JPS6341552A - Propylene based polymer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition, by reacting a specific modified propylene based polymer with amorphous ethylene-propylene polymer, having improved mechanical characteristics, moldability as well as weather resistance and capable of well adhering to polyurethane even without using a primer. CONSTITUTION:A composition, obtained by blending (A) propylene based polymer with (B) a modified propylene based polymer consisting of 100pts.wt. propylene based polymer or a blend thereof with an ethylene-propylene based copolymer, 0.1-50pts.wt. hydroxyl group-containing organic compound having at least one unsaturated bond in the molecule and 0.01-20pts.wt. organic peroxide and (C) an amorphous ethylene-propylene copolymer having 20-100 Mooney viscosity (100 deg.C) and 20-50wt% propylene content to give the following amounts and ratios. 5.0-50wt% component (B), 3-35wt% component (C), 5-90wt% ratio [component (B) to the total of the components (A) and (B)] and 0.1-10wt% ratio [organic compound in the component (B) to the total of the components (A), (B) and (C)].

Description

[Detailed description of the invention] The present invention relates to a propylene polymer composition that not only has excellent adhesion to polyurethane without using a primer but also has good weather resistance. Provides a propylene-based polymer composition that has excellent mechanical properties such as rigidity and impact resistance, and has good resistance to i4 (I4), and also has excellent adhesion to polyurethane without using a primer. The purpose is to

Conventional technology As is well known, propylene polymers (propylene small polymers, propylene copolymers) not only have excellent composition J[H)1, but also have excellent mechanical properties, heat resistance, solvent resistance, Because it has good properties such as oil resistance and chemical resistance, it is manufactured in large quantities industrially and is widely used in many fields as industrial parts and articles for automobiles, electrical appliances, electronic appliances, etc. However, since propylene polymers do not have polar groups in their molecules (so-called non-polar),
Adhesion with polyurethane is not good, which causes various problems. - As an example, a widely used automobile bumper will be explained.

In the past, bumpers made of metal or polyurethane were widely used, but in recent years, with the aim of reducing the weight of automobiles, reducing costs and lowering costs, propylene-based polymers containing propylene as the main component Coalescence, ethylene-
Bumpers made from propylene random or block copolymers) or propylene-based polymer-based compositions are widely used. When this bumper is installed on a vehicle, the surface of the molded product is often embossed in advance and used as is without painting. However, in order to give it an even more fresh and luxurious feel, the bumper is often painted with a polyurethane paint and installed on the vehicle, and this trend is increasing as cars become more luxurious. It's coming.

However, as mentioned above, propylene-based polymers are chemically extremely inert polymeric substances because they do not have polar groups in their molecules, so when painting polyurethane, it is generally necessary to prepare them in advance. The molded product can be processed using electrical processing methods (for example,
Surface treatment methods such as corona discharge treatment, plasma treatment), mechanical roughening, flame treatment, and oxygen or ozone treatment are commonly used.

Furthermore, prior to these surface treatments, it is necessary to clean the surface in advance with a solvent such as alcohol or aromatic hydrocarbon.
II': Recommended. It is also known to immerse the molded article in organic solvents such as tricrene, perchlorethylene, pentachlorethylene, and toluene at temperatures close to their boiling point or to expose them to solvent vapors [see, for example, Kenyuki Takagi, Hiroshi Sasaki] Edited by 3, “Plastic + i Fee Course■
, Volip Denkopylene Resin, pp. 216-219, published by Kogyo Shimbunsha in 1962].However, all of these methods not only require processing equipment; There was a problem in that the processing required a considerable amount of time.Therefore, the molded product (bumper) was undercoated with a primer that could adhere to the propylene-based electrolyte, and then a polyurethane paint was applied as a topcoat. In other words, with this method, you have to go through the process of primer undercoat 10 times baking → polyurethane painting → baking (2 coats 2 bakes or 3 coats 2 bakes), and this painting process takes about 1 hour (oil-tight, approx. For this reason, manufacturing bumpers made of propylene polymer coated with polyurethane requires a long painting cycle, which not only makes mass production difficult but also increases costs. .

In addition, when applying polyurethane when manufacturing automobile parts, motorcycle parts, electrical equipment parts, electronic equipment parts, etc. using propylene-based polymers, the same problems as mentioned above occur, although the application method is different. There is.

