JPS63284241A - Fiber-reinforced resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in weathering resistance and high-temperature dimensional stability and suitable as a material for, e.g., car trims, by mixing a crystalline propylene polymer with a potassium titanate fiber, a specified phosphorus compound, a light stabilizer, talc and an ethylene/ propylene copolymer rubber. CONSTITUTION:40-98wt.%, based on the total of components A, B, E and F, or 70-99wt.%, based on the total of components A and B (when neither component E nor component F is contained), crystalline propylene polymer (A) is mixed with 30-1wt.% potassium titanate fiber (B) of an average fiber diameter of 0.1-1mu, an average aspect ratio >=5 and a pH value <=10, 0.01-0.5pt.wt., per 100pts.wt. total of components A, B, E and F, phosphorus compounds (C) of structures of formulas I and/or II (wherein R<1> is an 8-30C alkyl, a cycloalkyl or an aromatic group, R<2> is any one group selected from among the same groups in formula I, except that the 8-30C alkyl is replaced by a 1-30C alkyl, and R<3> is t-butyl). 0.01-2pts.wt. hindered amine light stabilizer (D), 0-30wt.% talc (E) of an average particle diameter <=5mu and 0-40wt.% ethylene/propylene copolymer rubber (E) of a propylene content of 20-60wt.% and a Mooney viscosity ML1+4 (100 deg.C) of 5-120.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a fiber-reinforced resin composition, particularly in fields where dimensional stability and weather resistance at high temperatures are required, such as fenders and door panels. , la! is used for vehicle exterior parts such as bumpers, bumper skirts, and fascias. The present invention relates to a reinforced resin composition.

[Conventional technology]

Propylene-based resin compositions reinforced with fillers, etc. have excellent moldability and physical properties, and are economically advantageous, so they are widely used in the field of automobile parts and various other industrial parts. .

However, when calcium carbonate or barium sulfate is used as the reinforcing filler, the dimensional stability at high temperatures is insufficient.

For example, when glass fiber is used as a filler, the dimensional stability at high temperatures is improved, but problems such as molding warpage and deterioration of physical properties, particularly impact strength, occur.

As a method for solving these problems, a reinforcing method using fine Ta fibers (whiskers) as a filler has been proposed. Among them, products using fine fibers of potassium titanate as a filler not only improve dimensional stability and mold warping at high temperatures, but also have excellent physical properties, so they can be used not only for propylene-based plastics but also for various other plastics. A number of reinforcement materials have been proposed for use in combination with fillers (for example,
JP-A No. 1984-99848, JP-A No. 59-13F133
No. 8, JP-A-59-140245, JP-A-58-21
No. 3032, see each specification).

[Problem that the invention seeks to solve]

However, the potassium titanate-containing resin compositions that have been proposed so far do not necessarily have sufficient weather resistance, and may not be suitable for applications that are exposed to the outdoors for long periods of time, such as vehicle exterior parts. There were many.

Therefore, the present inventors first blended potassium titanate fibers with a specific shape and a specific light stabilizer to create fibers that had good dimensional stability at high temperatures, suppressed molding warping, and had good weather resistance. proposed a reinforcing resin composition (patent application 1981)
-297253).

However, depending on the application, the am-reinforced resin composition may have good dimensional stability at high temperatures and suppress molding warpage, but may not have sufficient weather resistance, and is often unsuitable for use as an exterior member for a vehicle, for example.

[Means for solving problems]

The present inventors have been searching for a propylene resin composition with extremely excellent weather resistance that can be applied to exterior parts of vehicles, especially automobiles, and as a result, they have found that potassium titanate fibers of a specific shape,
The above objective was achieved by blending a specific phosphorus compound and a specific light stabilizer.

That is, the present invention is a fiber-reinforced resin composition characterized by comprising each of the following components (a) to m.

