JP2833201B2 - Polypropylene resin bumper material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polypropylene resin bumper material containing an α-olefin copolymer rubber and an inorganic filler. More specifically, the present invention relates to a polypropylene resin bumper material which improves bleeding property in molding and the like and is stable against light.

[Prior art] Polypropylene-based resins have excellent physical, chemical and electrical properties and are therefore useful as materials for fibers, molded articles, sheets and films. In order to improve impact resistance, rigidity, heat distortion temperature, dimensional stability, etc., α-olefin copolymer rubber and an inorganic filler are blended and often used for automobile parts and electric products. .

Particularly recently, the use of a polypropylene resin bumper containing an α-olefin copolymer rubber and an inorganic filler is remarkable because of its excellent design properties. In this case, it is important to prevent deterioration due to light, and a method of adding a hindered piperidine-based compound such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is preferably used. I have.

On the other hand, the bumper is required to have a complex shape from the design point of view, and a lubricant is required to adjust the slip between the polypropylene resin and the surface of the processing machine and to improve the peeling property between the molded product and the mold surface. It has been. It is well known that compounds such as metal soaps or higher fatty acids are useful as these lubricants.

However, if a hindered piperidine-based compound added for light stabilization and a metal soap-based or higher fatty acid-based lubricant containing an acidic component coexist, a salt is formed between the two in a processing step or the like. In addition, there have been problems such as the occurrence of bleeding on the surface of the molded article and the deterioration of paintability.

Japanese Patent Application Laid-Open No. Sho 63-1222752 discloses that the coatability can be improved by using a hindered amine-based organic compound having an amine value of 5.2 or less. However, such a hindered amine organic compound is generally a high molecular weight type hindered amine compound as exemplified in the publication, and its light stabilizing performance is not always sufficient.

[Problems to be Solved by the Invention] Therefore, the bleeding property at the time of molding processing and the like has been improved,
Also, a polypropylene resin bumper material that is stable against light has been strongly desired.

An object of the present invention is to provide a polypropylene-based resin bumper material having improved bleeding property at the time of molding or the like and being stable to light.

Another object of the present invention is to stabilize a bumper material by blending a specific additive into a polypropylene-based bumper material containing an α-olefin copolymer rubber and an inorganic filler.

[Means for Solving the Problems] The present inventors have made intensive studies to solve the problems and found that a specific hindered piperidine compound is used in combination with a metal soap-based or higher fatty acid-based lubricant. As a result, the present inventors have found that bleeding, which is likely to occur when a polypropylene resin bumper material is molded, can be suppressed, and that it can be sufficiently stabilized against light, and the present invention has been accomplished.

That is, the present invention provides an α-olefin copolymer rubber 5
(A) The following formula (I) is used with respect to 100 parts by weight of a polypropylene resin composition containing 40 to 40% by weight and 5 to 40% by weight of an inorganic filler. 0.01 to 1 parts by weight of a hindered piperidine compound represented by the formula: and (B) a metal soap-based or higher fatty acid-based lubricant 0.01 to 1.5 parts by weight
To provide a polypropylene resin bumper material in which parts by weight are blended.

The present invention also provides a hindered piperidine compound represented by the formula (I) and a metal soap or a polypropylene resin composition containing the α-olefin-based copolymer rubber and the inorganic filler as described above. Provided is a method for stabilizing a polypropylene resin bumper material by blending a higher fatty acid-based lubricant.

In the present invention, the base polypropylene is, in addition to the homopolymerization of propylene, a copolymer containing propylene as the main component and an ethylene component, such as a propylene-ethylene block copolymer, and a block copolymer of propylene and ethylene-propylene rubber. And so on. Among these, the latter block copolymer containing an ethylene component is preferred. When a copolymer containing an ethylene component is used, the ethylene component is usually contained in a range of 20% by weight or less based on the weight of the copolymer. The polypropylene-based resin targeted in the present invention is such a polypropylene that further contains an α-olefin-based copolymer rubber and an inorganic filler.

The α-olefin-based copolymer rubber referred to herein is a rubber-like polymer obtained by copolymerizing two or more α-olefins, and α-olefins that can be a copolymer component are:
For example, it has 2 to 12 carbon atoms. Among the α-olefin-based copolymer rubbers, a copolymer rubber of ethylene and another α-olefin is preferred. In this case, the copolymerization component with ethylene is, for example, one having 3 to 12 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1- Octene, and mixtures thereof are exemplified. Among them, propylene or 1-butene is preferred. Ethylene and other α
-When a copolymer rubber with olefin is used, the ethylene content in the copolymer rubber is preferably in the range of about 45 to 95% by weight, more preferably about 50 to 80% by weight. The α-olefin-based copolymer rubber which is the object of the present invention includes a linear or cyclic monomer having a non-conjugated double bond as a third component, for example, 5-ethylidene-2-norbornene, dicyclopentadiene. And the like are also included.

