JPH01129052A - Reinforced modified propylene resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in heat-resistant rigidity, mar resistance, etc., by mixing a specified crystalline propylene/ethylene copolymer at least partially modified with an unsaturated carboxylic acid (derivative) with glass flakes, an ethylene rubber and an inorganic filler. CONSTITUTION:A modified propylene resin is obtained by grafting 0.01-20wt.% unsaturated carboxylic acid (derivative), e.g., acrylic acid, onto a crystalline propylene/ethylene copolymer of an ethylene content of 1-25wt.%, an MFR of 1-80g/10min and a xylene-soluble portion (at room temperature) of 3-35wt.% in the presence of an organic peroxide as a modification accelerator. 30-98wt.% this modified resin is mixed with 2-50wt.% glass flakes of an average thickness of 1-7mu and a mean particle diameter of 20-1000mu, optionally treated with a coupling agent to increase the adhesion to a resin, 0-30wt.% ethylene rubber of a Mooney viscosity ML1+4 of 5-120/100 deg.C, 0-35wt.% at least one inorganic filler selected from among talc, mica and glass fiber and, optionally, a filler other than the above, an antioxidant, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a modified propylene-based resin composition reinforced with a filler, comprising a specific glass flake and optionally selected from ethylene rubber, talc, mica, and glass fiber. A mechanical polymer obtained by blending at least one type of filler into a specific crystalline propylene-ethylene copolymer (hereinafter referred to as modified Pp) at least partially modified with an unsaturated organic acid or a derivative thereof. It has excellent strength (especially heat resistance rigidity), and also has good molded product appearance, scratch resistance, and mold warp deformation.
The present invention relates to a reinforcing modified propylene resin composition particularly suitable for molding large-sized molded products.

[Prior Art] Various attempts have been made to improve heat-resistant rigidity, mechanical strength, creep resistance, etc. by blending talc, mica, glass fiber, etc. into a crystalline propylene polymer.

However, if talc or mica is added,
The improvement in heat resistance rigidity was relatively small, and the scratch resistance of the molded product surface was unsatisfactory. on the other hand.

When glass fiber is added, these improvements are great, but on the other hand, there are problems with specific appearance defects (silver streaks) and warping of molded products caused by the orientation of glass fibers and the shrinkage difference between glass fibers and resin. Problems such as deformation1 have prevented its use in a wide range of applications, such as large automotive interior parts.

Therefore, the present inventors have previously identified fillers, colorants, glass fibers, and propylene polymers (Japanese Patent Application No. 55-8178Q).
, 55-91010, 57-218037, 2
No. 18038, No. 58-1021913, No. 58-1
No. 77724, No. 5948230), and as a result, it has become possible to apply it to various fields.

[Problems to be solved by the invention] However, despite the above-mentioned improvements, application to fields that require extremely high mechanical strength and formability (prevention of warpage deformation), etc. is still difficult in some cases. It is insufficient.

[Means for Solving the Problems] As a result of conducting various studies to improve the unsatisfactory points of these conventional techniques, the present invention has been developed as a result of conducting various researches to improve the unsatisfactory points of these conventional techniques. This was made based on the discovery that the mechanical strength, particularly the heat-resistant rigidity, is significantly improved, and the appearance, scratch resistance, and molding warp deformation of the molded product are also maintained at a good level.

That is, the present invention is a reinforced propylene resin composition characterized by comprising the following components (a) to (d).

(a)! Tyrene content l~25wt$, MFR1~
80g/10 minutes and room temperature xylene soluble content is 3-3
A modified propylene resin in which at least a part of a 5% by weight crystalline propylene/ethylene copolymer is modified with an unsaturated carboxylic acid or a derivative thereof, and the modifier concentration is 0.01 to 20% by weight2...30 to 98 weight 2 (b) Intestinal glass flakes with an average thickness of 1 to 7 grs and an average particle size of 20 to 1000 g...2 to 50 weight 2 (C) Ethylene rubber...0 to 30 weight % ( d
) At least one inorganic filler selected from talc, mica, and glass fiber... 0 to 35% by weight (a) Modified propylene resin Crystals used in the production of the modified resin, which is the above component (a) used in the present invention The propylene/ethylene copolymer is a block or random copolymer with an ethylene content of 1 to 25% by weight, preferably 2 to 20% by weight, and an MFR of 1 to 8.
0 g/10 minutes, preferably 2 to 40 g/10 minutes, and the xylene soluble content at room temperature is 3 to 35% by weight, preferably 2
Particularly preferred is a block copolymer having an ethylene content of 20 to 70% by weight, preferably 25 to 2% by weight of BO, in the xylene soluble matter at room temperature.