Generally, propylene polymers or their compositions used in bumpers etc. contain UV absorbers and UV absorbers to enhance weather resistance.
Ultraviolet stabilizers, antioxidants, and other additives are used in combination in arbitrary formulations. However, after several years of actual driving, the surface of the molded product becomes discolored, chalking or cranking occurs, and the current one cannot be said to be sufficient, and furthermore, the weather resistance is not good. The demand for bumper gray 1' is becoming more and more popular as automobiles become more luxurious and the proportion of cars used in regions with harsh climates increases.

As a countermeasure, it may be possible to increase the amount of conventional weather-resistant formulations or add new additives, but simply increasing or adding these ingredients may cause problems with appearance during molding (for example, surface gloss or whitening, etc.), additives increased or added to the surface of the molded product after molding may bleed, worsening the appearance, and WI caused by actual running.
There are various problems such as whitening of the surface of the molded product due to use during IJI.

The object of the present invention is to solve the problems or drawbacks of the conventional propylene polymer compositions described above, and to solve the various problems that propylene polymers have. It not only maintains or improves mechanical properties (such as impact strength and rigidity), but also has good moldability and excellent weather resistance, and at the same time exhibits good adhesion to polyurethane without using a primer. The object is to obtain a propylene polymer composition.

According to the first aspect of the present invention, the above-mentioned problems can be solved by using (A) a propylene polymer, (B) ( 1) 100 parts by weight of a propylene polymer or a mixture of a propylene homopolymer and an ethylene-propylene copolymer rubber; (2) an organic compound having at least one unsaturated bond in the molecule and containing one hydroxyl group; A modified propylene polymer obtained by treatment with 0.1 to 50 parts by weight of a compound and (3) 0.01 to 20 parts by weight of an organic peroxide, and (C) Mooney viscosity (Ml, I+4 (100 ° C.) ]
is 20 to 100, and the propylene content is 20
It is a composition consisting of an amorphous ethylene-propylene copolymer with an amorphous ethylene-propylene copolymer of ~50% by weight, and the component (B
) and (C) are 5.0 to 50% by weight and 3 to 35% by weight, respectively, and the composition ratio of component (B) to the total amount of components (A) and (B) is 5 to 50% by weight. 90% by weight
and the composition ratio of component (B) (2> to the total amount of components (A), (B) and (C) is 0.01 to 10% by weight
According to the second aspect of the present invention, the above problem can be solved by a propylene polymer composition comprising: (A) a propylene polymer; (B) (1) a propylene polymer; or 100 parts by weight of a mixture of propylene homopolymer and ethylene-propylene copolymer rubber; (2) 0.1 to 50 parts by weight of an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group; and (3) a modified propylene polymer obtained by treatment with 0.01 to 20 parts by weight of an organic peroxide, and (C) Mooney viscosity CM+, 1+. (100°C)) is 20 to 100, and the propylene content is 20 to 100.
50% by weight of an amorphous ethylene-propylene copolymer; (D) a high-density ethylene polymer having a density of 0.935 g/cJ or less; and (E) an inorganic filler; Ingredients in things (B)
, (C), (D) and (E), respectively,
5 to 50% by weight, 3 to 35% by weight, 3 to 20% by weight, and 3 to 35% by weight, and the component (B) that is attached to the gold side M of the eyelid components (A) and (B). The ratio of component (A> and (B) to the total NIM of component (A) is 5 to 90% by weight,
The problem is solved by a propylene polymer composition in which the composition ratio of B-2) is 0.1 to 10% by weight.

Intermediate book - modern book - 琲 - 戊MON - The present invention will be specifically explained below.

(8) Propylene polymer 8J, a propylene polymer blended into the composition of the present invention,
Propylene homopolymers, block copolymers containing propylene as a main component with ethylene and/or α-olefin, and propylene-based block copolymers with ethylene and/or α-olefins;
or a random copolymer with α-olefin. In both of these block copolymers and random copolymers, the copolymerization ratio of ethylene and α-olefin is 20% by weight or less as a total amount thereof, preferably,
15f: [ii% or less. Further, the α-olefin preferably has 4 to 12 carbon atoms, and representative examples of such α-olefins include butene-1, hexene-1,
Mention may be made of 4-methylhexene-1 and octene-1.

These propylene polymers are produced industrially,
It is used in many ways.

Furthermore, the physical properties and manufacturing methods of these propylene polymers are well known. Among such propene-based polymers, the use of the block copolymers and random copolymers is preferred.

