JPS6069146A - Glass fiber-reinforced pigmented propylene resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent colored appearance and mar resistance, consisting of a propylene/ethylene copolymer resin, glass fiber, a specified modified crystalline propylene polymer, an ethylene/alpha-olefin copolymer rubber and a pigment. CONSTITUTION:0.5-10pts.wt. pigment having an average particle size of 0.2mu or below and a weight ratio of a color component contg. at least 20vol% component having a specific surface area of at least 20m<2>/g to a dispersant of 0.05- 20, is blended with 100pts.wt. component consisting of 20-98wt% propylene/ ethylene copolymer resin having an ethylene content of 1-25wt%, a boiling xylene-soluble matter content of 1-25wt%, an MFR of 0.01-200g/10min and an isotactic index of 42 or above, 2-30wt% glass fiber having an average diameter of 15mu or below and a greige goods-depositing quantity of 0.01-0.3wt%, 0-10wt% crystalline propylene polymer modified with 0.05-20pts.wt. unsaturated org. acid (derivative), and 0-40wt% ethylene/alpha-olefin copolymer rubber having an ethylene content of 90-40wt% and a Mooney viscosity of 10-120.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides specific amounts of each of specific glass fibers and pigments.
In addition to crystalline propylene polymers modified with unsaturated organic acids or derivatives thereof (hereinafter referred to as modified PP) and ethylene-α olefin copolymer rubber (hereinafter referred to as ethylene rubber), specific propylene- The present invention relates to a colored resin composition that is blended with an ethylene copolymer resin and has excellent colored appearance and scratch resistance, and also has good physical property balance and molding warp deformation (including reheating warp deformation).

Various attempts have been made to improve heat-resistant rigidity, mechanical strength, creep resistance, etc. by blending glass fibers into propylene-based polymer resins. However, while glass fiber-reinforced propylene polymer resin (hereinafter referred to as FRPP) has the above-mentioned characteristics, it also suffers from poor appearance (particularly the unique silt pattern when colored), 13-rippling flow patterns, and scratches. Due to problems such as elasticity and molding deformation, the application of FRPP to a wide range of applications, such as automotive interior parts, has been limited. Regarding these problems, attempts have been made in the past to improve flowability, but these have not been sufficient, and the amount of glass fibers filled has been forced to be limited.

Therefore, the present inventors first specified the filler and colorant (Japanese Patent Application Nos. 57-218037 and 218038) and the glass fiber (Japanese Patent Application No. 58-1021).
No. 99 specification), and as a result, it has become possible to apply it to many fields. However, in some cases, application to fields that require extremely high colored appearance, scratch resistance, etc. is still insufficient.

The present invention aims to improve these unsatisfactory points of the prior art, and uses specific amounts of specific glass fibers and pigments, and in some cases, denatured PP and ethylene rubber. When blended with ethylene copolymer resin, the colored appearance and scratch resistance of the resin are greatly improved.
Furthermore, it was discovered that the physical property balance and molding warp deformation (including reheating warp deformation) are each maintained at favorable levels.

That is, the present invention is a colored propylene-based resin composition whose sexual characteristics include the following components (a) to (e).

(a) Propylene-ethylene copolymer resin with an ethylene content of 1 to 25% by weight and a boiling xylene soluble content of 3 to 30% by weight...20 to 98% by weight (b'l average diameter of 15% by weight)
Glass fiber with a particle size of less than μ and a sizing agent adhesion amount of 0.01 to 0.3% by weight, 2 to 30% by weight (c) Modified PP...... Curved... ...Tune 0-10% by weight (d) Ethylene rubber amount, song, song interval θ~
40% by weight (e) Average particle size is 0.2μ or less and specific surface area is 2゜rr? A pigment in which the coloring component ■ and the dispersant @ constitute at least 20 parts by volume of /v or more, and the mixing ratio [■/@] of ■ and @ is 0.05 to 2 degrees by weight...・0.5 to 10 parts by weight per 100 parts of the total amount of (a) to (d) above The composition of the present invention not only has improved colored appearance and scratch resistance, but also has a high balance of physical properties. (Especially a balance between heat-resistant rigidity and impact strength) L2, molding warpage and reheating warpage are small, weld strength is good, and the coefficient of linear expansion is also small (good dimensional stability in high-temperature atmospheres). It can be applied to industrial parts that require a high level of quality, such as large automobile parts such as instrument panels and bumpers, and various electrical product parts.