Here, to measure the xylene soluble content at room temperature, 2 g of the sample was immersed in boiling xylene 800IILe for 20 minutes to dissolve it, then cooled to room temperature, filtered with a G4 type glass filter, and dried. The value is determined by calculating backwards from the weight.

Moreover, the measured value of ethylene content is obtained by a conventional method using infrared spectrum analysis and NMR.

The lower limit of the ethylene content of this copolymer was determined for reasons of impact resistance, while the upper limit was determined for reasons of heat-resistant rigidity and scratch resistance. The lower limit of MFR (230° C., 2.18 kg) was determined based on warping resistance and appearance, while the upper limit was determined based on impact strength.

The lower limit of the xylene soluble content at room temperature was determined from the viewpoint of impact resistance, while the upper limit was determined from the viewpoint of heat resistance rigidity and scratch resistance. Further, those having an ethylene content of 20% by weight or more in the soluble content are particularly excellent in terms of impact resistance, while those having an ethylene content of 70% by weight or less are particularly excellent in terms of heat-resistant rigidity, scratch resistance, and resistance to warping and deformation.

Here, the MFR may be set by the polymerization conditions, or may be adjusted and set by appropriate post-treatment, such as peroxide treatment.

Although these polymers are polymerized using a Ziegler-Natsuta catalyst, they can be appropriately selected from commercially available polymers, or two or more types can be used in combination.

To modify these crystalline propylene-ethylene copolymers with unsaturated organic acids or derivatives thereof, unsaturated organic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid; maleic anhydride, itaconic anhydride, etc. Acids, anhydrides of unsaturated organic acids such as citraconic anhydride; esters of unsaturated organic acids such as methyl acrylate and monomethyl maleate; amides of unsaturated organic acids such as acrylamide and fumaric acid monoamide: itaconic acid It is modified by a grafting method by adding 0.01 to 20 parts by weight of an imide of an unsaturated organic acid such as imide to 100 parts by weight of the crystalline propylene/ethylene copolymer. Among these, those modified using acrylic acid or maleic anhydride are preferred, with maleic anhydride being particularly preferred.

This modification has improved heat resistance, rigidity, impact resistance, scratch resistance, dimensional stability,
It is effective in improving creep resistance, etc. During this modification, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, t
- Using an organic peroxide such as butyl hydroperoxide 0 Normally, the amount used is 1 1 of the propylene-ethylene copolymer.
0.01 to 3.0 parts by weight. The modification method is not particularly limited, but for example, a crystalline propylene Φ ethylene copolymer, an unsaturated organic acid or its derivative, and an organic peroxide are mixed thoroughly and the , generally 170-26
This is carried out by heating, melting and kneading at 0'O for 0.2 to 15 minutes. At this time, part or all of the component (C) described below may be kneaded at the same time. In this case, the component (C) is also modified. Please,
It is possible to improve the impact strength of the composition of the present invention and to reduce the amount of molding warpage and reheating warping deformation.

The modified PP only needs to be at least partially modified, so for example, one or more highly modified PP diluted with one or more unmodified PP can be used. This is a more preferable method because the concentration of the denaturing agent can be easily controlled. At this time, the modified PP and the unmodified PP do not necessarily have to be the same type of crystalline propylene-ethylene copolymer, and the desired quality can be selected by appropriately selecting the same type or different types.

The concentration of the modifier is 0.01 to 201 to 20 parts by weight or 0.01 to 201 to 20 parts by weight.
02 to 152 to 15 parts by weight The lower limit is determined for reasons of heat resistance and rigidity; on the other hand, the effect is saturated when added in excess of 200 parts by weight.

(b) Glass flakes The glass flakes which are the above component (b) used in the present invention have an average thickness of 1 to 7IL11, preferably 2 to θJL1.
1, with an average particle size of 20 to 11,000 μl, preferably 30 to 700 μl. Among them, the average particle size is 20
Those with a diameter of 0 to 700 are excellent in the balance between warping deformation and heat resistance rigidity. In addition, a narrow particle size distribution is also preferable. If the thickness is less than 1pm, it is difficult to manufacture; if the thickness exceeds 7 lpm, the effect of improving heat resistance rigidity is small and is not preferred; if the average particle size is 30 lpm, the heat resistance rigidity is low, and if the average particle size is 30 lpm, the heat resistance rigidity is low Exceeding the range is undesirable, as the appearance of the molded product deteriorates.

