JPH0762096B2 - Propylene polymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a propylene-based polymer composition having excellent adhesion with a chloroprene-based two-liquid mixed type adhesive without using a primer. More specifically, the propylene-based polymer composition not only has excellent adhesion to a chloroprene-based two-liquid mixed type adhesive without using a primer, but also has good mechanical properties such as rigidity and impact resistance. Regarding things.

[Prior Art] As is well known, propylene-based polymers not only have excellent moldability, but also have good properties such as mechanical properties, heat resistance, solvent resistance, oil resistance, and chemical resistance. It is widely manufactured industrially and is used in various fields as parts for automobiles, electric appliances, electronic devices, and daily necessities. However, not only does it have no polar group in the molecule (so-called non-polar), but its solubility in most organic solvents is extremely low, and therefore the adhesion to various adhesives (adhesives) is very poor. From these things, there are problems in various points. With respect to these problems, a door lining which is a part of an automobile interior material will be described as an example.

The door lining is usually made of PVC leather, and this PVC leather is made of laminated polypropylene foam, polyethylene foam, polyurethane foam, etc. It cannot be used, and it is bonded to a polypropylene resin board containing acrylonitrile-butadiene-styrene terpolymer resin (ABS resin) as a base material or a filler such as wood powder to increase rigidity as a lining material. It is used by interposing an agent and adhering it.

However, in recent years, in consideration of weight reduction and cost reduction of automobiles, inexpensive polypropylene polypropylene resin (propylene-based polymer), which has good molding processability, has been used in place of ABS resin and filler-containing polypropylene resin. It is becoming popular.

However, as described above, the propylene polymer is a chemically extremely inactive polymer substance because it does not have a polar group in the molecule, and therefore, when it is adhered to vinyl chloride leather,
The molded product (door liner substrate) is undercoated with a primer capable of adhering to a propylene-based polymer in advance, or after pretreatment such as plasma treatment, corona discharge treatment, and ultraviolet irradiation treatment is applied, and then an adhesive is applied, and a salt is applied. The reality is that the blazer is attached. Therefore, the production process takes time and the cost is high.

When manufacturing other automobile interior materials such as instrument panels, pillars, ceiling materials, armrests, and other linings, the same problem as above when using propylene-based polymer and adhering PVC leather There is.

[Problems to be Solved by the Invention] From the above, the present invention does not have these problems (deficiencies), that is, it does not require a pretreatment that requires a complicated operation, and the adhesiveness to the adhesive is high. Not only good, but also excellent in moldability, the propylene-based polymer has the same mechanical properties (for example, impact resistance and rigidity), and the appearance of the molded product is also excellent. To obtain a polymer composition.

[Means for Solving Problems] According to the present invention, these problems are as follows: (A) Melt flow index [measured under conditions of 14 according to JIS K7210, hereinafter referred to as "MFR (1)" 〕But
0.01 to 100 g / min propylene-based polymer, (B) unsaturated carboxylic acid ester copolymerization ratio of 5.0
To 50% by weight of ethylene-unsaturated carboxylic acid ester-based copolymer and (C) (1) 100 parts by weight of propylene-based polymer (2) "having at least one unsaturated bond in the molecule,
And 0.01 to 10 parts by weight of an organic compound containing a hydroxyl group (hereinafter referred to as "hydroxyl compound") and (3) 0.01 to 10 parts by weight of a modified propylene-based polymer [ Hereinafter referred to as "modified propylene-based polymer (1)"] or a composition comprising these and (D) a filler, which is a crystalline propylene-based polymer,
The ethylene-unsaturated carboxylic acid ester copolymer has a composition ratio of 5.0 to 30% by weight in the total amount of the polymer material comprising the ethylene-unsaturated carboxylic acid ester polymer and the modified propylene polymer (1). %, And the modified propylene polymer (1) is 5.0 to 40% by weight,
The crystalline propylene-based polymer is at least 45% by weight, and the unit derived from the unsaturated carboxylic acid ester in the polymer substance is 2.5 to 10% by weight, and the total amount of the polymer substance is 100 parts by weight. The composition ratio of the filler to the propylene-based polymer composition is at most 40 parts by weight,
Can be solved by. Hereinafter, the present invention will be specifically described.