The crystalline propylene polymer resin, which is the component (a) used in the present invention, contains 11 to 25% by weight of ethylene, preferably t
L, <2-20% by weight, boiling xylene soluble content 3-3
0% by weight, preferably 4-20% by weight of propylene-ethylene block or random copolymer.

Here, the measured value of ethylene content is determined by a conventional method using infrared spectrum analysis and NMR, and the boiling xylene soluble content is measured by immersing the 2f sample in 300 CC of boiling xylene for 30 minutes and dissolving it. After that, it is cooled to room temperature, filtered with a G4 type glass filter, and dried, and the value is calculated by back calculation from the weight of the solid phase.

5- If the ethylene content of this component is less than 1% by weight, it is unfavorable in terms of impact strength, while if it exceeds 25% by weight, the rigidity is insufficient.

Further, those having a boiling xylene soluble content of less than 3% by weight are unfavorable in terms of impact strength, while those having a boiling xylene soluble content of more than 30% by weight have insufficient scratch resistance and rigidity.

Such propylene-ethylene polymers must be crystalline and their isotactic index (II
) is generally 40 or more, preferably #Jr, 60 or more. Those with an II of less than 40 are unsuitable because they lack not only scratch resistance but also rigidity, hardness, and the like.

MFR of this component (JIS-7210, 230℃, 2
．． 16Kf load) is 0.01 to 200 f/10 minutes, especially those with 0.1 to 100 f/10 minutes do not have a good appearance, and those exceeding 200 r/x 0 minutes have poor impact resistance. It's inappropriate.

6 - Here, the MFRH polymerization conditions may be set, or they may be adjusted and set using an appropriate post-treatment, such as a peroxide addition method.

Note that these propylene-ethylene copolymer resins may be used together in any proportion.

These copolymers are polymerized and reduced using a Ziegler-Natsuta catalyst, and can be appropriately selected from commercially available copolymers.

Next, the glass fiber which is the component (b) used in the present invention is:
The average diameter is 15μ or less, preferably 2 to 14μ, and a sizing agent on the surface (this includes a surface treatment agent for the purpose of adhesion and compatibility between the sizing component and the resin) ) final adhesion amount after dry finishing is 0
．． 01 to 0.3% by weight. Here, those having an average diameter of 7 to 2 μm are particularly preferable in that they further improve the physical property balance (heat-resistant rigidity, impact strength) and further reduce molding warping and reheating warping. Moreover, such an effect using this 7-2μ material is (a
) component is expressed in the same way in thermoplastic resins such as polyolefin interlate such as polyethylene, modified polyphenylene oxide, etc. The manufacturing method of this glass fiber is, for example, the following method. Depends. First, the molten glass is formed into glass beads of a predetermined size called marbles, which are heated and softened in a collecting furnace called a bushing, and then flowed down from numerous nozzles on the furnace table to blow this material at high speed. While stretching, a sizing agent is applied by dipping in a sizing agent applicator installed in the middle of the stretching process, the sizing agent is applied and bundled, the film is dried, and then wound up on a rotating drum. At this time, the nozzle diameter, take-up speed, take-up atmosphere temperature, etc. are adjusted to make the average diameter of the glass fibers a predetermined size. At the same time, the concentration, type, coating time, etc. of the sizing agent are adjusted so that the final amount of sizing agent deposited after drying is o, o i ~0.3% by weight.

Further, the length of the glass fiber is not specified, so the shape may be measured such as roving, chopped strand, strand, etc., but the length of the glass fiber is about 1 to 8 cm for ease of mixing with the propylene polymer. Dostrands are preferred.

In this case, the number of bundles is preferably 100 to 5,000, particularly preferably 500 to 2,000. In addition, the final length after cross-wire to propylene polymer is 0.1 mm on average.
If it can be obtained by humans, crushed strands of so-called milled fiber or glass powder may be used.
Alternatively, it may be in the form of a continuous single fiber sliver. The composition of the raw material glass is preferably alkali-free, and one example is E glass.