Here, the thickness is measured by microscopic observation, and the average particle size is calculated from the particle size distribution determined by sieve separation (usually 10 to 400 mesh).

The surface of the glass flakes used in the present invention may be partially untreated, but in order to improve adhesion and compatibility with the resin, coupling agents such as silane, chrome, and titanium, such as γ It is preferable to use one treated with a silane coupling agent such as epoxysilane such as -glycidoxypropyltrimethoxysilane, vinylsilane such as vinyltrichlorosilane, or aminosilane such as γ-aminopropyltriethoxysilane.

In addition, at this time, treatment with various surfactants such as nonionic, cationic, and anionic surfactants, and dispersants such as fatty acids, metal soaps, and various resins can improve mechanical strength and kneadability. This is preferable from the viewpoint of improving.

The amount of components deposited by these treatments is preferably 0.4 weight 2 or less relative to the glass flakes, and if it exceeds this, the appearance of the molded product will deteriorate.

The glass flakes used in the present invention are manufactured, for example, by the following method. First, molten glass is formed into glass beads of a predetermined size called marbles, which are heated and softened in a furnace, extruded through a cylindrical pipe-shaped nozzle on the furnace table, and the bubble-shaped glass is cooled and lowered. The cooled bubbles are sandwiched between rolls, where they are crushed and crushed, and the crushed products are separated using a sieve to obtain glass flakes. The composition of the raw material glass is preferably alkali-free or low-alkali, such as E glass.

As described above, the glass flakes of component (b) used in the present invention are other than conventionally used glass powders,
This is distinctly different from that obtained by grinding, for example from rovings or strands. Glass flakes have good adhesion and compatibility with resins, especially component (a), and significantly improve heat-resistant rigidity. Because molding warpage is less likely to occur, the balance between these is good.

(C) Ethylene rubber The above (
The ethylene rubber of component c) is, for example, ethylene φ propylene copolymer rubber, ethylene/propylene/diene copolymer rubber, ethylene/butene-1 copolymer rubber, etc., and preferably has an ethylene content of 80 to 40% by weight. 2, and the Mooney viscosity MLl+4 (100°C) is about 5 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 the amount of molding warpage, and improving dimensional accuracy, printability, and paintability. Among these, when this component is used in an amount of 3 to 15% by weight, the balance between heat-resistant rigidity, impact strength, and molding warpage resistance is extremely good, which is preferable and more practical.

(d) Inorganic filler: The inorganic filler (d) that can be used in the present invention is at least one selected from talc, mica, and glass fiber. The filler may be surface-treated in advance, or may be left untreated.Surface treatments include various treatment agents such as silane coupling agent-based, higher fatty acid-based, fatty acid metal salt-based, polyethylene glycol-based, etc. In addition to the effects of the present invention, surface treatments, including chemical or physical surface treatments, are effective in improving weld strength, paintability, moldability, etc.

Here, talc preferably has an average particle size of 0.2 to 10J
Lm, especially 0.2 to 5 l, mica is also 1 to 1
50 gra, especially 2 to 50 lu shoes are suitable.

Further, it is preferable that the glass fiber has a diameter of 8 to tsg■, but in this case, the filling amount must be substantially 10 weight 2 or less from the viewpoint of warpage resistance, particularly 5 weight 2
The following is practical.

Here, the particle size and length were observed using an electron microscope or actually measured using a particle size distribution analyzer.

In the present invention, the presence of these inorganic fillers not only further improves the heat resistance rigidity but also is effective in reducing the amount of molding warpage and improving economic efficiency.

The composition of the present invention is characterized by containing the above components (a) and (b), and the above components (0) and (d), which may optionally be blended. Modified PP30-88 weight2. Preferably 40-85
Weight $; Component (b) Glass flakes 2-50 Weight 2
, preferably 5 to 45% by weight; (C) component ethylene rubber 0 to 30% by weight2. Preferably 3-15 weight $;(
d) Component filler 0-35% by weight 2, preferably 2-3
0 weight 2.