The compounding ratio of the α-olefin-based copolymer rubber to polypropylene is 5 to 40% by weight, preferably 5 to 30% by weight, based on the weight of the mixture of the polypropylene, the α-olefin-based copolymer rubber and the inorganic filler. It is.
If it is less than 5% by weight, the impact resistance is poor, and if it exceeds 40% by weight, problems arise in formability and the like.

As the inorganic filler used in the present invention, talc, carbon black, titanium oxide, zinc oxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, calcium silicate, magnesium silicate, mica, celite, Examples thereof include kaolin, zeolite, silica, asbestos, glass fiber, carbon fiber, titanium fiber, barium titanate, and lead titanate. These can be used alone or in combination of two or more. These inorganic fillers have an average particle size
It is preferably 20 μm or less, more preferably 5 μm or less.

The mixing ratio of the inorganic filler to the polypropylene is 5 to 40% by weight, preferably 5 to 30% by weight, based on the weight of the mixture of the polypropylene, the α-olefin-based copolymer rubber and the inorganic filler. If it is less than 5% by weight, the rigidity is poor, and if it exceeds 40% by weight, problems such as impact resistance arise.

In the present invention, the hindered piperidine compound (A) and the lubricant (B) are blended with the above-mentioned α-olefin copolymer rubber and a polypropylene resin containing an inorganic filler.

Hindered piperidine compound (A) used in the present invention
Is represented by the above formula (I), and its chemical name is 2-methyl-2- (2,2,6,6-tetramethyl-4-
Piperidyl) amino-N- (2,2,6,6-tetramethyl-
4-piperidyl) propionamide.

Among the lubricant (B) used in the present invention, specific examples of the metal soap lubricant include metal salts of stearic acid such as calcium stearate, zinc stearate, and aluminum stearate. Specific examples of the higher fatty acid-based lubricant include stearic acid, hydroxystearic acid, behenic acid, and ricinoleic acid. Among these lubricants, metal salts of stearic acid or stearic acid are particularly preferred.

In the bumper material of the present invention, the hindered piperidine compound (A) is used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the polypropylene resin composition containing the α-olefin-based copolymer rubber and the inorganic filler. Parts, preferably 0.02 to
0.5 parts by weight, and 0.01 to 1.5 parts by weight, preferably 0.02 to 1 part by weight, of the lubricant (B). The hindered piperidine compound (A) cannot provide sufficient weather resistance when added in an amount of less than 0.01 part by weight, and even when added in an amount exceeding 1 part by weight, has a weather resistance sufficient to be used. No improvement can be expected. Addition of less than 0.01 part by weight of the lubricant (B) does not provide a sufficient effect, and addition of more than 1.5 parts by weight adversely affects the processing step such as increasing bleeding properties.

The bumper material of the present invention may contain other additives such as an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a nucleating agent, an organic and inorganic pigment, an antistatic agent, and a metal, as long as the properties are not impaired. An inactivating agent may be used in combination.

Examples of the antioxidant that may be used in combination include a phenol-based primary antioxidant, a sulfur-based secondary antioxidant, and a phosphorus-based secondary antioxidant.

Examples of phenolic primary antioxidants include 2,6-di-t-butyl-4-methylphenol, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Methane, n-octadecyl 3- (3,5-di-t-butyl-4-
(Hydroxyphenyl) propionate, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, 3,9-bis [2- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyl Oxy) -1,1-
Dimethylethyl] -2,4,8,10-tetraoxaspiro [5
・ 5] Undecane.

Examples of sulfur-based secondary antioxidants include tetrakis [methylene-3- (laurylthio) propionate] methane, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl. 3,3'-thiodipropionate, 3,9-bis (2-laurylthioethyl) -2,4,8,10-
And tetraoxaspiro [5.5] undecane.

Further, examples of the phosphorus-based secondary antioxidant include tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-t-butyl-4-methylphenyl)
Pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-
Bisphenylenediphosphonite and the like.

Examples of the heat stabilizers that may be used in combination include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and 2- [1- (2 -Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate.

Examples of the light stabilizer which may be used in combination include 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl- 2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-di-t- Butylphenyl 3,5-di-t-butyl-
4-hydroxybenzoate, 2,2'-thiobis (4-octylphenolate) -2
-Ethylhexyl-amine nickel, ethyl 2-cyano-3,3-diphenylacrylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-] Giyle II (2,2,6,6-
Tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4 −
Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)-
And polycondensates with 4-hydroxy-2,2,6,6-tetramethylpiperidine.