Compared to conventional glass fibers used for reinforcing plastics, the glass fibers maintain an appropriate balance between bundling and opening properties, while minimizing the amount of sizing agent deposited, making them suitable for use with specific pigments (described below). Combined with the effect of adding , the color appearance was significantly improved.

Here, the average diameter is the one observed using an electron microscope, etc., and the amount of sizing agent attached is a value measured as loss on burning, and the specific burning conditions are 600°C and 60 minutes. If it exceeds 15μ, the degree of improvement in heat resistance rigidity will be small, and the amount of molding warpage and reheating warp deformation9- will also be large, and if the amount of sizing agent attached exceeds 0.3% by weight, the molded product will have a colored appearance. worsens, and each is unsuitable.

Although the glass fiber sizing agent does not need to contain a surface treatment agent, it usually contains a coupling agent such as a silane type, a rim type, a titanium type, or the like. Among these, it is preferable to include silane coupling agents such as epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, vinylsilanes such as vinyltrichlorosilane, and aminosilanes such as γ-aminopropyltriethoxysilane. The final content ratio of the focusing component and the surface treatment agent is not particularly limited, but is between 30 and 0.
A ratio of 70:30 provides a relatively good balance of heat resistance, stiffness, and appearance. Here, the focusing components are usually film forming agents, surfactants,
It is composed of a softener, an antistatic agent, a lubricant, etc., but it may also be composed of only modified or unmodified polyolefins.

Next, the modified PP which is the component (c) used in the present invention is:
Unsaturated organic acids or derivatives thereof, such as ac-10'-lylic acid, methacrylic acid, maleic acid, itaconic acid; unsaturated organic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride; anhydrides; esters of unsaturated organic acids such as methyl acrylate and monomethyl maleate; amides of unsaturated organic acids such as acrylic acid amide and fumaric acid monoamide; imides of unsaturated organic acids such as itaconic acid imide, etc. It is modified by a grafting method by adding 0.05 to 20 parts by weight to 100 parts by weight of a polypropylene polymer. Among these, those modified using acrylic acid or maleic anhydride are preferred.

This component is effective in improving heat-resistant rigidity, dimensional stability, creep resistance, etc. In this modification, organic peroxides such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, etc. are used to accelerate the degree of modification. Usually, the blending amount is 0.0 parts by weight per 100 parts by weight of propylene polymer.
It is 1 to 3.0 parts by weight. The method for producing modified PP is not particularly limited, but for example, a propylene polymer, an unsaturated organic acid or its derivative, and an organic peroxide are mixed thoroughly using a Henschel mixer, etc. , generally 0.2-1 at 170-260℃
This is done by heating, melting and kneading for 5 minutes. At this time, part or all of the component (d) described below may be kneaded at the same time. In this case, component (d) may also be modified to improve the impact strength of the composition of the present invention and to reduce the amount of molding warpage and reheating warpage.

However, the ethylene rubber as component (d) used in the present invention is
For example, ethylene-propylene copolymer rubber, ethylene-propylene copolymer rubber,
Propylene-diene copolymer rubber, ethylene-butene-
1 copolymer rubber, etc., preferably with an ethylene content of 9
0 to 40% by weight, and Mooney viscosity M Ll-H (1
00°C) is about 10 to 120.

Further, this component may be modified in advance with an unsaturated organic acid or a derivative thereof. This component is effective in improving impact strength, reducing molding warpage, reducing reheating molding warping, and improving dimensional accuracy.

Furthermore, the pigment which is the component (e) used in the present invention,
The average particle size is 0.2μ or less, preferably 0.18μ or less, and the specific surface area is 20rr? / or more, preferably 25t
r? /f or more components occupy at least 20 volumetric units, preferably 30 volume units, and a dispersant @, and the blending ratio of ■ and @ [■/@] is 0.05 to 2 by weight.
0, preferably 0.1 to 10.

However, the average particle diameter means a value measured by an electron microscope, and the specific surface area means a value measured by a gas adsorption method.

