JPS603413B2 - Talc-containing propylene polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a crystalline propylene polymer in which talc having an extremely fine particle size and a specific particle size distribution is blended with a crystalline propylene polymer.
The present invention relates to a resin composition that is well balanced in physical properties (especially the balance between impact resistance and rigidity), surface properties of molded products (especially scratch resistance and appearance), and weld strength.

Various attempts have been made to add talc to propylene polymers to impart good impact resistance, rigidity, gloss, paintability, etc.
64257, 53-92856, 54-3945, and 55-34271).

・However, in some of these proposals, it is difficult to manufacture such talc because it is made of only ultrafine particles, and the resin composition containing it is also prone to molding defects and has poor impact resistance. It is also difficult to improve weld strength, scratch resistance, and prevention of appearance deterioration such as silver streaks, flow marks, wrinkles, and deterioration of weld appearance. In some cases, there is no limit to the proportion of talc present in the fine grain region (less than one peak), resulting in disadvantages such as the occurrence of zero silver streaks, decreased fluidity (if there are too many fine grains), and decreased rigidity (
If the fine grain area is too small), no adjustment is made to prevent this. Furthermore,
For other products, a method of adding a soft resin component (rubber component) as a third component has been attempted, but this method is insufficient, especially in terms of scratch resistance and appearance, because the particle size distribution of talc has not been sufficiently studied. It has drawbacks such as only being able to obtain certain products and not being able to maintain a balance in quality. In view of this situation, the present inventors first investigated the balance between impact resistance and rigidity and the surface properties (resistance resistance) of molded products made by blending talc with a specific particle size distribution into polypyrene polymers. Samurai Sho 55-81760, Samurai Nukasho 55-91010 specifications), but subsequently, we aimed to further improve the level of talc-containing propylene polymer compositions. As a result of our investigation, we found that by using talc with finer particle size and sharper particle size distribution, we were able to create a resin that greatly improved the balance between impact resistance and rigidity, the surface properties of molded products, and weld strength. It was discovered that a composition could be obtained, and the present invention was achieved.

That is, the present invention has a specific surface area of 45,000 mm or more, an average particle size of 0.2 to 1.5 mm, and a particle size distribution of 6 mm to 95% with a particle size of 1 mm or less by weight, and 2 mm. The following are 6
0% or more, 5 French or less is 90% or more, and 10 or less is 9
Adding 5% or more of tungsten to crystalline propylene polymer
6% by weight of the propylene polymer composition.

(However, the above specific surface area means the value measured by the air permeation method, and the particle size and average particle diameter mean the values measured by the light transmission method using the liquid phase sedimentation method.

) In addition to being excellent in the above points, the composition of the present invention also has gloss,
Heat deformation resistance, tapping properties, paintability, adhesion, printability,
Cree resistant.

The resin has excellent properties and has little sink marks or warping, making it possible to apply the resin to the field of industrial parts such as home appliance parts and automobile parts, which require a high level of quality balance. Detail the ingredients.

The turquoise used in the present invention satisfies the following properties.

That is, the specific surface area is 45,000/ta or more, preferably 5
5000/ta or more, and at the same time, the average particle size is 0.2
~1.5 French, preferably 0.2 to 1.2 French, and the particle size distribution is such that the particle size of 1 French or less exceeds 6 French by weight ~
95%, preferably 70-95%, 60% or more with 2 French or less, preferably 70% or more, 90% or more with 5 French or less, preferably 95% or more, 95% or more with 10r or less, preferably 97% or more It is.

Particularly preferred are those whose substantially total particle diameter is 10 French or less.

Here, the specific surface area is measured using a constant pressure aeration type specific surface area measuring device, such as the powder specific surface area measuring device SS-100 model manufactured by Shimadzu Corporation, based on the generally widely used air permeation method (
The Oroyama constant conditions are standard conditions, such as SS-10
In the case of a head-type device, the sample is 1 inch, the cross-sectional area of the sample tube is 2 mm, the sample layer thickness is 3 to 5 mm, and the height difference between the air hole and the lower water outlet is 600 mm). .