(a) Crystalline propylene polymer: (a) when containing component (e) and/or (n component),
4 for the total amount of components (b), (e) and (f).
0 to 98 weight tons, and if component (e) and (f) are not included, 7 to the total amount of components (a) and (b).
0 to 99 weight 2 (b) Potassium titanate fiber Ia with an average male diameter of 0.1 to 1 and an average aspect ratio of 5 or more: (a), (b), (a) and ( f) 30 to 1 weight 2 based on the total amount of components (e) General formula (wherein R1 is an alkyl group having 8 to 30 carbon atoms.

It is a cycloalkyl group or an aromatic group, R2 is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, or an aromatic group, and l (l and R2 may be different in the same compound. RM is a t-butyl group.) A phosphorus compound having the structure represented by: (a), (
b), (e) and (f) Total amount for Jli 100
0.01 to 0.5 parts by weight per part by weight (d) Hindered amine light stabilizer: Total amount of components (a), (b), (e) and (f) 0.01 to 0.5 parts by weight per 100 parts by weight. 01-2 parts by weight (e) Talc with an average particle size of 51 Lm or less: 0-30 weight 2 CF> Ethylene with a propylene content of 20-60 weight 2 and a Mooney viscosity ML1+4 (100°C) of 5-120.
Propylene copolymer rubber: θ ~ 40 weight 2° [Detailed description of the invention] Urohiro Satsuma (a) Crystalline propylene polymer The propylene polymer (a) component used in the present invention (
(hereinafter abbreviated as PP) is a stereoregular propylene homopolymer (polypropylene), other α-olefins other than propylene, preferably ethylene, butene-1, pentene-1, hexene-1, heptene-1, etc. -1
, octene-1 and other α-olefins having 8 or less carbon atoms, particularly preferably ethylene, butene-1, 40% by weight or less,
Preferably containing 30% by weight or less, propylene and α-
These include two or more block or random copolymers with olefins, or those modified by melting, chlorinating, sulfonating, glycidylating, or modifying with unsaturated organic acids.

Among these PPs, propylene/ethylene block copolymers have a density of the propylene homopolymerized portion of 0.908 or more, an ethylene content of the entire polymer of 3 weight 2 or more, and an MFR of 4 g/10 minutes or more. is preferable, especially when the density of the propylene homopolymerized portion is 0°907 or more, the ethylene content of the whole polymer is 3 to 7 wt.$, and the MFR is 5
0 to 120 g/10 min is preferable, and furthermore, this propylene/ethylene block copolymer has an ethylene content of 20 to 50 g/wt/xylene solubles at room temperature of 5 to 15 g/10 min.
It is more preferable that the weight is 2.

Here, the density is JIS-7112, and the MFR is JIS-7112.
Based on S-7210 (230℃, 2.18Kg),
In addition, the ethylene content is a value measured by NMR method, and the xylene soluble content at room temperature is 2 g of sample mixed with boiling xylene 60%.
The value was calculated back from the weight of the solid phase obtained by immersing it in 0 g for 20 minutes to dissolve it, cooling it to room temperature, filtering it with a G4 type glass filter, and drying it.

Here, this PP may be a mixture of two or more types.

(b) Potassium titanate fiber Next, the potassium titanate fiber used in the present invention (b) has an average fiber diameter of 0.1 to 1 island layer, and an average aspect ratio (ratio of fiber length to fiber diameter). average value) is 5 or more. Among these, fibers with an average diameter of 0.54 gm or less and an average aspect ratio of 7 or more, especially 10 or more are preferred.The manufacturing method of this fiber is not particularly limited, but the shape must be within the above range. . Here, the pH value is desirably 1O or less, particularly 7 to 3.
5, especially those from 7 to B are preferred, where the p)I value of potassium titanate is the value measured when the fibers are dispersed in water, for example 1 g of potassium titanate in 100-g water for 24 hours. Measured after immersion. Further, the fiber diameter and aspect ratio are values obtained by cross-dispersing the fibers in the resin and then observing and measuring the cross section thereof using a microscope.