Specifically, the average particle size is determined by measuring the colored component particles within an arbitrary measurement field using an electron microscope, taking the average value, and calculating the specific surface area by plotting the amount of adsorbed gas against its equilibrium pressure. From the isothermal adsorption curve obtained, calculate the amount of gas required for the surface of the particle to be covered with a monomolecular film of adsorbed gas molecules (therefore, the number of gas molecules), and calculate this value and the average cross-sectional area per molecule of adsorbed gas. It is determined by a method (for example, the BET method) that calculates the surface area of the particle from

(2) The ingredients may be either inorganic or organic, or mixtures thereof, and may also be natural or synthetic. The manufacturing method is also not limited.

The specific coloring component that must occupy at least 20 volumes of the coloring component (2) has an average particle size of 0.2μ or less and a specific surface area of 20rr? / is the above-mentioned coloring component, and specific examples thereof include: Blue: Phthatercyanine Blue, Phthalocyanine Green, Peacock Blue Yellow: Quinophthalone Yellow, Isoindolinone Yellow, Polyazo Yellow, Hansa Yellow, Benzidine Yellow Red: Alizarin Lake, Quinacridone Red, Watching Red, Perylene Red, Polyazo Red, Permanent Red, Lysol Red, Anthraquinone Red, Isoindolinone Red Black Secondary Carbon Black, Aniline Black White:
White carbon (finely powdered silicic acid), etc., and other coloring components include, for example, blue: ultramarine, navy blue 14- yellow: yellow yellow lead, medium yellow lead, yellow iron oxide Red color: red iron oxide, iron oxide Black type: iron Black and white type: lead white, zinc white, zinc sulfide, etc.

These coloring components can be used regardless of the presence or absence of the above-mentioned surface treatment, and can also be used in combination.

■Ingredients with an average particle size of 0.2 μ or less and a specific surface area of 2 O
n? / If the amount of coloring components is less than 20 volume, that is, if the number of coloring components with an average particle size of more than 0.2 μ or a specific surface area of less than 20 m'/f is 20 volume or more, the effect of the present invention will not be obtained. I can't perform.

This component (e) essentially consists of a blend of the above-mentioned component (1) and a dispersant, which is the @ component described below, in a specific ratio.

This dispersant◎ includes ordinary metal soaps, various resins,
Surfactants etc. can be used, such as higher fatty acids such as stearic acid and lauric acid, gold salts such as calcium, magnesium, aluminum and zinc; resins such as polyethylene wax and polyethylene powder; polyethylene glycol, polypropylene glycol, etc. These include polyalkylene glycol or a salt thereof, and these can also be used in combination.

The mixing ratio of the above-mentioned coloring component (1) and this dispersant @ is preferably such that [■/@] is 0.05 to 20 in terms of weight ratio.

If this value exceeds 20, the coloring components have poor dispersion;
If it is less than 0.05, the colored appearance and scratch resistance of the resin molded article will be unsatisfactory, and the mechanical strength will also decrease due to the dispersant.

The particle size and specific surface area of the coloring component dispersed in the resin composition containing component (e) can be measured by separating the components of the composition using an organic solvent extraction method (e.g. xylene extraction method). 1-2 at medium 140-150℃
After dipping and dissolving the composition for about an hour and separating the colored components and filler from the resin using thimble filter paper, or baking the composition to take out the filler and colored components, the filler is separated (for example, using acids, etc.). There are methods such as dissolving the filler and calculating the measured value of the coloring component taken out.

In addition to the above-mentioned components (1) and (@), other components such as fillers and modifiers may be added to the component (e).

The blending ratio of these components is (a) 20 to 98% by weight of the specific propylene-ethylene copolymer resin, preferably 30% by weight;
~97% by weight; (b) 2 to 30% by weight of specific glass fiber;
Preferably 3-25% by weight; (C) modified PP 0-10% by weight, preferably 0-8% by weight; (d) ethylene rubber 0-40% by weight, preferably 0-35% by weight; and (e
) 0.5 to 10 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the above-mentioned components (a) to (a) of the specific pigment.
5 parts by weight.

If component (a) is less than 20%, moldability is poor;
On the other hand, if it exceeds 98% by weight, the effects of the present invention cannot be expected.