This propylene polymer melt flow rate-1 (MF
R) (Measured under condition 14 according to JISK72]0)
is usually 1.0 to 100 g/10 minutes, and 1.0 to 80
g/10 minutes is desirable, and 2.0 to 60 g/10 minutes is particularly preferred. If a propylene polymer with an MFR of less than 1.0 g/10 minutes is used, not only the kneading properties with the modified propylene polymer tend to deteriorate, but also the moldability of the resulting composition may deteriorate. , conversely MFR
However, it is not preferable to use a propylene polymer having a LoOg/10 min because the resulting composition tends to have lower mechanical strength.

(B) Modified propylene polymer The modified propylene polymer of the present invention is obtained by treating a propene polymer or a mixture of a propylene homopolymer and an ethylene-propylene copolymer rubber with a hydroquine compound and an organic peracid compound. can be obtained by
Regarding the manufacturing method and others, for example, JP-A-58-
This is as described in detail in Japanese Patent No. 154732.

(1) Propylene polymer (Variation of the present invention) The propylene polymer used to produce the 1L propylene polymer is exactly the same as the propylene polymer described above except for MFR. The system polymer components need not be identical.

Instead of the propylene polymer, a mixture of a propylene homopolymer and an ethylene-propylene copolymer rubber described later in the composition ratio described later can also be used. The ethylene-propylene copolymer rubber used in this manner has ethylene and propylene as its main components. This ethylene-propylene copolymer rubber includes copolymer rubber obtained by copolymerizing ethene and propylene, and ethylene and propylene as main components, 1,4-pentadiene, L5-hexadiene, and 3,3- Linear or branched diolefins containing two double bonds at the ends such as dimethyl-1,5-hexadiene, 1,4-hexadiene and 6-
Terminal linear or branched diolefins such as methyl-1,5-hebutadiene or bicyclo(2,2,
l )-hebutene-2 (norbornene) and its derivatives, such as ethylidene norbornene).
(Generally, 10% by weight or less) It is broadly classified into multicomponent copolymer rubber obtained by copolymerization. In both the copolymer rubber and multicomponent copolymer rubber described above, the preferred propylene content is 20 to 50% by weight. Further, the preferable Mooney viscosity (ML l+4 (100°C)) of the ethylene-propylene copolymer rubber is 10 to 50.
, more preferably 10-40, especially 15-40
40 is preferred. When an ethylene-propylene copolymer rubber with a Mooney viscosity of less than 10 is used, the moldability is good, but the adhesion strength with the urethane paint described later is not sufficiently improved; If it is used, flow marks etc. will occur on the surface of the molded product, resulting in an unfavorable appearance (11).

When producing the modified propylene polymer of the present invention using an ethylene-propylene copolymer rubber, the ethylene-propylene copolymer rubber accounts for the total amount of the propylene homopolymer and the ethylene-propylene copolymer rubber. The proportion of is usually at most 40% by weight and 1
-40% by weight is preferred, especially 2-35% by weight. If the proportion of ethylene-propylene copolymer rubber in the total amount of propylene single ffl and ethylene-propylene copolymer rubber exceeds 40% by weight, the adhesion strength with the coating film is good, but the molded product This is not preferable because not only flow marks occur on the surface, but also the gloss tends to be low T.

This propylene polymer melt flow rate-1 (MF
R) is usually 0.0 from the viewpoint of moldability, mechanical properties of the resulting composition, etc. Old ~] OOg/10 minutes, 0.01~
80g/10 minutes is preferred, especially 0.02-60g
/10 minutes is suitable.

(2) Hydroxyl compound The hydroxyl compound used to produce the modified propylene polymer described above has at least one unsaturated bond (double bond, double bond) and contains a hydroxyl group. It is a compound that

Typical examples of such hydroxyl compounds include alcohols having double bonds, alcohols having double bonds, esters of -valent or divalent unsaturated carboxylic acids and unsubstituted dihydric alcohols, and esters of unsaturated carboxylic acids and unsubstituted dihydric alcohols. Examples include esters with substituted trihydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted trihydric or higher alcohols.

Representative examples of such hydroxy compounds include 1,2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate-1, and 2-hydroxybutyl methacrylate-1.

In producing the modified propylene polymer according to the present invention, the hydroxyl compound is added to the propylene polymer 1.
0.1 to 50 parts by weight, preferably 0.00 parts by weight
．． 2 to 30 parts by weight are used, particularly preferably 0.3 to 20 parts by weight. If the ratio of the hydroxyl compound to 100 parts by weight of the propylene polymer is less than 0.1 part by weight, the effect of improving adhesion is insufficient. On the other hand, even if it is used in an amount exceeding 50 parts by weight, the effect of improving adhesion depending on the amount used is not observed, and rather the original properties of the propylene homopolymer are impaired, which is not preferable.