(C) Phosphorus Compound Next, the phosphorus compound as component (C) used in the present invention is shown below. That is, the present compound has the following general formula (I)
or (n), in which R1
is an alkyl group, cycloalkyl group, or aromatic group having 8 to 30 carbon atoms; R2 is an alkyl group, cycloalkyl group, or aromatic group having 1 to 30 carbon atoms; R', Rz
may be different in the same compound R1 is t
-Butyl.

And/or specific examples of the above compound (I) include (1) distearyl pentaerythritol diphosphite (2) bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite (3) Bis(2-t-butyl-4-methylphenyl)pentaerythritol diphosphite (4)bis(2,8,di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, etc., and the compound ( Regarding II), (5) tetrakis (2
, 4-di-t-butylphenyl)-4°4°-biphenylene phosphite (6) tetrakis(2-t-butyl-4-methyl-phenyl)-4,4-biphenylene phosphonite.

Among them, the above (1), (2), (4) and (5)
) are preferred, and (2) and (5) are particularly preferred.

The amounts of these phosphorus compounds added are (a), (b),
(e) and (f) 0.01 per 100 parts by weight of the total amount
-0.5 parts by weight, preferably 0.03-0.3 parts by weight.

(d) Hindered amine light stabilizer In the method, the hindered amine light stabilizer as component (d) used in the present invention is, for example, (7) bis-2,2,8,8-tetramethyl-4-piperidyl sebacate. (8) Tetrakis(2,2,8,El-tetramethyl-
4-piperidyl) 1,2,3,4-butanetetracarboxylate (9) 2-(3,5-di-t-butyl-4-hydroxybenzyl)2-n-butylmalonic acid bis(1,2,
2,6,8-pe-phthamethyl-4-piperidyl) (10) 1.1'-(1,2-ethanediyl)bis(3
,3,5,5-tetramethylpiperazine) (11)) Lis(2,2,2,2-tetramethyl-4-
piperidyl)-dodecyl-1,2,3,4-butanetetracarboxylate (12)) lis(1,2,2,8,El-pentamethyl-4-piperidyl)-dodecyl-1,2,3,4- Butane tetracarboxylate (13) bis-1,2,2,8,8-pentamethyl-4
-piperidyl-sebacate (14) poly[(El-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-
diyl) ((2゜2.6.8-tetramethyl-4-
piperidyl)imino)hexamethylene((2,2,8,
13-tetramethyl-4-piperidyl)imino)1, among others, but not limited to (7)
, (8) and (14) are preferred, and the compound (7) is particularly preferred.

The amount of component (d) added is (a), (b),
0.01 per 100 parts by weight of the total amount of (e) and Cn
~2 parts by weight, preferably 0.03 to 1 part by weight. Further, weather resistance can be further improved by using a light resistance imparting agent other than these, such as an ultraviolet absorber.

(e) Talc The talc component (e) that can be used in the present invention has an average particle size of 51L11 or less.

The addition of talc has the effect of improving dimensional stability at high temperatures, suppressing molding warpage, and rigidity, among others, with a specific surface area of 35
,000 cbog or more, with an average particle size of 0.2 to 2.5
The particle size distribution is substantially 15 layers or less, 95% or more of particles with a particle size of 10 layers or less, 80X or more of particles with a particle size of 51 L or less, and 5 to 11 layers or less.
50% and an average aspect ratio of 5 or more, more preferably a specific surface area of 37.000 cm''
/g or more, the average particle size is 0.3 to 2.2 l■, the particle size distribution is substantially all the particles are 15IL11 or less, and 10IL■
The following items are 97% or more, 5 gm or less are 82X or more, and lpm or less are 10 to 45%, and the average aspect ratio is 8 or more.