If the component (a) is 300% by weight, the moldability is poor;
On the other hand, if the content of component (b) exceeds 888 weight 2, the effect of the present invention cannot be expected; if the content of component (b) is less than 2 weight 2, the heat-resistant rigidity is insufficient;
On the other hand, if it exceeds 500 weight 2, the appearance and kneading properties of the molded product will deteriorate, and it will also be economically disadvantageous. (C) component is 300
When the weight exceeds 2, the heat resistance rigidity decreases significantly. If the amount of component (d) exceeds 355% by weight, the appearance of the molded product will deteriorate and it will also be economically disadvantageous.

The composition of the present invention may contain these substances within a range that does not significantly impair the expression of its effects (usually 30% by weight or less of the total amount of the composition).
Various additional components can be added in addition to components (a) to (d).

These additional components include surface-treated or untreated inorganic or organic fillers other than the above components (b) and (d), such as calcium carbonate (heavy, light, colloid), barium sulfate. , calcium silicate,
Clay, magnesium carbonate, alumina, silica, calcium sulfate, glass peas, glass powder (other than flakes), hollow glass spheres, silica sand, silica stone, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, asbestos, zeolite, Molybdenum, diatomaceous earth, sericite, shirasu, graphite, calcium hydroxide, sulfite,
Lucium, gypsum fiber, carbon fiber 1 synthetic silicic acid fiber (PMF: processed mineral fiber), quartz powder, bentonite, metal whisker, wood flour, aromatic polyamide fiber, sulfuric acid, -Da; other than the above (c) component Modified or unmodified rubber or latex components such as styrene-butadiene rubber, 1,2-polybutadiene, butyl rubber, styrene-butadiene-styrene block copolymer, hydrogenated nitrile butadiene rubber, polyisobutylene, polybutadiene, polyisoprene etc; above (
Thermoplastic resins other than components a), such as polypropylene,
Copolymers of α-olefins other than ethylene and propylene, homopolymers of α-olefins other than polypropylene such as high density, medium density or low density polyethylene, polybutene, copolymers of α-olefins other than propylene, α-olefin polymer resins other than propylene such as ethylene/vinyl acetate copolymers and maleic anhydride grafted polyethylene, as well as polyamides, polycarbonates,
Acrylonitrile butadiene styrene resin (ABS)
), polystyrene, polyvinyl chloride, polyphenylene ether, resins other than olefin polymer resins such as various polymer alloys, thermosetting resins, antioxidants (phenol-based, sulfur-based, etc.), lubricants, various colorants, ultraviolet absorbers agent, antistatic agent, dispersant, copper damage inhibitor, neutralizing agent, foaming agent,
plasticizer, antifoaming agent, flame retardant, crosslinking agent, flow improver,
Examples include weld strength improvers, paintability improvers, light stabilizers, and nucleating agents.

The addition of these various resins, fillers, and auxiliary agents affects physical property balance, wire crosstalk, molded product surface characteristics (molded product appearance, scratch resistance, gloss, weld appearance, silver streaks, flow marks, etc.), printability, and paintability. There are some that are effective in improving adhesion, plating properties, tapping properties, moldability, crosstalk properties, 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 single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll, a Brabender plastograph, a kneader, or the like.

At this time, some of the above components (b), (c), or (d) are removed and granulated using a twin-screw extruder, etc., and then the remaining components are added. It may be granulated using a single-screw extruder or the like. For example, in a twin-screw extruder, components (a) and (c) are first thoroughly kneaded, and from the latter half of the kneader process, the components (b) and (C) are granulated. ) components are supplied, filled and kneaded simultaneously or separately. In this case, the balance of physical properties is improved compared to the usual granulation method using -1 batch blending.

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)
It is also possible to directly supply each of the components to (d) alone or in advance kneaded in part to various molding machines, and mold them while kneading them in the molding machine. In addition, in advance (a) component (b) ~
(d) Asterbatch is obtained by kneading the components alone or in a blend of -parts to a high concentration, and then separately diluting it with component (a) or (C) for blend compounding or molding. You can also do it.

The composition of the present invention can be molded by extrusion molding and various thermoforming methods for those with a relatively low MFR, and injection molding for those with a relatively high MFR. The effects of the present invention can be exhibited in molded products regardless of the molding method used, such as blow molding, injection molding, sheet molding, aged molding, rotary molding, and lamination molding, but injection molding is particularly suitable.

[Example] The present invention will be specifically explained with reference to Examples below, in which various test methods are as follows.

■Heat-resistant rigidity (100℃ three-point bending modulus) JIS-72
Compliant with 03.