(3) Organic peroxide The organic peroxide used to produce the above-mentioned modified propylene polymer is generally used as an initiator in radical polymerization and as a crosslinking agent for polymers.
Those having a half-life of 1 minute or more are preferably 00°C or more, and those having a 1-minute half-life of 130°C or more are particularly preferred. If an organic peroxide whose temperature is less than 100° C. is used, it is not only difficult to handle, but also the effects of its use are not very noticeable, which is not desirable.

The usage ratio of the organic peroxide to 100 parts by weight of the propylene polymer is 0.01 to 20 parts by weight, and 0.05 to 20 parts by weight.
10 parts by weight is preferred, and 0.1 to 7 parts by weight is particularly preferred. If the mixing ratio of organic peroxide to 100 parts by weight of the propylene polymer is less than 0.01 parts by weight, not only will the effect of improving adhesion with polyurethane be low, but also the durability of the adhesion strength of the mixture will decrease. Unfavorable, on the contrary, 2
If the amount exceeds 0 parts by weight, it is undesirable because the inherent mechanical properties of the propylene polymer deteriorate.

(4) Method for producing modified propylene polymer In order to produce the modified propylene polymer used in the present invention, the propylene polymer, hydroxyl compound, and organic peroxide described above are treated (heated) in the above proportions. It can be manufactured by At this time, the propylene polymer, hydroxyl compound, and organic peroxide may be mixed together during the treatment, but these should be mixed in advance in l-"liblend, or at a relatively low temperature
It can also be obtained by kneading at a temperature at which the xyl-based compound does not react, and heating the resulting mixture as described below.

If a propylene copolymer is processed at high temperatures, the propylene polymer may deteriorate.
It must be carried out at a temperature at which the organic peroxide used in the combination decomposes.

Therefore, although it depends on the type of organic peroxide used, this treatment is generally carried out at a temperature of 160 to 300゛C1.
Preferably, it is carried out at 170-280°C.

The general formula and representative examples of the hydroxyl compound and organic peroxide, as well as the mixing method and treatment method, are as described in detail in, for example, Japanese Patent Application Laid-Open No. 58-154732-).

(C) Amorphous ethylene-propylene copolymer Mooney viscosity CM +-1+4(10
0° C.)) is 20 to 100, preferably 20 to 80, and particularly preferably 30 to 75. Mooney viscosity is 20
If an amorphous ethylene-propylene copolymer of less than On the other hand, if a material with a Mooney viscosity exceeding 100 is used, not only will it be difficult to uniformly disperse it with other composition components during kneading, but even if a uniform composition is obtained, the surface of the molded product will be Hitachi such as flow marks and weld lines become severe, making it impossible to obtain a molded product with a good appearance. Furthermore, the propylene content of this copolymer is generally 20 to 50% by weight, and 25 to 45% by weight.
A content of 25 to 40% by weight is particularly preferred. This amorphous ethylene-propylene copolymer has rubber-like properties, is industrially produced and used in a wide range of fields, and its manufacturing method is also widely known.

The amorphous ethylene-propylene copolymer is a copolymer rubber obtained by copolymerizing ethylene and propylene, and contains ethylene and propylene as main components, 1.4-pentadiene, 1.5-hexadiene and 3. Straight chain or branched diolefins containing two double bonds at the end such as 3-dimethyl-1,5-hexadiene, 1,4-hexadiene and 6-methyl-1,5- Terminal linear or branched diolefins such as hebutadiene or bicyclo(2,2,1)-
Copolymerizing a monomer having a double bond such as a cyclic diene hydrocarbon such as hebutene-2 (norbornene) and its derivatives such as ethylidene norbornene (generally 10% by weight). It can be broadly classified into multicomponent copolymer rubber obtained by

1) High-density ethylene polymer The high-density ethylene polymer used as component (1') in the present invention has a density of 0.935 g/cta.
The above ethylene polymer is 0.935 g/cJ ~
0.980g/c+J is preferred, especially 0.980g/c+J.
935-0.975 g/cIl! Preferably. Such ethylene polymers are generally ethylene homopolymers and copolymers of ethyne and an α-olefin (generally having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms). Suitable alpha-olefins include propylene, butene-1, hexene-1,4-methylpentene-1 and octene-1.