Here, the specific surface area is measured using a constant pressure aeration type surface area measuring device, such as powder specific surface area measuring device 5S-20 manufactured by Shimadzu Corporation, based on a conventional method, the so-called air permeation method. Further, the particle size distribution is measured by an integrated distribution value by a light transmission method using a liquid phase sedimentation method. As an IM determination device, for example, 5A-CP type manufactured by Shimadzu Corporation (for example, 5A-CP 2-2
0).

On the other hand, the average particle size is the particle size value at the 50% point in the particle size cumulative distribution curve measured with the same device as the particle size distribution measuring device. Here, it is preferable to use an aqueous solution of about 30 parts alcohol by weight 2 parts as the dispersion medium used in the measurement because it increases the degree of dispersion of talc and makes it easier to measure. It is the average value of the ratio of length to thickness, and its measurement was performed by observation using a microscope.

In addition, the above physical properties of the filler dispersed in the resin are:
A method of extracting the boiling point of this composition with an organic solvent, such as a method of immersing and dissolving it in xylene at 130 to 140°C for several hours and separating the talc and resin through a thimble filter paper, or a method of baking this composition, etc. The extracted filler can be determined by the method described above.

Talc with an average particle size of 1.5 g or less can be easily obtained by wet classification, and talc with an average particle size of 0.7 g or more can be obtained by dry classification. Such talc can be produced, for example, by the following classification method. be done.

That is, raw talc is crushed using equipment such as a tube mill type crusher, impact type crusher, micron mill type crusher, centrifugal roller type Imond mill, etc., and if fine crushing is required, a micron mill, jet type crusher, etc. Dry or wet pulverization is performed using a jet-o-mizer, micronizer, jet pulpelizer, stirring mill (tower mill), vibration mill, colloid mill, etc. Next, the pulverized talc is pulverized using a cyclone, multilon, etc. Dry or wet classification is performed repeatedly one or more times using a device such as a micron separator, micronplex, cyclonea separator, ultra separator, jet chron, classiflon, rake classifier, hydrocyclone, hydraulic classifier, centrifugal classifier, etc. Adjust its physical properties.

Talc from China, Australia, the United States, etc. is preferred as raw talc, but talc from China is especially preferred.In addition, these talcs can be used for various esters, glycols, coupling agents, fatty acids and their metal salts, and surfactants. Surface treatment may also be carried out, and this treatment is effective in improving performance.

(f) Ethylene-propylene copolymer rubber Also, the ethylene-propylene copolymer rubber (1!PR) of component (f) that can be used in the present invention is ethylene-propylene binary copolymer rubber (EPM). ) or ethylene/propylene/non-conjugated diene terpolymer rubber (EPDM)
, the propylene content (weight) is 20 to 8 oz, preferably 25 to 50 oz, and the Mooney viscosity is ML1+4 (10
0°C) is 5 to 120, preferably 35 to 70, particularly preferably 40 to 60, and further preferably has an iodine value of 20 or less in EPD)1.

If the propylene content is less than 20 oz or more than 6 oz, the impact resistance of the composition is insufficient, and the Mooney viscosity is 5 oz.
If it is less than 120, the paintability is poor and mold delamination is likely to occur, while if it is more than 120, the appearance (flow marks, etc.), paintability, and prevention of paint gloss change are poor, so both are unfavorable. Mooney viscosity range is 5~
120 (preferably 35-70), its EPR
For example, a blend of EPM and EPDM, a high viscosity amount and a low viscosity amount may be used, and in this case, it is also possible to use materials outside the viscosity range in combination.

The blending ratio of ingredients (a) to (f) as above is (a) +
(b) + (e) + (f) Total 100 weight 2 (parts), when each contains (a): (e) and/or (f) component 4
0-98 weight 2, preferably 50-95 weight t 70-99 when not containing component (e) and/or (f)
Weight 2, preferably 80-97 Weight 2(b): 1-30
weight! , Good * L < t * 3~20 Weight 2 (c
): 0.01 to 0.5 parts by weight, preferably 0.03 to 0
．． 3 parts by weight (d): 0.01 to 2 parts by weight, preferably 0.03 to 1 part by weight
Part by weight (e) 0-30 weight 2, preferably 5-25 weight (f
) 0 to 40 weight units, preferably 5 to 35 weight units.