Although there are various methods for measuring the average particle diameter, the following method is used as a simple method.

That is, the average particle diameter is defined as the value at the 50% point of the particle size distribution cumulative curve obtained by measurement using a liquid phase sedimentation permeation method. Examples of such devices include the CP type manufactured by Shimadzu Corporation and the SKN type manufactured by Seishin Enterprises, and the measurement conditions are standard. For example, in the case of Shimadzu CP-5 intensifying layer, the sedimentation method is centrifugal type, Dispersed soot is distilled water, no dispersant or sodium hexametaphosphate (0.1-2%) or commercially available liquid detergent) (5
%), ultrasonic irradiation time is 15 minutes, cell rotation speed is 600 ~
The sample rate was 180 pm, the sample amount was 0.5 pm, the distance between the axes per rotation of the liquid level was 7 pm, and the measured temperature was 230 C. Next, the particle size distribution is based on the particle size distribution cumulative curve from which the average particle size was previously determined. ; Here, the cumulative amount may be expressed in weight % or volume %, but the former is generally used in many cases.

When using a material with a specific surface area of less than 45,000,
The balance of physical properties, especially the impact strength, deteriorates, and the surface properties of the molded product, especially the scratch resistance and anti-wrinkle properties, deteriorate. Average particle size is 0
．． If less than 2 degrees is used, fluidity will be reduced, secondary agglomeration will easily occur, physical properties, particularly impact strength, will be poor, and the appearance of surface properties, particularly silver streaks, will be more likely to occur.

Furthermore, if the current exceeds 1.5 A, the impact strength will be low and the image resistance will be poor. In the particle size distribution, if the particle size lr or less is less than 6% by weight, the physical property balance, scratch resistance, appearance, etc. of the composition will be poor;
If it exceeds the weight percentage, silver streaks are particularly likely to occur, the flowability is poor, and the appearance and resistance to acceptance are poor.

If a material containing less than 6% by weight of 2A or less, less than 9% by weight of less than 5A, and 95% by weight of less than 10A is used, the balance of physical properties, scratch resistance, appearance, and weld strength will be poor.

In addition, the specific surface area, average particle size, and
The particle size distribution is determined by boiling point extraction of xylene or the like, for example, by soaking the resin composition in xylene at 130 to 140 qo for 1 hour to dissolve the resin, and then passing it through a cylindrical furnace paper to remove the remaining talc, or The resin composition is fired and the remaining talc content is measured using the methods described above.
The average value of the aspect ratio (ratio of either length or width to thickness) of the talc is preferably 3 or more (particularly preferably 4 or more. The process, conditions, and method for producing the talc are not particularly limited. However, it can be manufactured, for example, by the following method.

First, for general pulverization of raw ore, a dry or wet pulverizer such as a tube mill type pulverizer, an impact type pulverizer, a micron mill type pulverizer, a centrifugal roller type Raymond mill, a ball mill, a vibration mill, a colloid mill, etc. is used.

If further fine pulverization is required, micron mills, jet-type pulverizers, jet-o-misers, micronizers,
Finely pulverize using a dry or green type pulverizer such as a jet/gluverizer, ball mill, tower mill, vibration mill, or colloid mill.

