JPS60248765A - Filler-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent scratch resistance, dimensional stability under heat, and low-temperature impact resistance, by compounding a (modified) crystalline propylene polymer with a metal salt of an ethylene/ alpha,beta-unsaturated carboxylic acid copolymer, a filler and an ethylene rubber. CONSTITUTION:The objective composition can be prepared by compounding (A) 20-96(wt)% crystalline propylene polymer which may be modified with an unsaturated organic acid or its derivative, with (B) 2-70% metal salt of a copolymer of ethylene and an alpha,beta-unsaturated carboxylic acid, (C) 2-30% filler, and (D) 0-40% ethylene rubber. The component A is preferably polypropylene or a propylene-ethylene copolymer. The neutralization degree of the compound B with metal ion is >=5%, preferably 10-60%, and the component C is preferably talc having an average particle diameter of 0.5-2.5mu.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a resin composition suitable for a soft molding material having excellent scratch resistance, heat-resistant dimensional stability, and low-temperature impact resistance.

<Prior art> Crystalline propylene polymer (hereinafter simply abbreviated as PP)
It has been widely attempted to improve the balance between rigidity and impact resistance and improve dimensional stability by adding various fillers, rubbers, etc. It is applied to automobile parts and home appliance parts.

However, these have the disadvantage of poor scratch resistance on the surface of the molded product (resistance to linear scratches that occur when the surface of the molded product is rubbed with a foreign object).For example, soft polyolefin materials with relatively high flexibility In many cases, the level was not applicable to bumpers, fascias, etc., to which the standard was applied.

In order to improve the scratch resistance of
Attempts have been made to select P or add specific components (JP-A-56-88447, JP-A-57-8235).
, 57-16042, 57-73033, 57-
Publication No. 73034, etc.).

In addition, the present inventors have previously proposed improvements by using specific pigments (Japanese Patent Applications No. 57-218037, No. 57-21
8038, specification 5B-177724).

However, especially in conjunction with recently advanced technologies in other fields, extremely high performance is required, and in particular, soft resins that provide molded products with excellent scratch resistance and outstanding low-temperature impact resistance and heat-resistant dimensional stability. It was wanted.

<Problems to be Solved by the Invention> The present invention aims to solve the deficiencies of the prior art, that is, to develop a material with excellent scratch resistance, low-temperature impact resistance, and heat-resistant dimensional stability. The inventors have discovered that this object can be achieved by blending a metal salt of 1, a filler, and optionally an ethylene rubber into modified or unmodified PP.

<Means for solving the problems> That is, the present invention is a filler-containing resin composition characterized by comprising each of the following components (a) to (d).

(a) Crystalline propylene polymers 20 to 96 modified or unmodified with unsaturated organic acids or derivatives thereof
Weight% (b) Metal salt of copolymer of ethylene and α,β-unsaturated carboxylic acid 2-70% by weight (C) Filler 2-30% by weight (Small ethylene rubber 0-40% by weight <Function> The pH of the component (a) used in the present invention is unmodified or at least partially modified with an unsaturated organic acid or a derivative thereof, and the concentration of the modifier is 0.01 to 20% by weight.
This is PP. Here, unmodified or modified P
P may be a homopolymer of propylene (polypropylene), consisting of a majority of the weight of propylene and other α-olefins (e.g., ethylene, butene, pentene, hexene, heptene, 4-terpentene, octene, etc.), vinyl esters ( For example, vinyl acetate), aromatic vinyl monomer (
For example, it may be a block, random or graft copolymer of two or more elements (a mixture of these may also be used) with vinylsilane (eg, tJi', vinyltrimethoxysilane, vinyltrimethylsilane), etc. Among these, polypropylene and propylene-ethylene copolymers are preferable from the viewpoint of achieving the effects of the present invention, and particularly polypropylene with an ethylene content of 1 to 1.
25% by weight (preferably 2 to 20% by weight), especially boiling xylene soluble content of 3 to 30% by weight (preferably 4 to 25% by weight) and an ethylene content in the soluble content of 20 to 20% by weight. 60% by weight (preferably 25-50% by weight)
) propylene-ethylene block copolymers are preferred.

Here, the measurement 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 2F of woven material in boiling xylene 600cc for 20 minutes and dissolving it. After that, it was cooled to room temperature, filtered through a G4 type glass filter and dried, and the value was calculated by back calculation from the weight of the solid phase.