(A) Crystalline propylene-based polymer The crystalline propylene-based polymer used in the present invention is a polymer containing propylene as a main component, and contains propylene homopolymer and propylene and ethylene and / or other α-olefins. Random and block copolymers are preferably used. The copolymerization ratio of ethylene and α-olefin in the random or block copolymer is at most 20% by weight as a total amount, preferably 18% by weight or less, particularly preferably 16% by weight or less. Also, other α
As the olefin, an α-olefin having 4 to 12 carbon atoms is desirable, and an α-olefin having 4 to 8 carbon atoms is particularly preferable. Suitable α-olefins include butene-
1, Heptene-1,4-methylpentene-1 and hexene-1.

The MFR (1) of the propylene-based polymer is 0.01 to 100 g / 10 minutes, preferably 0.01 to 80 g / 10 minutes, particularly 0.1 to 70 g.
It is preferably 10 minutes.

When a propylene-based polymer having an MFR (1) of less than 0.01 g / 10 minutes is used, the kneading property is not good. On the other hand, when a propylene-based polymer exceeding 100 g / 10 minutes is used, the composition has poor impact resistance.

(B) Ethylene-unsaturated carboxylic acid ester-based copolymer Further, the ethylene-unsaturated carboxylic acid ester-based copolymer used in the present invention is a copolymer of at least ethylene and an unsaturated carboxylic acid ester described later (first It also includes multi-component copolymers with three comonomers). The copolymerization ratio of the unsaturated carboxylic acid ester in the ethylene-unsaturated carboxylic acid ester copolymer is 5.0 to 50% by weight and 5.0 to 50% by weight.
40% by weight is preferred. Use of an ethylene-unsaturated carboxylic acid ester-based copolymer having an unsaturated carboxylic acid ester copolymerization ratio of less than 5.0% by weight is not preferable because the effect of modification is not satisfactory. On the other hand, when an ethylene-unsaturated carboxylic acid ester-based copolymer in which the copolymerization ratio of the unsaturated carboxylic acid ester exceeds 50% by weight is used, not only the physical properties of the composition are deteriorated but also delamination occurs. Therefore, it is not preferable. The melt flow index of the ethylene-unsaturated carboxylic acid ester-based copolymer [JI
According to S K7210, measured under condition 4, below "MFR
(2) ”] is generally 0.5 to 300 g / 10 minutes,
0.5 to 200 g / 10 minutes is preferable, and 0.5 to 150 g / 10 minutes is particularly preferable. If an ethylene-unsaturated carboxylic acid ester-based copolymer having an MFR (2) of less than 0.5 g / 10 minutes is used, the kneading property is not good. On the other hand, ethylene exceeding 300 g / 10 min
If an unsaturated carboxylic acid ester-based copolymer is used, the resulting composition has poor mechanical strength.

The unsaturated carboxylic acid ester usually has 4 to 40 carbon atoms, and particularly preferably 4 to 20 carbon atoms. Representative examples of the unsaturated carboxylic acid ester include methyl (meth) acrylate and ethyl (meth) acrylate. And alkoxyalkyl (meth) acrylate. The alkoxy group of the alkoxyalkyl (meth) acrylate has 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms), and the alkyl group has 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms).
Individual) are preferred. Representative examples of suitable alkoxyalkyl (meth) acrylates include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate.

Further, as the third comonomer, those having at most 20 (preferably 4 to 16) carbon atoms are desirable. Representative examples thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl piperate and the like. The copolymerization ratio of the third comonomer is usually at most 10% by weight, preferably 5.0% by weight or less.

(C) Modified propylene-based polymer (1) The modified propylene-based polymer (1) of the present invention is obtained by treating a propylene-based polymer described below with a hydroxyl-based compound and an organic peroxide. The manufacturing method is described in detail in JP-A-58-154732.