The melt flow index (measured under conditions 4 according to JIS K-7210, hereinafter referred to as rMFR(1)J) of this high-density ethylene polymer is generally 0.5 to 100 g.
/10 minutes, preferably 0.5 to 80 g/10 minutes, particularly preferably 1.0 to 60 g/10 minutes. If a high-density ethylene polymer with an MFR (1) of less than 0.5 g/10 minutes is used, it will not only be difficult to disperse it uniformly during kneading, but also cause flow marks to appear on the surface of the resulting molded product. There is a risk that

On the other hand, if an ethylene polymer having a MFRN) exceeding 100 g/10 minutes is used, it is still difficult to uniformly disperse it during kneading, and moreover, the resulting composition tends to have a lower iIi impact resistance.

(E) Inorganic filler The inorganic filler used as component (E) in the present invention is generally one widely used in the fields of synthetic resins and rubber. Such an inorganic filler is preferably an inorganic compound that does not react with oxygen or water and does not decompose during kneading and molding. The inorganic fillers include metals such as aluminum, iron, lead and nickel, these metals and magnesium,
Oxides of metals such as calcium, barium, zinc, zirconium, molybdenum, silicon, antimony, titanium, etc.
It can be broadly classified into compounds such as hydrates (hydroxides), sulfates, carbonates, silicates, double salts thereof, and mixtures thereof.

Representative examples of such inorganic fillers are described in Japanese Patent Application No. 59-8535 (Japanese Unexamined Patent Publication No. 60-153202). Among these inorganic fillers, those in powder form preferably have a diameter of 30 microns or less (preferably 10 microns or less). In addition, fibrous materials have a diameter of 1 to 50 mm.
0 micron (preferably 1 to 300 micron), and the width is 0.1 to 6 mm (preferably 0.1 to 5 mm).
Preferably. Furthermore, it is preferable that the diameter of the flat plate is 30 microns or less (preferably 10 microns or less). Among these inorganic fillers, flat (flake) and powdered fillers are particularly preferred. Suitable inorganic fillers include talc, mica, silica, glass fiber, graphite, and the like.

The composition ratio of component (B), that is, the modified propylene polymer, in the composition of the present invention is 5.0 to 50 p%.
．． 0 to 40% by weight is preferred, especially 7.0 to 40% by weight
is preferred. If the composition ratio of the modified propylene polymer in the composition is less than 5.0% and 9%, the resulting composition will not have good adhesion to polyurethane, and even if it is blended at 50% by weight. However, depending on the amount used, not only is it not possible to achieve the same effect of improving adhesion and weather resistance 11I, but the mechanical strength of the resulting composition tends to decrease.

The composition ratio of the component (C), that is, the amorphous ethylene-propylene copolymer blended in the composition of the present invention is 3 to 35%, preferably 3 to 30%, particularly preferably 5 to 35%.
30% of senior ministers. If the composition ratio of component (C) is less than 3% by weight, the impact resistance will not be sufficiently improved, and if it exceeds 35% by weight, the rigidity of the composition will decrease and the composition will be less than 100%, which will cause flow marks during molding. There is.

The composition ratio of component (B) to the total amount of components (A> and (B)) in the composition of the present invention is 5 to 90% by weight, preferably 5 to 60% by weight. If it is less than 90% by weight, the adhesion with the urethane paint will not be sufficiently improved, and if it exceeds 90% by weight, the stiffness and heat resistance of the composition will decrease, and the characteristics of the propylene composition will tend to be impaired.

In addition, the composition 'N11 of component (B) (2> relative to the total amount of components (8) and (C) in the composition of the present invention is 0.
．． 01-10% by weight, preferably 0.02-10% by weight
It is. If this proportion is less than 0.1% by weight, the adhesion of the composition to the urethane paint will not be sufficiently improved;
Even if it exceeds this, adhesion and weather resistance will not improve at the same time, and on the contrary, rigidity, heat resistance, etc. will tend to decrease, which is not preferable.

In the second aspect of the present invention, the above-mentioned component (A),
In addition to (B) and (C), component (r)) (i.e., high-density ethylene polymer) and component (IK) (i.e., inorganic filler) are blended.

The composition ratio of component (D) blended into the composition of the present invention is 3 to 20% by weight, preferably 3 to 15% by weight. If this proportion is less than 3% by weight, the improvement in gloss and impact resistance will be insufficient, and if it exceeds 20% by weight, heat resistance will deteriorate and the characteristics of the propylene composition will tend to be impaired.