If component (b) is less than 2% by weight, heat-resistant rigidity will be insufficient, while if it exceeds 30% by weight, the appearance will deteriorate. (e) component is 10
If it exceeds % by weight, hardly any further improvement in heat-resistant rigidity is observed. (If the di-acid component exceeds 40% by weight, the heat resistance stiffness will be significantly reduced. If the (e) component is less than 9.517% by weight, the colored appearance and scratch resistance will be insufficient.
If it exceeds 0 parts by weight, the physical properties will deteriorate due to the dispersant and the like, and it will also be economically disadvantageous.

The composition of the present invention contains these (a
) to (e), various additional components can be added.

These additional components include surface-treated or untreated inorganic or organic fillers other than component (b), such as talc, mica, calcium carbonate (heavy,
light, colloid), barium sulfate, calcium silicate, clay, magnesium carbonate, alumina, silica, calcium sulfate, glass peas, glass powder, hollow glass bulbs, silica sand, silica stone, aluminum hydroxide, magnesium hydroxide, basic Magnesium carbonate, asbestos, zeolite,
Molybdenum, diatomaceous earth, sericite, shirasu, graphite,
Calcium hydroxide, calcium sulfite, gypsum fiber, carbon fiber, synthetic silicate fiber (PMF: processed mineral fiber), quartz powder, 18-bentonite, metal whisker, wood powder, sodium sulfate):
Modified or unmodified rubber or latex components other than the above (mountain components) (e.g. styrene-butadiene rubber, 1.
2-polybutadiene, butyl rubber, styrene-butadiene-styrene block copolymer, nitrile-butadiene rubber, polyisobutylene, polybutadiene, polyisoprene, etc.): Propylene-ethylene copolymer resin other than the above components (a) and (e), or Thermoplastic resins (e.g., high, medium or low density polyethylene, homopolymers of α-olefins other than polypropylene such as polybutene, copolymers of α-olefins other than propylene, ethylene-vinyl acetate copolymers, maleic anhydride) Olefin polymer resins such as copolymers of α-olefins other than propylene and vinyl monomers such as acid kraft polyethylene, as well as nylon, polycarbonate, and acrylonitrile.
Butadiene-styrene resin (ABS), polystyrene,
Resins other than olefin polymer resins such as polyvinyl chloride and polyphenylene oxide; Antioxidants (phenol-based, sulfur-based, etc.): Lubricants; Various coloring agents other than component (e) above: Ultraviolet absorbers; Antistatic agents: Dispersion Agent: Copper damage inhibitor;
Neutralizing agents; foaming agents; plasticizers; antifoaming agents; flame retardants; crosslinking agents; flowability improvers; weld strength improvers and the like.

The addition of these various resins, fillers, and auxiliary agents affects the physical property balance, molded product surface characteristics (colored appearance, scratch resistance, gloss, weld appearance, silver streaks, flow marks, etc.),
It is effective in improving printability, paintability, adhesion, plating performance, tapping performance, moldability, wire crosstalk, weld strength, durability, etc. These additional components can also be added in combination.

The composition of the present invention can be produced using a conventional mixing machine such as a -screw extruder, twin-screw extruder, Banbury mixer, roll, Brabender Plastograph 7, or kneader.

At this time, components (b) and (C) are removed and granulated using a twin-screw extruder in advance, and then components (b) and (e) are added and granulated using a single-screw extruder. You may.

Usually, it is kneaded with an extruder etc. to make a pellet-like compound and then subjected to processing, but in special cases, the above (a) to
It is also possible to directly supply each of the components (e) alone or in advance kneaded in part to various molding machines, and mold the product while kneading it in the molding machine. In addition, in advance, a masterbatch is prepared by blending components (b) to (,) alone or in part with component (Xun) to a high concentration, and while separately diluting it with component (a) or (e), It can also be blended, compared, and shaped.

As for the molding method for the composition of the present invention, for example, extrusion molding and various thermoforming methods are suitable for those having a relatively low MFR, and injection molding is suitable for those having a relatively high VFR. That is,
Extrusion molding, blow molding, injection molding, sheet molding, thermoforming,
The effects of the present invention are exhibited in molded products regardless of the molding method used, such as rotational molding or lamination molding.

The composition of the present invention thus obtained has a beautiful colored appearance and high scratch resistance, which are not found in conventional glass fiber reinforced propylene resin compositions, and has a high physical property balance (heat resistance stiffness - impact strength). ) and reduced warping deformation (during molding and reheating), and at the same time, paintability, printability, tapping performance, moldability, cross-wire performance, etc. were also good.