(1) Propylene-based polymer The propylene-based polymer includes a propylene homopolymer, a block copolymer of ethylene and propylene, and a block copolymer of propylene and a large number of α-olefins having at most 12 carbon atoms. An example is a combination (the copolymerization ratio of α-olefin is at most 20% by weight). The MFR (1) of this propylene-based polymer is usually 0.01 to 100 g / 10 minutes from the viewpoint of moldability, mechanical properties of the resulting composition, and the like.
It is preferably from 1 to 50 g / 10 minutes, particularly preferably from 0.02 to 50 g / 10 minutes.

(2) Hydroxyl Compound Further, the hydroxyl compound is a compound having at least one unsaturated bond (double bond, triple bond) and containing a hydroxyl group. Typical examples thereof include an alcohol having a double bond, an alcohol having a triple bond, an ester of a monovalent or divalent unsaturated carboxylic acid and an unsubstituted dihydric alcohol, an unsaturated carboxylic acid and an unsubstituted trivalent alcohol. Examples thereof include esters with polyhydric alcohols, esters with unsubstituted tetrahydric alcohols, and esters with unsubstituted pentavalent or higher alcohols.

(3) Organic peroxide Further, the organic peroxide is generally used as an initiator in radical polymerization and a cross-linking agent of a polymer, and one having a half-life of 1 minute or more of 100 ° C. or more is preferable, and A temperature of 130 ° C or higher is suitable. Above temperature is 100
If the temperature is lower than 0 ° C, not only is it difficult to handle, but also the effect of use is not so noticeable, which is not desirable.

(4) Mixing ratio In producing the modified propylene polymer (1) of the present invention, the mixing ratio of the hydroxyl compound to 100 parts by weight of the propylene polymer is 0.01 to 10 parts by weight, and
05 to 10 parts by weight is preferable, and 0.1 to 7.0 parts by weight is particularly preferable. If the mixing ratio of the hydroxyl compound to the propylene polymer of 100 parts by weight is 0.01 parts by weight or less, the effect of improving the adhesion is insufficient. On the other hand, even if it is used in an amount of 10 parts by weight or more, the effect of improving the adhesiveness depending on the amount used is not recognized, and rather the original properties of the propylene polymer are impaired, which is not preferable.

Further, the mixing ratio of the organic peroxide to 100 parts by weight of the propylene-based polymer is 0.01 to 10 parts by weight, 0.05 to 7.0
Parts by weight are preferable, and 0.1 to 5.0 parts by weight is particularly preferable. If the mixing ratio of the organic peroxide to 100 parts by weight of the propylene-based polymer is less than 0.01 parts by weight, not only the effect of improving the adhesiveness is low, but also the durability of the adhesive strength of the mixture is reduced. On the other hand, if the amount exceeds 10 parts by weight, the original excellent mechanical properties of the polymer are deteriorated, and therefore it is not desirable in any case.

(5) Method for producing modified propylene polymer (1) To produce the modified propylene polymer (1) of the present invention, the above propylene polymer, hydroxyl compound and organic peroxide are mixed as above. It can be produced by treating (heating) at a ratio. At this time, the propylene-based polymer, the hydroxy-based compound and the organic peroxide may be treated while being mixed, but these may be mixed in advance by dry blending, or at a relatively low temperature (a temperature at which the hydroxyl-based compound does not react). Knead with
It is obtained by heating the resulting mixture as described below.

If the treatment is carried out at a high temperature, the propylene-based polymer may deteriorate. However, it must be carried out at a temperature at which the organic peroxide used for graft-polymerizing the propylene-based polymer and the hydroxyl-based compound used decomposes. From the above, this treatment is generally 180-300 depending on the type of organic peroxide used.
It is carried out at ℃ (preferably 200 to 280 ℃).

The general formulas and typical examples of the hydroxyl compounds and organic peroxides, and the mixing method and treatment method are described in detail in JP-A-58-154732.