In this case, wet pulverization is preferable. These crushed talcs are passed through a wet classifier such as a hydrocyclone, centrifugal classifier, drag classifier, rake classifier, Eakins spiral classifier, hydraulic classifier, pot classifier, ball rake classifier, or , Cyclone, Multilon,
Classification is carried out once or multiple times using a dry classifier such as Micron Separator, Microplex, Cyclone Air Separator, Ultra Separator, Jet Chron, or Cracyclon, and the resulting particle size distribution is can be obtained by adjusting. In this case, so-called wet classification is preferable. Further, talc that has been dry classified in advance using a so-called dry classifier such as a cyclone, multilon, or micron separator may be subjected to the above-mentioned wet classifier to obtain wet classified talc, or vice versa.
The surface treatment of the talc may be carried out with or without chemical treatments such as silane coupling agent-based, higher fatty acid-based, fatty acid metal salt-based, maleic anhydride-based, acrylic acid-based, organic titanate-based, resin acid-based, etc. Targeted or physical surface treatments can also be applied. These treatments improve physical property balance, molded product surface characteristics (scratch resistance, appearance, gloss, weld appearance, etc.), paintability, printability, adhesion, tapping performance, moldability, kneading performance, weld strength, etc. It is valid. The amount of the surface treatment agent can be set in the range of 0.01 to 8% by weight based on the talc depending on the purpose. Next, the crystalline propylene polymer resin used in the present invention is a propylene homopolymer (polypropylene) having stereoregularity.

pyrene), Q-olefins other than propylene, such as ethylene, pten-1, bentene-1, hexene-1,
hebutene-1, octene-1, etc. (preferably Q-olefins having 8 or less carbon atoms, especially ethylene, butene-1)
(preferably) up to 4% by weight, preferably 3% by weight
Hereinafter, two or more block or random copolymers of propylene and these Q-olefins, these polypropylene and propylene-Q-olefin copolymers may be mixed with unsaturated organic acids or their derivatives (for example, acrylic acid, methacrylic acid, or their derivatives). ester, maleic anhydride, etc.), organic silanes (e.g. vinyltrimethoxysilane, etc.), and those treated with chlorination, oxidation, sulfonation, etc., and these are Tactical index (11) is 4
It is 0 or more. 11 is preferably 60 or more.

If 11 is less than 4 degrees, rigidity and hardness are insufficient.

Among these, in particular polypropylene, propylene-ethylene random or block copolymers, propylene-ethylene-butene-1 copolymers, especially those with an ethylene content of 1
A propylene-ethylene block copolymer of ~3% by weight, more preferably 3-25% by weight, is preferred (as the ethylene content in the propylene-ethylene copolymer increases, the impact strength is particularly improved. The ethylene content can be measured by conventional methods such as infrared spectroscopy or NMR).
In order to improve fluidity during molding, these crystalline propylene polymer resins generally have a melt flow rate (MFR) of 0.01 to 15 M/10 min, preferably 0.3 to 15 M/10 min.
It is 80 evenings/10 minutes.

If M'R is less than 0.01 minutes/10 minutes, molding defects tend to occur, resulting in poor molded appearance. Also, 150 tano 1
If the time exceeds 0 minutes, the impact strength is insufficient. Here MFR
was measured in accordance with JIS-K7210 (230oo, 2.16k9 load). Note that these crystalline propylene polymer resins may be used together in any proportion.

These polymers are polymerized using a Ziegler-Natta catalyst, and can be appropriately selected from commercially available polymers. The present invention uses the above-mentioned specific talc and propylene polymer, and regarding their blending ratio, the ratio of talc to the total amount of propylene polymer and talc is 5 to 6. % by weight, and preferably 5 to 5% by weight.

If it is less than 5% by weight, not only the rigidity will be insufficient, but also sink marks and warping will be noticeable, making it unsuitable.

If it exceeds 6% by weight, the balance of physical properties, surface properties (appearance, scratch resistance, gloss) and weld strength will be insufficient, and moldability will also be markedly deteriorated, making it unsuitable. In addition to the above-mentioned talc and propylene polymer, other additional components may be added to the composition of the present invention as long as the effects of the present invention are not significantly impaired.