Furthermore, the composition ratio of component (E) blended into the composition of the present invention is 3 to 35% by weight, preferably 3 to 30% by weight. If this proportion is 3% by weight, the improvement in the elasticity is insufficient, and if it exceeds 35% by weight, the impact resistance tends to decrease and cause flow marks and sill permeation.

In addition, in the composition of the present invention containing components (D) and (E), component (A>component (B) relative to the total amount of components (B) and component (A) relative to the total amount d of components (A) and (B); (B)(
The composition ratios of 2) are 5-90% and 0.0%, respectively. Old content is ~10% by weight. If the ratio of each of components (B) and (B) (2) to components (A) and (B) is too small, the adhesion of the composition to the urethane paint will not be sufficiently improved, while if it is too large, the rigidity and Heat resistance tends to decrease.

In order to produce the composition of the present invention, the components (A), (B
) and (C) and the above (A) to (E) are mixed uniformly by applying a mixing method practiced in the field of ordinary olefin polymers so that the composition ratios are within the above range. Just mix.

At this time, all the composition components may be mixed at the same time, or some of the composition components may be mixed in advance to produce a so-called master hatch, and this master hatch and the remaining composition components may be mixed. In this case, stabilizers against heat, oxygen or ultraviolet rays, metal deterioration inhibitors, plasticizers, flame retardants, hot water agents, fillers, colorants, and antistatic agents that are generally blended (added) to olefin polymers. Additives such as electrical property improvers may also be added depending on the purpose of use of the composition, as long as the physical properties of the composition do not essentially change by 10%.

The composition obtained in this way is usually molded into pellets, and manufactured into the desired molded product by injection molding, extrusion molding, or other molding methods commonly used in the field of thermoplastic resins. be done.

Whether the composition is melt-kneaded or molded during production, the temperature is higher than the melting point of the polymer used, but at a temperature that does not cause thermal decomposition. For these reasons, the temperature is generally 180 to 300°C (preferably 190 to 300°C).
250°C).

Generally, olefin polymers have extremely poor adhesion with polyurethane, so when applying polyurethane paint to molded products of olefin polymers or their compositions, a roughening primer is applied and dried, and then polyurethane paint is applied. I have to throw it. However, since the propylene polymer composition of the present invention has poor adhesion with polyurethane, polyurethane can be applied directly to the surface of the molded product without applying a primer to the surface of the molded product ( Using a primer will improve adhesion.)
.

] The present invention will be explained in more detail with reference to examples below, but the technical scope of the present invention will be explained in more detail by way of examples. Needless to say, the present invention is not limited to this example.

Note that physical property measurements in Examples and Comparative Examples were carried out as follows.

(i) Flexural modulus was measured according to ASTM D790.

(11) Izot impact strength was measured according to A37M port 256.

(iii) Paint film adhesion strength was measured using a flat plate test piece (thickness 2 mm,
130 x 130 mm) was placed in the atmosphere of 1.1.1-) lychloroethane for 30 seconds and thoroughly dried,
High urethane paint (Nippon B Chemical Ceremony, product name R2
57, Solisoto) was applied to a dry thickness of 20 to 30 microns. After leaving it to stand for about 15 minutes, a urethane paint (manufactured by Nippon P Chemical Co., Ltd., trade name R266, Wasokatsop) was applied so that the dry thickness was 30 to 40 microns, and dried at 90° C. for 30 minutes.

Then, it was allowed to stand in a constant room temperature (temperature 23°C, humidity 65%) for 48 hours. The obtained coated material (test piece) was cut into 10 mm width pieces, and a part of the coating film (approximately 10 mm) was cut from the resin part of the test piece.
) was forcibly peeled off, and then the remaining adhesion was tested using a tensile testing machine in the opposite direction (1
80 degrees) and measuring the peel strength.

(iv) In the second test, polyurethane paint II (Nippon P Chemical Co., Ltd., trade name R255, Metallic Red) was used instead of the high urethane paint used to measure the adhesion strength of the paint film. Apply in the same manner as
Treatments such as drying were performed. On the coating surface of the obtained test piece, 100 squares were cut at 1 mm intervals, and cellophane tape was completely adhered to the squares H using finger pressure. This cellophane tape was suddenly peeled off at an angle of 45 degrees. This operation was repeated twice to determine the percentage of the remaining coating film.