This block copolymer having an ethylene content of 1 weight or more has excellent impact resistance. Further, those having a boiling xylene soluble content of 3% by weight or more are preferable in terms of impact resistance, while those having a boiling xylene soluble content of 30% by weight or less are excellent in terms of scratch resistance. Furthermore, those having an ethylene content of 20% by weight or more in the soluble matter are excellent in impact resistance, while those having an ethylene content of 60% by weight or less are excellent in terms of scratch resistance.

Isotactic distribution (II) of these PPs
is generally 40 or more, preferably 60 or more. Those with II less than 40 have not only scratch resistance but also rigidity,
It is unsuitable due to lack of hardness etc.

In addition, MFR (JIS-7210.230℃, 2.1
6 shame load) is generally 0.01 to 20. Ot710 minutes, preferably 0.1 to 100 t/10 minutes, particularly 1 to 10 minutes is most suitable for injection molding. Those with an MFR of less than 0.019710 minutes have poor moldability and appearance, while those with an MFR of more than 200 flL 0 minutes have poor impact resistance and are unsuitable. Here, the MFRH polymerization conditions may be used, or they may be adjusted and set using appropriate post-treatment, such as peroxide treatment.

These polymers are polymerized using a Ziegler-Natsuta catalyst, and can be appropriately selected from those with normal polymer numbers, or two or more types can be used in combination.

To modify these PPs with unsaturated organic acids or their derivatives, for example, unsaturated organic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid; maleic anhydride, itaconic anhydride, citraconic anhydride. Anhydrides of unsaturated organic acids such as; esters of unsaturated organic acids such as methyl acrylate and monomethyl maleate; amides of unsaturated organic acids such as acrylamide and fumaric acid monoamide; unsaturated organic acids such as itaconic acid imide It is modified by a grafting method by adding 0.01 to 20 parts by weight of an acid imide or the like to 100 parts by weight of a crystalline propylene polymer. Among these, those modified using acrylic acid or maleic anhydride are preferred. This modification is effective in improving scratch resistance, rigidity, impact resistance, dimensional stability, etc. During this modification, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, etc. are added to increase the degree of modification.
An organic peroxide such as butyl hydroperoxide is used. Usually, the blending amount is 0.0'01 to 3.0 parts by weight per 100 parts by weight of the pyrene polymer. The denaturation method is
Although not particularly limited, for example, by blending PP with an unsaturated organic acid or its derivative and an organic peroxide and mixing thoroughly7,
This is carried out by heating, melting and kneading at 0°C for 0.2-15 minutes.

Modified PP only needs to be at least partially modified.
It is possible to use P diluted with one or more types of unmodified PP, and this is a preferred method since the concentration of the modifier 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 polymer, and the desired quality can be selected by appropriately selecting the same type or different types.

Next, the metal salt of the copolymer which is the component (b) used in the present invention is an ionic copolymer metal salt of ethylene and α,β-unsaturated carboxylic acid. It is obtained by copolymerizing 0.2 to 25 moles of α,β-unsaturated carboxylic acid, which is partially or entirely cross-linked (neutralized) with a metal ion having a valence of 1 to 3. Here, α
, β-unsaturated carboxylic acids include monoesters of methacrylic acid, itaconic acid, acrylic acid, ethacrylic acid, maleic acid, fluoric acid, and dicarboxylic acids (e.g., eva, monomethyl fumarate, monoethyl fumarate, maleic acid monomethyl ester, etc.). Also, α
, metal ions having a valence of 1 to 3 used for cross-linking (neutralizing) β-unsaturated carboxylic acids are metal ions of groups 1, ■, III, IV-A and ■ of the periodic table of elements. 1
~A metal ion having a trivalent valence, such as
K+, Na+, M+, C8+, r=i+, Cu+, C+
, Be+, Mg++, sr++, ca++, Ba++,
cu++, cd+'-1-1Hg++, h++, sn+
士、co++、HH++、At++、z、++、S、+
-1-At"", Fe+++, y+++, and the like. In addition, the degree of neutralization by metal ions is preferably 5% or more, particularly preferably 10 to 60%. The degree of neutralization referred to herein is defined as the molar ratio of the carbo/acid metal salt contained in the copolymer to the sum of the carboxylic acid group and the carboxylic acid metal salt, and is expressed as follows. M represents a metal ion.

Degree of neutralization (Morti) = ((COOM)/((COOM)+
(COOH)))xto.