These additional components include surface-treated or untreated inorganic or organic fillers other than turk, such as calcium carbonate (heavy, vertical, porcine, etc.), mica,
Glass fiber, barium sulfate, poppy, calcium acid, clay, magnesium carbonate, alumina, silica, iron oxide, calcium sulfate, glass beads, glass powder, white carbon, hollow glass bulb, poppy, sand, lenite, carbon black, aluminum hydroxide, magnesium hydroxide,
Zinc oxide, basic magnesium carbonate, asbestos, zeolite, white enamel, molybdenum, titanium oxide, lenacite, sericite, shirasu, graphite, calcium hydroxide, calcium sulfite, gypsum fiber, carbon fiber, synthetic silicate fiber ( PMF: Processed Mineral Fiber),
quartz powder, bentonite, metal whiskers, wood flour, sodium sulfate), rubber or latex components (e.g. ethylene-propylene copolymer rubber, styrene-butadiene rubber, styrene-butadiene-styrene flock copolymer, polybutadiene, polyisobutylene, Polyisoprene, 1/2 polybutadiene, nitrile-butadiene rubber,
butyl rubber, etc.), thermoplastic resins or thermosetting resins other than the above-mentioned propylene polymers used in the present invention (e.g., high, medium or low density polyethylene, homopolymers of Q-olefins such as polybutene, copolymers of Q-olefins) olefin polymer resins, such as copolymers of Q-olefin and vinyl monomer, as well as nylon, polycarbonate, acrylonitrile-butadiene-styrene resins (
Resins other than olefin polymer resins such as polystyrene, polyvinyl chloride, polyphenylene oxide, petroleum resins, and phenolic resins), antioxidants (phenol-based, sulfur-based, etc.), lubricants, organic and inorganic various pigments, ultraviolet absorbers, antistatic agents, dispersants, copper damage inhibitors, neutralizing agents,
Foaming agents include plasticizers, antifoaming agents, foaming agents, crosslinking agents, flow improvers (eg, various peroxides), weld strength improvers (eg, various peroxides), nucleating agents, and the like.

The addition of these fillers, various resins, and auxiliary agents not only improves the physical property balance and surface characteristics of molded products (scratch resistance, gloss, weld appearance, silver streaks, flow marks, etc.), but also improves printability, paintability, adhesion, It is effective in improving plating properties, tapping properties, moldability, cross-wire properties, weld strength, durability, heat resistance, weather resistance, etc. These additional components can also be added in combination.

The addition of an inorganic filler as an additional component not only contributes to the effects of the present invention, but also improves plating properties, paintability, adhesion, gloss, moldability, tapping properties, kneading properties, weld strength, creep resistance, It is effective in improving dimensional stability, heat resistance, etc.

Note that the addition of finely divided calcium carbonate (pig, heavy), barium sulfate, titanium oxide, and zinc oxide with an average particle diameter of about 0.05 to 1 significantly improves these effects. In particular, the specific surface area is 16,000 or more and the average particle size is 0.1
When 5 to 7 parts by weight of 6 to 1.0r of settled pig matter or wet-ground heavy calcium carbonate is added to the total weight of 10 of the talc and propylene polymer, the physical property balance (especially stiffness) is improved. and impact resistance strength), and surface properties (particularly scratch resistance and appearance).

At the same time, it also dramatically improves secondary processability, especially paintability. The composition of the present invention can be produced using a single screw extruder, a twin screw extruder,
It can be produced using a conventional drilling machine such as a Banbury mixer, roll, Brabender plastograph, or kneader.

Normally, it is kneaded into a pellet-like compound using an extruder, etc., and then subjected to processing. However, in special cases, talc and propylene polymer are directly fed to various molding machines, and the molding machines are used to form the compound while mixing the wires. You can also. Alternatively, talc is kneaded in advance to a high concentration (in this case, various additives are added at the same time as necessary) to form a masterbatch, which is then diluted separately with propylene polymer or talc-containing propylene polymer for blend compounding. It can also be molded. The method of molding the composition of the present invention is not particularly limited, but extrusion molding and various ripening methods are suitable for compositions with a relatively low MFR, and injection molding is suitable for compositions with a relatively high MFR.