In order to produce the propylene-based polymer composition of the present invention, the above crystalline propylene-based polymer, ethylene-unsaturated carboxylic acid ester-based copolymer and modified propylene-based polymer (1) are uniformly mixed at the composition ratios described below. However, the rigidity of the composition can be improved by further blending these polymeric substances with the below-mentioned filler. In addition, the impact resistance of the composition can be improved by incorporating an ethylene polymer. Furthermore, the impact resistance of the composition can be improved by blending the ethylene-propylene polymer. In addition, “a modified propylene polymer obtained by treating a propylene polymer with an α, β-unsaturated carboxylic acid and / or an anhydride thereof and an organic peroxide” [hereinafter, referred to as “modified propylene polymer (2 It is possible to improve the rigidity of the composition.

(D) Filler The filler used in the present invention is generally widely used in the fields of synthetic resins and rubber. Among these fillers, the inorganic filler is preferably an inorganic compound that does not react with oxygen and water and does not decompose during kneading and molding. As the inorganic filler, aluminum, copper, iron, lead, nickel,
Oxides of metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony and titanium, their hydrates (hydroxides), compounds such as sulfates, carbonates and silicates, and compounds of these compounds. It is roughly classified into salts and mixtures thereof. Typical examples of the inorganic filler are described in Japanese Patent Application No. 59-8535. Of these inorganic fillers, powdery ones having a diameter of 30 μm or less (preferably 10 μm or less) are preferable. For fibrous materials, the diameter is 1 to 500 μm (preferably 1 to 3 μm).
00 micron) with a length of 0.1-6 mm (preferably 0.1-5)
mm) is preferable. Furthermore, the flat plate has a diameter of 30.
Those having a size of micron or less (preferably 10 microns or less) are preferable. Of these inorganic fillers, flat plate-shaped (flake-shaped) and powdered ones are particularly preferable. Suitable inorganic fillers include talc, mica, silica, glass fibers, graphite and the like.

Examples of the organic filler include wood powder, organic fiber, straw, chaff, peanut mustard and the like.

The wood powder is usually 12 mesh pass, and particularly preferably has an average particle size of 45 mesh pass or less. In addition,
The type of wood flour is not particularly limited.

The organic fibers are animal fibers such as wool, vegetable fibers such as cotton, jute and pulp, and synthetic fibers such as vinylon fibers, polyester fibers, nylon fibers and acrylic fibers that are commonly used. The length and average diameter of the organic fibers differ depending on the use of the polypropylene composition to be finally obtained, mixing conditions, etc., and therefore cannot be unconditionally specified, but generally the average diameter range is 3 to 500 microns. It is suitable that the average length is 0.1 to 6 mm.

In addition, straw is used after being cut so as to have the same average diameter and length as the organic fiber from the viewpoint of mixing properties.

In addition, chaff and peanuts are crushed and used like the above-mentioned wood powder.

(E) Ethylene-based polymer The density of the ethylene-based polymer that can be mixed with the composition of the present invention is 0.900 g / cm ³ or more, and
900 to 0.970 g / cm ³ is preferable, especially 0.910 to 0.970 g
It is preferably / cm ³ .

Examples of the ethylene-based polymer include ethylene homopolymers and random or block copolymers of ethylene and α-olefin. Generally, the α-olefin having 3 to 12 carbon atoms (preferably 3 to 8 carbon atoms) is preferable. Typical examples of the α-olefin include propylene, butene-1, hexene-1, octene-1 and 4
-Methylpentene-1. The copolymerization ratio of this α-olefin is generally at most 20% by weight,
Above all, 10% by weight or less is desirable.

The MFR (2) of the ethylene-based polymer is at least 0.1 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes, and particularly 0.5.
It is preferably about 50 g / 10 minutes. If the MFR (2) used is less than 0.1 g / 10 minutes, the dispersibility is poor, and it is difficult to obtain a uniform composition. Even if a uniform composition is obtained, the adhesion is improved. It is slight and the appearance of the formed product is not good.