In addition, the filler of component (C) used in the present invention is an inorganic or organic filler that has been subjected to surface treatment or is untreated, such as talc, glass fiber, milled fiber, cut-off innocuum, mica, and calcium carbonate. (heavy, light, colloid), barium sulfate, calcium silicate (wollastonite), clay, magnesium carbonate,
Alumina, silica, calcium sulfate, glass peas, glass powder, hollow glass spheres, silica sand, silica stone, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, asbestos, zeolite, molybdenum, silica, sericite , whitebait, graphite, calcium hydroxide,
Calcium sulfite, gypsum fiber, carbon fiber, synthetic silicic acid fiber (PMF': processed mineral fiber, Rockfino<-, microfiber, etc.), quartz powder, bentonite, metal whisker, wood flour, aromatic polyamide fiber, sulfuric acid fiber -da etc. Among them, talc, glass fiber (including so-called chopped strands and cut fibers, etc.), glass powder (including so-called milled fibers, glass flakes, surf strands, etc.), wollastonite, synthetic silicate fibers, and sulfuric acid. Preferred are barium and calcium carbonate mica, and particularly preferred are talc with an average particle diameter of 0.5 to 2.5 μm, glass fibers, wollastonite, and milled fibers with an average diameter of 6 to 13 μm.

In addition, the above (
The ethylene rubber of component d) is, for example, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, ethylene-butene-1 copolymer rubber, etc., and preferably has an ethylene content of 90 to 401%. and has a Mooney viscosity (at 100°C) of about 5 to 120. Further, this component may be modified in advance with an unsaturated organic acid or a derivative thereof.

In the present invention, the amount of each of these components (a) to (d) used is preferably 20 to 96% by weight of PP in (a) and 30 to 8% by weight.
5 weight t%; (b) 2 to 70 weight % of copolymer metal salt, preferably 10 to 50 weight %; (C) filler 2 to 30 weight %, preferably F! 3-20% by weight: (mountain rubber 0-40
The weight percent is preferably 5 to 30 weight percent.

If component (a) is less than 20% by weight, moldability is poor;
On the other hand, if it exceeds 96% by weight, the effects of the present invention cannot be expected. If component (b) is less than 2% by weight, the effect of the present invention cannot be expected, while if it exceeds 70% by weight, heat resistance will decrease, and
It will be economically disadvantageous. If the amount of component (c) is less than 2% by weight, the effects of the present invention cannot be expected, while if it exceeds 30% by weight, the impact strength, scratch resistance, and appearance of the molded product will deteriorate. (
When the content of component d) exceeds 40% by weight, the heat-resistant dimensional stability deteriorates significantly, and the scratch resistance also deteriorates.

The composition of the present invention contains (a) 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 component (d). Additional components include thermoplastic resins other than the ω component (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), α- other than propylene, such as polymerization, ethylene-vinyl acetate copolymer, maleic anhydride grafted polyethrene, etc.
Olefin polymer resins such as copolymers of olefins and vinyl monomers, as well as polyamides, polycarbonates, acrylonitrile-butadiene-styrene resins (ABS)
, polystyrene, polyvinyl chloride, polyphenylene ether, and other resins other than olefin polymer resins; thermosetting resins; modified or unmodified rubber or latex components other than component (d) (e.g. styrene-butadiene rubber, 1,2- Polyfridiene, butyl rubber, styrene-butadiene-styrene block copolymer, hydrogenated product thereof,
(nitrile-butadiene rubber, polyimbutylene, polybutadiene, polyimprene, etc.); metal salts of copolymers of α-olefins other than component (b) and α,β-unsaturated carboxylic acids (for example, propylene and α,β-unsaturated carboxylic acids); -Metal salts of random spanning graft copolymers with unsaturated carboxylic acids, etc.); Antioxidants (phenolic, sulfur, etc.); Lubricants:
Colorant; UV absorber; Antistatic agent; Dispersant: Copper damage inhibitor; Neutralizing agent; Foaming agent; Plasticizer: Antifoam agent; Flame retardant; Crosslinking agent; Flowability improver; Weld strength improver; Painting Modifiers; light stabilizers; nucleating agents, etc. can be mentioned. 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, or kneader.

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 and It may be granulated using an extruder.

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 feed the components (d) individually or in advance by kneading some of them directly to various molding machines and mold them while mixing the parts in the molding machine. Alternatively, components (b) to (d) may be blended singly or in part with component (a) at a high concentration, mixed with masterbatch 12, and then separately mixed with (a) or (b).
) or (it is also possible to carry out blend comparison or molding while diluting with component (a).For example, component (c) can be continuously supplied from the vent hole or die part of the extruder. For example, extrusion molding and various thermoforming methods are suitable for those with a relatively low MFH, and injection molding is suitable for those with a relatively high MFR. ,
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.