■A test piece (10 mm) installed above the impact strength support (hole diameter 40 mm)
A dart, which is a load sensor, was dropped (1.2 s x 7 kgf) onto a 0 x 100 The energy was calculated and used as the impact strength of the material. The measurement atmosphere temperature is 2
It is 3℃.

■Molding warpage, molded product appearance, and scratch resistance A box-shaped molded product model with a wall thickness of 2 cm as shown in Figure 1 was injection molded, and the amount of deformation (a-b) of the molded product was measured, and the appearance and scratch resistance was determined by observation as follows.

Appearance is "good" if there are almost no silver streaks and the surface is smooth, "fair" if there are some noticeable silver streaks and the surface is slightly rough, but there is no problem in practical use. If the surface roughness was also severe, it was judged as "r poor".

Scratch resistance was determined by pressing the side of a 100 yen coin against side A and rubbing it, and visually inspecting the area.
It was judged as ``fair'' and ``defective.''

In addition, Ca) to (d) used in the following Examples and Comparative Examples
Each component of is as follows.

(a) Component: Modified propylene/ethylene block copolymer (modified pp) (B) Component Nigaras flakes (C) Component: Ethylene rubber C-1: Mooney viscosity 15, ethylene content 74 weight 2
Ethylene propylene rubber (EPR) (d) component: other fillers Examples 1 to 6 and Comparative Examples 1 to 4 In addition to the components (a) to (b) shown in Table 1, 1 part by weight of carbon masterbatch 0.1 parts by weight each of a phenolic antioxidant and a sulfur antioxidant were mixed and granulated using a vented screw extruder (double screw diameter: 451) at a temperature of 210°C. At this time, components (b) and (d) were separately fed from the rear half of the kneader.

Each of the obtained pellets was molded into a test piece for evaluation and a box-shaped molded product model shown in FIG. 1 using a screw in-line injection molding machine, and evaluated. The results are shown in Table 1.

The compositions of Examples 1-6 showed a good quality balance.

That is, the molded product had good appearance and scratch resistance, had high mechanical strength, and had a small amount of molding warpage.

Width 300 mm x length 600 mm using the composition of Example 2
When we molded a model plate assuming an industrial part with a thickness of 3ffI11, we found that the molded product had good moldability, had no problems with warping in its appearance, had sufficient physical properties for practical use, and had good paintability and scratch resistance. was gotten.

On the other hand, the compositions of Comparative Examples 1 to 4 had poor quality balance, such as excessive warping, low mechanical strength, and poor molded product appearance and scratch resistance. there were.

[Effects of the Invention] By blending flaky glass with specific modified PP, the composition of the present invention maintains high mechanical strength, especially heat-resistant rigidity, equivalent to that of conventional glass-reinforced propylene resin compositions. At the same time, it exhibits a beautiful molded product appearance, scratch resistance, and reduced warpage deformability that were previously unobtainable. Furthermore, the coating properties, printability, tapping properties, moldability, weld strength, etc. were also good. In addition, the elastic modulus in the large deformation range, which is important for practical use, also showed good values.

The composition of the present invention not only has significantly improved mechanical strength and molded product appearance, but also has good scratch resistance, small mold warping, and has sufficient impact strength for practical use, and has good weld strength. Therefore, it can be applied to fields that require a high level of quality, such as large interior parts for automobiles.

In addition, since the molding warpage deformation is small, it is suitable for large automobiles FF1L.
When applied to products such as instrument panels and engine fan shrouds, more diverse designs than before are possible.

[Brief explanation of the drawing]

Figure 1 is a perspective view of a box-shaped molded product model, and the wall thickness of each side is 2 mm. Figure 1 Procedural Amendment Form ＼7 December 10, 1986

Claims (1)

[Claims] (1) (a) Ethylene content 1 to 25% by weight, MFR 1 to
80g/10 minutes and room temperature xylene soluble content 3-35
A modified propylene resin in which at least a portion of a crystalline propylene/ethylene copolymer of % by weight is modified with an unsaturated carboxylic acid or a derivative thereof, and the concentration of the modifier is 0.01 to 20% by weight...30 to 98% by weight (b) The average thickness is 1 to 7 μm and the average particle size is 20
~1000 μm glass flakes...2-50% by weight (c) Ethylene rubber...0-30% by weight (d) At least one inorganic filler selected from talc, mica, and glass fiber...0-35 % by weight of a reinforced modified propylene resin composition.