If it is outside the above range, the weather resistance will be insufficient, which is not preferable.

In addition to the above-mentioned components, the composition of the present invention may contain other additional components as long as the effects of the present invention are not significantly impaired.

Those additional ingredients used in the present invention include (
Treatment areas other than component b) and component (e) include untreated inorganic or organic fillers, various antioxidants other than component (c) used in the present invention, and rubbers other than EPR of component (f) used in the present invention. Body latex component used in the present invention (a)
In addition to the components, there are thermoplastic resins or thermosetting resins, pigment dispersants, crosslinking agents, foaming agents, flame retardants, core materials, antistatic agents, and paintability improvers. Adding 2 to 5 parts by weight of high-density polyethylene is effective for improving paintability and appearance.

Squeezing plate 11 The resin 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, Nigoo, etc. Usually, it is kneaded with an extruder etc. to form a pellet-shaped compound and then subjected to processing, but in special cases,
It is also possible to directly supply the components to various molding machines and mold them while kneading them within the molding machine. In addition, filler or EPR may be used in advance.
It is also possible to knead the mixture to a high concentration (with various additives as necessary) to form a masterbatch, which can then be separately diluted with a propylene polymer or the like for blend compounding or molding.

The molding method for the resin composition of the present invention is not particularly limited, and includes extrusion molding, blow molding, injection molding, sheet molding, aging molding, rotational molding, and lamination molding. Although the effects of the resin composition of the present invention can be exhibited in any molded product, molding by injection molding is the most suitable.

The fiber-reinforced resin composition of the present invention thus obtained has weather resistance not found in conventional potassium titanate filler-reinforced resin compositions, as well as excellent dimensional stability at high temperatures and high It has a good balance of physical properties (rigidity to low-temperature impact strength), good appearance, and moldability.In addition, sink marks and warping are not noticeable, and printability, adhesion, and scratch resistance are good, and weld lines are not noticeable and weld strength. It also has good tensile elongation and is highly suitable for applications that are exposed to the outdoors for long periods of time, such as automotive exterior parts.

〔Example〕

EXAMPLES The present invention will be specifically described below with reference to Examples. The various measurement methods used here are as follows.

(1) Weather resistance: A sheet of 100 x 100 x 2 layers was molded using injection molding (an in-line screw injection molding machine (230°C) manufactured by Taki Seisakusho), and the sheet was molded using a sunshine type molding machine manufactured by Suga Test Instruments Co., Ltd. Using an isermeter, the sheet was irradiated for 1800 hours at 83° C. in the presence of rain, and the surface appearance of the sheet was observed using a magnifying glass.

(2) Dimensional stability: The coefficient of linear expansion was measured according to ASTM-0996, however, the temperature range was 23°C to 80°C. 80, × 10 × 3 Il■) was used. Furthermore, the measured values are in the flow direction (vertical) of the resin.

(3) Molding warpage resistance: A 200X 200■■ thick disc-shaped specimen (Goo: 1mm diameter pinpoint) was injection molded, and after being left in an atmosphere of 23°C and 50% RH for 72 hours, it was was placed on a surface plate, and the maximum amount of deformation was measured using calipers as the amount of molding warpage.

(4) Rigidity: Compliant with JIS-7203.

The measurement temperature was 23° C., and the specimens were injection molded as described above.

(5) Impact strength (Izot): JIS-71
10 compliant.

Measurement temperature was -30°C, and the specimen was the same as above.

The components (a) to (6) used in the following Examples and Comparative Examples and their properties are shown below.