That is, the effects of the present invention can be exerted on molded products regardless of the different molding methods, such as press molding, blow molding, injection molding, sheet molding, aging molding, rotary molding, and lamination molding. The composition of the present invention thus obtained has a highly Z physical property balance (impact strength - stiffness) and good molded product surface properties (scratch resistance, , appearance) and high weld strength. In addition, heat deformation resistance, moldability, printability, paintability, plating performance, tapping performance, and creep resistance are good in Z, and sink marks and warpage are not noticeable, and weld lines are not noticeable. EXAMPLES The present invention will be explained in more detail with reference to Examples below, but these Examples are not intended to limit the invention.

2 The various measurement methods used here are as follows. ■ Impact strength ■ Surface impact strength (Dupont impact strength) Using a sheet of 35 sides x 5 sides x 2 sides, JIS-K54
00, pages 6-13, 2, method B (reference test), the diameter of the curvature of the dart and receiving plate is 1/2.
The experiment was conducted under the condition of 2 inches, and the impact strength value was determined by the fall energy at 50% failure (measurement temperature 23 oo
).

■ Bending impact strength (notched impact strength 3 degrees) J
Conforms to IS-K7110 (measured temperature 2yC).

■ Rigidity (three-point bending modulus) based on JIS-K7203 (measured at 23 temperatures).

■ Resistance to 3JI
By modifying the pencil scratch test device shown in S-K5401, a 100 yen coin was set in the pencil setting part*, and while applying a load of 250M on the uneven side surface, 35 skin x 50 side x 2
A rough grained sheet (average height of protrusions: 0.1 side, average area of protrusions: 4 grains), which is a sail test piece, was rubbed and the marks were visually judged as follows (measurement temperature: 230C). Visual results
Judgment: No scratches are observed.No grade 1 scratches are observed.Some grade 2 scratches are observed.Grade 3 scratches are observed.
Grade 4 ■ Silver streaks, flow marks, grain marks, etc. on the coarse sheet used in the section before appearance (
Visually observe the occurrence of defects (hereinafter referred to as defects) and weld lines.

Visual inspection results: No defects were observed at all, and the weld line was hardly noticeable, making it extremely good. Almost no grade 1 defects were observed, and the weld line was hardly noticeable, making it good.
A slight grade 2 defect is observed, and the weld line is not noticeable.A grade 3 defect is observed, and the weld line is noticeable and extremely poor.
Grade 4■ Weld strength: 10 x 30 x 2 x 2 rib sheets are injection molded using a double cage mold, and from the weld line area that occurs in the center of the molded product and the non-weld line area in the vicinity,
No. 2 tensile test pieces specified by JIS-K7113 were punched out from the weld line part with the longitudinal direction perpendicular to the weld line, and from the non-weld line part in any direction. The graph shows that it is pulled at a speed of 5 gw/min (temperature 2300),
It is calculated from the following formula using each obtained maximum tensile stress (k9/average).

Weld strength = non-worker hand ragigiraigo; Maximum writing strength X・oo (%) of the part test piece.Example 1
'Chinese talc is wet-pulverized using a colloid mill, and then precisely wet-classified using a hydrocyclone.
Table 1 No. Fine-grained talc having the specific surface area, average particle size and particle size distribution shown in 1 and 2 was obtained.