The present invention will be described in more detail with reference to Examples below, in which various test methods are as follows.

■Colored appearance (degree of coloring, sill pursing, IJ-ri situation, etc.) 200m diameter x 2m thick disc-shaped specimen (gate: 11111
11 diameter pinpoint) degree of coloring, Silperth) I
The J-driving conditions were visually observed and judged as follows.

Beautiful coloring with almost no silver streaks Grade 21 Beautiful coloring with only silver streaks observed near the gate; Grade 2 Coloring unevenness, unclear coloring, or silver streaks are noticeable and cannot be used for practical use; Grade 3 ■ Scratch resistance JIS- The pencil scratch test device shown in 5401 was modified, a 100 yen coin was set in the pencil setting part, and a 35X5
Rough grain of each 0X2 test piece (average height of convex part is 0.2+
The surface of the sheet was rubbed at a speed of 8 cI11/sec, and the marks were visually judged as follows.

The measurement temperature was 23°C.

Scars are white and noticeable; 1st grade L Slightly white and noticeable; 2nd grade 1 Quite white and cannot be used for practical use; 3rd grade Heat resistant rigidity (100℃ three-point bending modulus) JIS-72
Compliant with 03.

■Test piece (100X) installed on impact strength support (hole diameter 40 steel)
A dart, which is a load sensor, was dropped (1 m x 6 K4 f) on a surface of 1 m x 6 K4 f, and the deformation and fracture behavior of the test piece under impact load was measured.The impact absorbed up to the point of crack initiation in the resulting impact pattern was The energy was calculated and used as the impact strength of the material. The measurement atmosphere temperature is 2
It is 3℃.

■Warp deformation (molding warp, reheating warp deformation) After leaving the disk specimen from (■) above in an atmosphere of 23°C and 50% RH for 72 hours,
Place it on a surface plate, and measure the maximum amount of deformation with a caliper as the amount of molding warpage. In this case, those with a warping amount of 10 m or less are particularly good for practical use. In addition, the same specimen was heated to 100℃.
The sample was treated in a hot air oven for 5 hours, and further left in a room at 23° C. and 50% RH for 24 hours, after which the amount of warpage was measured using the above method, and the amount calculated using the following formula was defined as the amount of reheating deformation. In this case, a power of 5 W or less is particularly good for practical use.

Amount of reheating warpage = 1 Amount of molding warpage - Warpage after heat treatment (Example) %, MFR30f/10min), and (b
) As a component, the average diameter is 6 μ and the amount of sizing agent attached is 0.1
Each glass fiber is 2% by weight or 13μ and 10% by weight (each fiber length is 6m, number of bundles is 1200, surface treatment agent r-aminopropyl silane, sizing agent ingredients are surfactant, lubricant, softener) The composition of the agent, antistatic agent, film forming agent, etc., the ratio of surface treatment agent / sizing agent component is 50: 50),
And, as component (e), dispersant (aluminum stearate) is used in a proportion of 10% by weight to coloring component 4 consisting of blue pigment [40% by volume of phthalocyanine blue and 60% by volume of ultramarine, zinc sulfide, and iron oxide]. A dispersant (consisting of coloring component 9 consisting of 30% by volume of alizarin lake and 70% by volume of red iron oxide and zinc white)
Polyethylene wax) 1], gray pigment [carbon black and white carbon combined 25% by volume, zinc sulfide, iron black, zinc white carbon combined 75% by volume], dispersant (stearic acid) The coloring component 1 consists of a brown pigment [penzidine yellow, resol red, carbon black, and white carbon, totaling 20% by volume], red iron oxide, yellow iron oxide, zinc white, and iron black, totaling 80% by volume. In contrast, a dispersant (aluminum stearate) composed of 1 part by weight was used.

Average particle size (μ) and specific surface for each coloring component used here = 2
5- Product Cn? /f> is as follows.