Component (a): Propylene/ethylene block copolymer (b) Component:
Potassium titanate m-fiber average fiber diameter: 0.3IL, average aspect ratio: 12, pH (dispersed in water) = 8 (C) component niline compound C-1 = bis(2,4-di-t-butylphenyl)
Pentaeris, ridoru diphosphite C-2: Tetrakis (2,4-di-t-butylpheni(f) component (EPR) 1/-no 1.-no AJ!, Tsuri 4&凰!
+--- Eaves #, ■ Le) -4,4°-biphenylene phosphonite C-3: ) Lis(2,4-di-t-butylphenyl)bosphite (d) component (light stabilizer) Hindered amine System D-1: Bis-2,2,8,8-tetramethyl-4
-piperidyl sebacate D-2= poly[(8-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4
-diyl) ((2,2,8,8-tetramethyl-4-
piperidyl)imino)hexamethylene((2,2゜6.
6-tetramethyl-4-piperidyl)imino)] Benzoate D-3: 2,4-di-t-butylphenyl-3,5
-Di-7-butyl-4-hydroxybenzoate (e) component (talc) / ``Shiv/-t2ri, ``HLBLk, 4''
l? 011L, “Examples 1 to 4 and Comparative Examples 1 to
5 The above-mentioned components were blended in the proportions shown in Table 1, and per 100 parts by weight of the blend, tetrakis[methylene-3-(3°-5”-di-t-butyl-4° -Hydroxyphenyl)propionate] Methane 0°10
Parts by weight, 2-(2'-hydroxy-3°-t-butyl-
5 parts by weight of methylphenyl and 3.5 parts by weight of a gray pigment mainly composed of carbon black and titanium oxide were blended and mixed for 2 minutes in a super mixer made by Yoda Seisakusho, and then mixed in an FCM twin-shaft mixer. The mixture was kneaded and granulated at 230°C to obtain composition pellets. Thereafter, specimens were molded at 230°C using a screw in-line injection molding machine, and their dimensional stability, weather resistance, rigidity, and impact strength were evaluated. The results are shown in Table 1.

As a result, the compositions of Examples 1 to 4 showed a good quality balance, whereas the compositions of Comparative Examples 1 to 5 had a poor quality balance.

Furthermore, as shown in Comparative Example 5, it is clear that resin compositions that do not contain potassium titanate fibers have problems in terms of dimensional stability and rigidity.

〔Effect of the invention〕

The fiber-reinforced resin composition of the present invention has particularly excellent weather resistance and also has good dimensional stability at high temperatures, so it is excellent as a material for vehicle exterior parts and is extremely useful industrially. be.

Claims (1)

[Claims] (1) A fiber-reinforced resin composition comprising the following components (a) to (f). (a) Crystalline propylene polymer: (a) when containing component (e) and/or component (f),
40 to 9 for the total amount of components (b), (e) and (f)
8% by weight, and when component (e) and (f) are not included, it is 70 to 9% based on the total amount of components (a) and (b).
9% by weight (b) Potassium titanate fibers with an average fiber diameter of 0.1 to 1 μm and an average aspect ratio of 5 or more: Total amount of components (a), (b), (e) and (f) (c) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) and/or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R^1 is It is an alkyl group, cycloalkyl group, or aromatic group having 8 to 30 carbon atoms, R^2 is an alkyl group, cycloalkyl group, or aromatic group having 1 to 30 carbon atoms, and R^1, R Both ^2 may be different in the same compound, R^3 is a t-butyl group.) Phosphorus compounds having the structure represented by: (a), (b), (e) and (f) Total amount of ingredients 10
0.01 to 0.5 parts by weight relative to 0 parts by weight (d) Hindered amine light stabilizer: Total amount of components (a), (b), (e) and (f) 10
0.01 to 2 parts by weight relative to 0 parts by weight (e) Talc with an average particle diameter of 5 μm or less: 0 to 30% by weight (f) Propylene content of 20 to 60% by weight, Mooney viscosity ML_1_+_4 (100°C) Ethylene-propylene copolymer rubber having a weight of 5 to 120: 0 to 40% by weight.