In addition, talc from China is dry-pulverized using a micron mill,
After that, the same wet classification as described above was carried out, and No.
Fine-grained talc having the powder physical properties shown in 3 was obtained. These talcs were not subjected to any particular surface treatment, and the average aspect ratio of each No. 1 is 5, no. 2 is 5. Fu No. 3 was 5. These talc and MFR2.0 evening/10 minutes (J
IS-K6758, 2.16k9 load), ethylene content 11.5% by weight, 1185 propylene-ethylene block copolymer A pellet (prototype), MFR5.5/
10 minutes, ethylene content 4.5% by weight, 1196 propylene-ethylene flock copolymer B pellet (prototype)
, MFR9 min/1 min, ethylene content 3% by weight, 116
8 propylene-ethylene random copolymer pellet (
Prototype) and MFR5 evening/10 minutes, 1198 polypropylene (MH4 manufactured by Mitsubishi Yuka Co., Ltd.) in each prescribed ratio, a mixture consisting of pengara as a pigment and carbon black 5:1 (1% by weight based on the total composition) The mixture was mixed for 2 minutes with a super mixer manufactured by Kawata Manufacturing Co., Ltd., and granulated using a PCM type Nito extruder manufactured by Ikegai Iron Works Co., Ltd. to obtain a pellet-like compound. Thereafter, specimens were molded using a screw-in line injection molding machine manufactured by Meiki Seisakusho, and their impact strength, rigidity, scratch resistance, appearance, and weld strength were evaluated. The results are shown in Table 1 No. 1 to 8. All of these exhibited a good quality balance. Comparative Example 1 Using talc from China, wet-pulverize it with a colloid mill,
Further, it was dry classified using a cyclone (Table 1 No. 91)
7), ■Wet milling in a colloid mill and then wet classification in a hydrocyclone (Nos. 10 and 11 in the same table), ■
Dry pulverization with a microso mill and then dry classification with a micron separator (No. 12 in the same table) and ■Example IN
o. Talc identical to 1 (Nos. 13 to 16 in the same table) and the aforementioned propylene-ethylene floc copolymer A, MFR
O. 01 tano 10 minutes or less, ethylene content 6% by weight, 11
96 propylene-ethylene block copolymer C (prototype), MFR 160/10 minutes, ethylene content 4% by weight
, 1193 p.

Pyrene-ethylene block copolymer D (prototype) and the aforementioned polypropylene were mixed, kneaded, prepared as test pieces, and evaluated in the same manner as in Example 1 at predetermined ratios. The results are shown in Table 1 N
o. 9 to 17.

All had poor quality balance.

That is, those using talc with an irregular particle size distribution, an irregular particle diameter, or an excessively small specific surface area had low impact strength, poor image reception resistance, poor appearance, and low weld strength.

The same problem also occurred in cases where the blending ratio was outside the range specified in the present invention or where the MFR of the propylene polymer used was extreme. Ship Renno Mi Ren S Gokbe [Single smoke Mi S Yari honor weight Steam Erren Umaki Millen Mountain [Glass curtain [9 %＾S].

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Using a Mitsubishi Natco 80 female XL type screw-in line injection molding machine, we manufactured automobile and home appliance parts such as instrument panels, consoles, air conditioners, televisions, etc. with width of 30 m x length of 60 m x wall thickness of 3 sides. The assumed model molded flat plate (
(with coarse grain) was molded.

At this time, moldability and fluidity were good. The obtained molded flat plate has practically sufficient impact strength (including low-temperature impact), rigidity, scratch resistance, and weld strength for automobiles, home appliance parts, etc., and has no flow marks, silver streaks, or grain marks. Weld lines are less noticeable, the gloss is excellent, it has a good appearance, no sink marks or warping, and has good heat deformation resistance and creep resistance, as well as secondary processability such as paintability and printability, tapping performance, and durability. It also showed a good level.

Claims (1)

[Claims] 1 The specific surface area is 45,000 cm^2/g or more, the average particle size is 0.2 to 1.5μ, and the particle size distribution is such that 60% to 95% of particles with a particle size of 1μ or less and 2μ or less are by weight. 60% or more,
5 to 60% by weight of talc with 90% or more of 5μ or less and 95% or more of 10μ or less to crystalline propylene polymer
A propylene polymer composition comprising: (However, the above specific surface area means the value measured by the air permeation method, and the particle size and average particle diameter mean the values measured by the liquid phase sedimentation method light transmission method.)