(v) For the weather resistance test, the flat test piece was
The sample was cut into 2 mm pieces and irradiated using a Sunshine Weatherometer (manufactured by Suga Test Instruments) at a black panel temperature of 83°C and rainfall conditions of 12 minutes/60 minutes, and was taken out at each irradiation time to observe changes in the appearance of the sample. observe,
The results are shown below.

◎: No change O: Slightly occurring chalking △: Cracking occurring ×: Severely cracking (vi) For the gloss test, the above-mentioned flat plate specimen was rated according to JIS K 7.
Measured according to 150.

The modified 7'o helene polymer, ethylene-propylene copolymer, stabilizer against heat, oxygen or ultraviolet rays, and other compositions used in the Examples and Comparative Examples, as well as their physical properties and manufacturing methods, are shown below. .

Kawa 71 Doy-14 Thread - Heavy Life Spirit ■ PP (A) Ethylene-propylene broth copolymer (ethylene content 8.8% by weight) with MFR July 5g / 10 minutes ■
PP(B) Ethylene-containing I'pyl non-block copolymer (ethylene content 7,5%) with MFR 30g/10min■
PP (C) Ethylene-propylene broth copolymer with an MFR of 1.5 g/10 minutes (ethylene content: 110.1% by weight) ■ PP (4)) Ethylene-propylene broth copolymer with an MFR of 100 g/10 minutes Copolymer (ethylene content 8.5% commercially) ■ PP (E) Propylene homopolymer with a VFR of 10 g / 10 minutes ■ PP (F) Ethylene-propylene random with an ethylene content of 3.1ii1% Copolymer use 4!2-boon-mono-mono'1 (Polymerization - As a biomodified propylene homopolymer, 85 parts by weight of a propylene homopolymer with an MFR of 0.5 g/10 minutes and Mooney viscosity (M L l+4.100°C) is 20 parts by weight of amorphous ethylene-propylene copolymer, 30 parts by weight of 2-hydroxyethyl methacrylate and 0.7 parts by weight of 2,2'-bis(tertiary). (butylperoxyisopropyl) Hensen was pre-blended for 5 minutes using a Henschel mixer.The resulting mixture was transferred to an extruder with a vent (i.
200° C.) (hereinafter referred to as modified PPJ) was used.

3)% constant ethylene-propylene copolymerization 44 As an amorphous ethylene-propylene copolymer, Mooney viscosity (
ML+ 4 (100° C.)] Amorphous ethylene-propylene copolymer Propylene content: 27% by weight, hereinafter referred to as EPR).

AQ - High density ethylene yarn 1 test - As a high density ethylene polymer, the density is 0.945g
/c-copolymer of ethylene-butene-1 (MF
R(1) 0.7 g/10 min, hereinafter referred to as HD P E (
A) and an ethylene homopolymer (MFR (1) 20 g/10 min, hereinafter referred to as HDPR (B)) having a density of 0.960 g/cl were used.

5) Inorganic fillers Inorganic fillers include talc with an average particle size of 2.0 microns, calcium carbonate (CaCO3) with an average particle size of 2.0 microns, and average particle size of 7.0 microns. Wollastonite was used.

6) Stabilizer Various stabilizers include bis(2,2,6,6-tetramethyl-4-piperidine sebacate (hereinafter referred to as stabilizer (1)), 2(3-tertiary-butyl- 5-methyl-2-hydroxyphenyl-5-chlorobenzotriazole (hereinafter referred to as stabilizer (2)) and tetra[methylene-3
-(3,5-ditertiary-phthyl-4-hydroxyphenyl)propionate comethane (hereinafter referred to as stabilizer (3)) was used.

Examples 1 to 11 and Comparative Examples 1 to 3 Propylene polymers, modified propylene polymers, and amorphous ethylene polymers whose respective blending amounts are shown in Table 1
The propylene random copolymer and stabilizer were mixed in a super mixer for 5 minutes.

The resulting mixtures were kneaded using a vented twin-screw extruder (cylinder temperature 180-200°C, diameter 30+ nm) to produce pellets (compositions).
A flat plate (thickness 2 mm, 13
0 x 130 mm), a specimen for measuring the flexural modulus of elasticity, and a specimen for measuring the Izod impact strength. The flexural modulus and Izod impact strength (temperature 2
3°C), weather resistance test, coating film adhesion strength, and cross-cut test. The results are shown in Table 2.