Examples of flame retardants that may be used in combination include, for example, tetrabromobisphenol A, decabromodiphenyl oxide,
Examples include antimony trioxide and aluminum hydroxide.

Examples of nucleating agents that may be used in combination include sodium benzoate, p-ethylbenzylidene sorbitol, sodium di (4-t-butylphenyl) phosphite, and the like.

Organic pigments that may be used in combination include, for example, polycyclic pigments such as phthalocyanine, quinacdrine, perylene, anthraquinone, and isoindolinone, and inorganic pigments such as titanium white, titanium yellow, and oxidized pigments. Iron and cadmium red.

Examples of the antistatic agent that may be used in combination include polyoxyethylene alkylamine, polyoxyethylene alkylamide, and glycerin fatty acid ester.

Examples of the metal deactivator which may be used in combination include N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine and dodecandioic acid bis [2 -(2-hydroxybenzoyl) hydrazide] and the like.

In producing the polypropylene resin bumper material of the present invention, for example, after mixing using a Henschel mixer and the like, kneading using a roll, a Banbury mixer, a single-screw extruder, a twin-screw extruder and the like to pelletize. A method of molding the obtained resin into a predetermined shape by a molding method such as an ordinary injection molding method or an extrusion molding method can be adopted. A hindered piperidine compound (A) and a metal soap or higher fatty acid lubricant (B) used in the present invention;
In addition, various additives that are optionally blended can be added separately or simultaneously at any stage of the production process.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. All percentages and parts in the examples are on a weight basis unless otherwise specified.

Example 1 Ethylene-propylene copolymer rubber (ethylene content: 75
%), 10% talc, and unstabilized propylene-ethylene block copolymer (7.3% ethylene content)
Is used, 100 parts of a polypropylene-based resin composition consisting of 65% is mixed with each component shown in Table 1, mixed with a Henschel mixer, and further kneaded with a 30 mmφ twin-screw extruder.
Pelletized.

Using the obtained pellets, a bumper was molded by an injection molding machine, and the surface was visually observed to determine the presence or absence of a bleed. In addition, the releasability was determined based on the required pressure when the bumper was released from the mold. A case where the air pressure was less than 5 kgf · cm / cm ² was regarded as good, and a case where the air pressure was more than 5 kgf · cm / cm ² was regarded as bad.

On the other hand, using the pellets obtained in the same manner as described above, a test piece of 60 × 40 × 1 mm was prepared by injection molding and subjected to a weather resistance test. The weathering test was performed using a sunshine weather meter, a black panel temperature of 33 ° C, and a water spray cycle of 18 minutes / 1.
Irradiation was performed under the conditions of 20 minutes, and the surface of the test piece was observed every 60 hours, and the time until cracks were generated on the surface of the test piece (crack life) was measured and used as a measure of light stabilization.

 The results are shown in Table 1.

In addition, the symbol of the test compound in Table 1 means the following, respectively.

AO-1: tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane UVA-1: 2- (3-tert-butyl-2-hydroxy-5-methylphenyl ) -5-Chlorobenzotriazole (I): 2-methyl-2- (2,2,6,6-tetramethyl-4
-Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide HALS-1: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate HALS-2 : Poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} (2,
2,6,6-tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino}] K-1: calcium stearate [Effects of the Invention] The polypropylene resin bumper material of the present invention has improved bleeding property during molding and the like, and is stable against light.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08L 53/00 C08L 53/00 (56) References JP-A-61-31466 (JP, A) JP-A-63-284241 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 23/00-23/36 C08L 53/00 B60R 19/03 CAS ONLINE

Claims (3)

(57) [Claims] (1) To 100 parts by weight of a polypropylene-based resin composition containing 5 to 40% by weight of an α-olefin-based copolymer rubber and 5 to 40% by weight of an inorganic filler: And 0.01 to 1.5 parts by weight of a hindered piperidine-based compound represented by the formula: and (B) 0.01 to 1.5 parts by weight of a metal soap-based or higher fatty acid-based lubricant. 2. The bumper material according to claim 1, wherein the lubricant is a metal salt of stearic acid or stearic acid. 3. A polypropylene-based resin composition containing 5 to 40% by weight of an α-olefin copolymer rubber and 5 to 40% by weight of an inorganic filler: A method for stabilizing a polypropylene resin bumper material, comprising adding a hindered piperidine compound represented by the formula: and (B) a metal soap-based or higher fatty acid-based lubricant.