<Effects of the Invention> The composition of the present invention thus obtained has high scratch resistance and heat-resistant dimensional stability, which are not found in conventional filler-containing propylene resin compositions, as well as good low-temperature impact 52 strength and moderate strength. Since this material appears under soft textures (low rigidity), it is suitable for application to products in the industrial parts field that require a high level of performance, such as interior and exterior parts for automobiles such as bumpers and fascias. It is.

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

■Scratch resistance 100X100X3 A sapphire needle with a radius of 0.5 tms is pressed against the injection molded sheet of each bite under a certain load, and the sheet is moved at a speed of 4150 van/min to scratch. Measure the depth of the scratch at this time and find that it is 5.
Measure the load that reaches μ (therefore, the better the scratch resistance, the higher the load value).

■Heat resistant dimensional stability ■Heat sag resistance 300 x 25 ) e @Coefficient of linear expansion Based on ASTM-D696 (temperature range is 20-80℃)
.

■Test piece (100X) installed on impact strength support (hole diameter 40mm)
A dart, which is a load sensor, was dropped onto 100×3 III+I+) (9f on IWrM×7), and the deformation and fracture behavior of the test piece under impact load was measured.
- The impact energy absorbed up to the point of crack initiation at the point was calculated and was taken as the impact strength of the material. The measurement atmosphere temperature was -30°C.

■Rigidity (three-point bending modulus) Compliant with JIS-7203 (measurement atmosphere temperature 23℃)
.

Example 1 In addition to the components (a) to (d) shown in Table 1, 0.1% by weight each of a phenolic antioxidant and a sulfur antioxidant were blended, and the mixture was heated in a vented screw extruder at a temperature of 230°C. (Single axis 4
The mixture was kneaded and granulated using a screw-in-line injection molding machine (0 ttrm diameter), and then molded into evaluation specimens using a screw in-line injection molding machine and evaluated. The results are shown in Table 1. Compositions with Nα1-5 showed good quality balance. That is, it exhibited good scratch resistance, excellent heat-resistant dimensional stability, high low-temperature impact strength, and a moderately soft texture. Also, using a composition of N[12, the width is 30
When we molded a model flat plate assuming an industrial part with a length of 600 m and a thickness of 3 m, we obtained a molded product with good moldability, no problems with appearance, sink marks, or warping, and with the above-mentioned performances sufficient for practical use. It was done. On the other hand, compositions with Nα6 to 8 had poor quality balance, that is, lacked soft texture, low impact strength, insufficient scratch resistance, and poor heat-resistant dimensional stability. The components (a) to (d) used here are as follows.

(a) Component: PP EPP-1: MFR 15P/10 min, ethylene content 8wt 1%, boiling xylene soluble content 21wt%, ethylene content of the same component 26wt%, modification amount of maleic anhydride 0
．． 03 heavy R-ethylene ethylene-propylene block copolymer EPP-2: MFR 25f 710 minutes, ethylene content 6% by weight, boiling xylene soluble content 11% by weight, ethylene content 39% by weight of the same component. (Blank component: copolymer metal salt (ionomer) IM-1
: Z of ethylene-methacrylic acid copolymer with MFR 5, or/l o min, ethylene content 97 molar, and degree of neutralization 20 m
n salt 1M-2: MFRl, 55'/10 min, ethylene content 8
Nam (c) component of ethylene-methacrylic acid copolymer with 5 molti and neutralization degree of 60%: Filler talc: average particle size 1.9μ, specific surface area 39000tyl
Glass fiber: average diameter 9μ, the surface is treated with aminosilane, and the adhesion amount of the sizing agent containing it is 0.5μ. 21% by weight.

Milled fiber average diameter is 9μ, average length is 150
μ's.

(d) Component: Rubber EPR: x-y-vy content 76 Weight L Mooney viscosity ML1+4 (100°C) 20 ethylene-propylene copolymer rubber (blank below)

Claims (1)

[Scope of Claims] A filler-containing resin composition characterized by comprising each of the following components (a) to (d'l): (a) Crystals modified or unmodified with an unsaturated organic acid or a derivative thereof. propylene polymer 20-9
(b) Metal salt of copolymer of ethylene and α,β-unsaturated carboxylic acid 2-70% by weight (c) Filler 2-30% (d) Ethylene rubber θ-40% by weight Bud Chi