Phthalocyanine blue (0.05μ, 79η?/?),
Ultramarine blue (0,25,13), zinc sulfide (0,38,15)
, iron oxide (0,10,16), alizarin lake (sail 0
9.53), red iron (0,10,16), zinc white (0
, 45, 12), carbon black (0, 03, 106
), white carbon (0,02,178), iron black (0
,02,7), benzidine yellow (0,16,22),
Lysol red (O, OS, 36), yellow iron oxide (0,1
0,17).

Furthermore, as component (c), acrylic acid-modified polypropylene or maleic anhydride-modified polypropylene, and (
As a main component, ethylene-propylene copolymer rubber (ethylene content 75% by weight, Mooney viscosity ML1+4 (10
0°C]70), and other components such as phenolics and
Using 0.1 parts by weight of sulfur No. 6 antioxidant, mixing for 2 minutes using a tumbler mixer at the ratio shown in Table 1,
Cross-wire granulation (230°C) was performed using a vented single-screw (65 neck diameter) screw extruder. After that, the above-mentioned disk-shaped specimen and specimen for physical property measurement were molded using a screw-in-line injection molding machine 26-1, and their colored appearance, scratch resistance, heat-resistant rigidity, impact strength, molding resistance, and recyclability were evaluated. The amount of heating warp deformation was evaluated. The results are shown in Table 1 A.
Shown in 1 to 9. All showed excellent performance balance. Next, the composition of the first surface plate 2 was molded using a Mitsubishi Natco 800EXL screw inlay/injection molding machine to form an instrument panel with a width of 300 mm, a length of 600 t+m, and a thickness of 3 mm.
Model flat plates were molded for large automobile parts such as consoles and bumpers, and home appliance parts such as air conditioners and televisions. At this time, the moldability and fluidity were good, the coloring was beautiful, and the unique silver streak-like flow pattern was not very noticeable and was satisfactory for practical use. In addition, the obtained molded products exhibit particularly excellent scratch resistance and heat resistance rigidity for automobile parts, home appliance parts, etc., and have sufficient impact strength and dimensional stability for practical use, as well as weld strength and paintability. It was good.

Comparative Example> In addition to the propylene-ethylene block copolymer, glass fiber, background pigment, acrylic acid-modified polypropylene, and antioxidant used in the example, polypropylene (II99, MFR 30v/10) as component (a) was added. The average diameter of component (b) is 6μ and the amount of sizing agent attached is 0.85% by weight, and the average diameter of 17μ is 0.65% by weight (both fiber length, number of bundles, surface treatment agent, sizing agent component, The combination ratio of the surface treatment agent and the sizing agent component is the same as in the example), each glass fiber (e)
Dispersant (
weight of aluminum stearate) 1], red (8) pigment [10% by volume of alizarin lake and red iron
Samples were prepared in the same manner as in the examples using a weight ratio of dispersant (polyethylene wax) of 1 to 9 of the coloring component consisting of 90% by volume including zinc white, respectively, and in the proportions shown in Table 1 A10~4. did.

In both cases, the performance balance was poor. That is, when pigments other than those specified are used, the scratch resistance is poor and the colored appearance is also unsatisfactory. However, glass fibers with a sizing agent content of more than 0.3% by weight will have poor colored appearance, and those with an average diameter of more than 15μ will have poor heat resistance, molding warpage, and reheating warp deformation. were all at low levels. Also, those using polypropylene had poor impact strength.

(Margin below) 29-

Claims (1)

[Scope of Claims] (a) Propylene-ethylene copolymer resin with ethylene content of 1 to 25% by weight and boiling xylene soluble content of 3 to 30% by weight...20 to 98% by weight (b) Average Diameter is 15μ
Glass fiber with a sizing agent coating amount of 0.01 to 0.3% by weight: 2 to 30% by weight (c) Crystalline propylene polymer modified with an unsaturated organic acid or its derivative ...0 to 10% by weight (d) Ethylene-α olefin copolymer: I"m...
0 to 40% by weight (e) Average particle size is 0.2μ or less and specific surface area is 20-
72 or more components occupy at least 20 volumes of the coloring component ■ and the dispersant O, and the mixing ratio of ■ and @ is [■/@
] is 0.05 to 20 in weight ratio...0.5 to 100 parts by weight of the total amount of (a) to (d) above
A colored propylene resin composition reinforced with glass fibers, characterized in that the composition comprises 10 parts by weight.