From the results of the following two examples and comparative examples, it is clear that the propylene polymer composition obtained by the present invention has a high mechanical strength (
Not only is the flexural modulus and impact resistance low,
It is clear that the processability is good and the adhesion to polyurethane is also excellent. Furthermore, it is clear that the most characteristic effect is that by adding stabilizers against heat, oxygen, and ultraviolet rays, an effect that can be called a synergistic effect is exerted.

Examples 12 to 19 and Comparative Examples 4 to 6 Propylene polymer (PP resin), modified propylene polymer (modified PP), amorphous ethylene-propylene random whose respective blending amounts are shown in Table 3 The copolymer (F,PR), high density ethylene polymer (HDPE), inorganic filler and stabilizer were mixed for 5 minutes using a supermixer. Each of the resulting mixtures was kneaded using a twin-screw extruder with a hent (cylinder temperature 180-200°C, (pre-30 mm)) to produce pellets (compositions). Each pellet was injection molded into 5 oz. A flat plate (thickness: 2 mm, 130 x 130 mm), a specimen for measuring the flexural modulus of elasticity, and a specimen for measuring the Izod impact strength were manufactured using a machine.The flexural modulus and Izod impact strength of each specimen obtained were (Temperature: 23°C), weather resistance test and coating film adhesion strength measurement were conducted.The results are shown in Table 4.

From the results of the following Examples and Comparative Examples, it is clear that the propylene polymer composition obtained by the present invention has a high mechanical strength (
Not only is the flexural modulus and impact resistance low,
It is clear that the processability is good and that the adhesion to polyurethane is poor. Furthermore, it is clear that the most characteristic effect is that by adding stabilizers against heat, oxygen, and ultraviolet rays, an effect that can be called a synergistic tjJ+ effect is exerted.

(Hereinafter, blank space) Moxibustion Soku-9-Xianguo1 The propylene polymer composition obtained by the present invention is as follows:
It exhibits the following effects compared to conventional propylene polymer compositions.

(1) Workability and moldability are the same or better.

(2) Weather resistance is good due to the synergistic effect described above.

(3) Adhesion with polyurethane paint is poor, and by applying polyurethane paint to the surface, the step of undercoating the primer can be omitted.

(4) Generally practiced activation treatment methods (for example,
By applying corona discharge treatment, plasma treatment, ultraviolet treatment) to the surface of the molded product, it is possible to achieve a satisfactory level of adhesion with the polyurethane paint.

(5) The propylene polymer composition of the present invention can be used in a wide variety of ways to exhibit the above effects. Typical applications include exterior parts such as automobile bumpers and bumper corners, interior parts such as door liners, and motorcycle parts such as fenders.

Claims (1)

[Scope of Claims] 1. (A) Propylene polymer, (B) (1) Propylene polymer or mixture of propylene polymer and ethylene-propylene copolymer rubber 1
00 parts by weight with (2) 0.1 to 50 parts by weight of an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group and (3) 0.01 to 20 parts by weight of an organic peroxide. Modified propylene polymer obtained by the treatment, and (C) Mooney viscosity [ML_l_+_4 (100°C)]
is 20 to 100, and the propylene content is 20
~50% by weight of an amorphous ethylene-propylene copolymer, and the component (B
) and (C) are 5.0 to 50% by weight and 3 to 35% by weight, respectively, and the composition ratio of component (B) to the total amount of components (A) and (B) is 5 to 90% by weight. weight%
A propylene polymer composition in which the composition ratio of component (B) (2) to the total amount of components (A), (B) and (C) is 0.1 to 10% by weight. 2. (A) propylene polymer; (B) 100 parts by weight of a mixture of (1) propylene polymer or propylene homopolymer and ethylene-propylene copolymer rubber; A modified propylene polymer obtained by treatment with 0.1 to 50 parts by weight of an organic compound having a saturated bond and containing a hydroxyl group and (3) 0.01 to 20 parts by weight of an organic peroxide, and ( C) Mooney viscosity [ML_l_+_4 (100°C)]
is 20 to 100, and the propylene content is 20
~50% by weight of an amorphous ethylene-propylene copolymer, (D) a high-density ethylene polymer having a density of 0.935 g/cm^3 or more, and (E) an inorganic filler, Component (B) in the composition
, (C), (D) and (E), respectively,
5 to 50% by weight, 3 to 35% by weight, 3 to 20% by weight, and 3 to 35% by weight, and the ratio of component (B) to the total amount of components (A) and (B) is 5 to 90% by weight. % of component (B-2) relative to the total amount of components (A) and (B).
) in a proportion of 0.1 to 10% by weight.