition was obtained in the same manner as in Examples 1 to 9. Next, the physical properties of the obtained thermoplastic resin composition were measured in the same manner as in the examples. Table 1 shows the results.

Comparative Example 2 A thermoplastic resin composition was obtained in the same manner as in Examples 1 to 9, except that the surface treatment agent for aluminum hydroxide was changed to sodium stearate. Next, the physical properties of the obtained thermoplastic resin composition were measured in the same manner as in the examples. Table 1 shows the results.

Comparative Example 3 A thermoplastic resin was prepared in the same manner as in Examples 1 to 9 except that the surface treatment agent for aluminum hydroxide was changed to potassium oleyl phosphate having an unsaturated bond in the alkyl chain. A composition was obtained. Next, the physical properties of the obtained thermoplastic resin composition were measured in the same manner as in the examples. Table 1 shows the results.

Comparative Example 4 In the method of Examples 1 to 9, the surface treatment agent of aluminum hydroxide was used as a mixture of potassium isostearyl phosphate and potassium isopalmityl phosphate having a side chain in the alkyl chain. A thermoplastic resin composition was obtained in the same manner except for changing the composition. Next, the physical properties of the obtained thermoplastic resin composition were measured in the same manner as in the examples. Table 1 shows the results.

Comparative Example 5 A thermoplastic resin composition was prepared in the same manner as in Example 3, except that the amount of surface-treated aluminum hydroxide was changed to 350 parts by weight with respect to 100 parts by weight of polyethylene beads. I got Next, the physical properties of the obtained thermoplastic resin composition were measured in the same manner as in the examples. Table 1 shows the results.

Comparative Example 6 A thermoplastic resin composition was prepared in the same manner as in Example 3, except that the amount of the surface-treated aluminum hydroxide was changed to 5 parts by weight based on 100 parts by weight of polyethylene beads. I got Next, the physical properties of the obtained thermoplastic resin composition were measured in the same manner as in the examples. Table 1 shows the results.

Comparative Example 7 In Example 3, the amount of potassium stearyl phosphate added to aluminum hydroxide was 0.08% by weight.
A thermoplastic resin composition was obtained in the same manner except that the composition was replaced with the above. Next, the physical properties of the obtained thermoplastic resin composition were measured in the same manner as in the examples. Table 1 shows the results.

[0028]

[Table 1]

Example 10 The thermoplastic resin compositions obtained by the methods of Example 1, Example 2 and Comparative Example 2 were molded at a temperature of 150 ° C. to a thickness of 2 mm. 30 in a 60 ° C constant temperature bath
After holding for one day, the color tone (YI) of the molded body was measured. Table 2 shows the results. For comparison, in the method of Example 1, magnesium hydroxide (trade name; Kisuma 5, manufactured by Kyowa Chemical Industry Co., Ltd.) 150 was used instead of aluminum hydroxide.
A resin composition was obtained in the same manner except that parts by weight were used, and the color change of the resin composition over time was measured in the same manner as described above. Table 2 shows the results.

[0030]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (3)

(57) [Claims] 1. A of the thermoplastic resin 100 parts by weight, Han
Aqueous acid aluminum hydroxide terpolymers whiteness of 95 or more
Alkyl with alkyl group linear to aluminum halide
0.1% by weight of phosphoric acid ester or metal salt thereof
A thermoplastic resin composition for an interior material, comprising 10 parts by weight to 300 parts by weight, which has been surface-treated at a weight percentage . 2. The thermoplastic resin composition for an interior material according to claim 1, wherein the color tone of the composition is 3.0 or less in b value. 3. The thermoplastic resin composition for an interior material according to claim 1, wherein the central particle size of the aluminum hydroxide is 0.1 μ to 10 μ as measured by a sedimentation balance method.