(F) Ethylene-propylene rubber Further, the ethylene-propylene rubber used that can be mixed with the composition of the present invention is an ethylene-propylene copolymer rubber obtained by copolymerizing ethylene and propylene, and ethylene. And propylene as the main components, and a linear or branched chain containing two double bonds at the end such as 1,4-pentadiene, 1,5-hexadiene and 3,3-dimethyl-1,5-hexadiene. Linear or branched diolefins containing only one double bond at the end, such as diolefins, 1,4-hexadiene and 6-methyl-1,5-heptadiene, or bicyclo [2,2,1] -heptene-2 and Multi-component copolymer obtained by copolymerizing a small amount (generally 10% by weight or less) of a monomer such as a cyclic diene hydrocarbon such as its derivative. It is a non. The weight ratio of ethylene monomer unit: propylene monomer unit of these copolymer rubbers and multicomponent copolymer rubbers is usually preferably 20:80 to 80:20, and more preferably 20:80.
To 75:25 are preferred. These ethylene-propylene rubbers are produced by copolymerization or multi-copolymerization of ethylene, a catalyst system ethylene obtained from a transition metal compound and an organic aluminum compound, or propylene, or ethylene, propylene and the above-mentioned monomer.

The ethylene-propylene rubber of the present invention has a Mooney viscosity [ML _{1 + 4} (100 ° C.)] of 10 to 140, preferably 15 to 120, and more preferably 30 to 110. If an ethylene-propylene rubber having a Mooney viscosity of less than 10 is used, the moldability is improved, but not only the impact improving effect is low, but layer delamination may occur during gate cutting of the molded product. , It may cause trouble. On the other hand, if it exceeds 140, not only the dispersion at the time of kneading becomes difficult, but even if a uniform composition is obtained, the markedness of flow marks, weld lines, etc. on the surface of the molded product is severe. As a result, a product having a good appearance cannot be obtained.

(G) Modified propylene-based polymer (2) The modified propylene-based polymer (2) that can be mixed with the composition of the present invention is a propylene-based polymer treated with a carboxylic acid-based compound and an organic peroxide. Can be obtained by

The propylene polymer and organic peroxide used for producing the modified propylene polymer (2) are the same as those used for producing the modified propylene polymer (1). Can be used.

(1) Carboxylic Acid Compound The carboxylic acid compound used for producing the modified propylene polymer (2) of the present invention is an α, β-unsaturated carboxylic acid and its anhydride. The number of carbon atoms of the unsaturated carboxylic acid compound is usually at most 30, especially 25
Less than or equal to one is desirable. The unsaturated carboxylic acid compounds are roughly classified into monobasic unsaturated carboxylic acids, dibasic unsaturated carboxylic acids and their anhydrides. Representative examples of the monobasic unsaturated carboxylic acid include acrylic acid and methacrylic acid. Further, as typical examples of the dibasic unsaturated carboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and 3,6-endomethylene-1,2,3,6
-Detrahydro-cis-phthalic acid. Also,
An anhydride is an anhydride of the dibasic unsaturated carboxylic acid,
Maleic anhydride, citraconic anhydride, citraconic anhydride and 3,6-endomethylene-1,2,3,6-tetrahydro-
An example is cis-phthalic anhydride.

(2) Usage ratio In producing the modified olefin polymer (2),
The proportion of the carboxylic acid compound used relative to 100 parts by weight of the propylene polymer is 0.01 to 10 parts by weight, preferably 0.02 to 1 part by weight, and particularly preferably 0.02 to 7.0 parts by weight. 1
If the amount of the carboxylic acid compound used is less than 0.01 parts by weight with respect to 00 parts by weight of the propylene polymer, the effect of improving rigidity is insufficient. On the other hand, even if it is used in an amount of more than 10 parts by weight, the effect of improving rigidity is not observed depending on the amount used.

Further, the mixing ratio of the organic peroxide is 0.01 to 10 parts by weight for the same reason as that of the modified propylene polymer (1), and
01 to 7.0 parts by weight is preferable, and 0.02 to 5.0 parts by weight is particularly preferable.

(3) Method for producing modified propylene-based polymer (2) The modified propylene-based polymer (2) of the present invention is a propylene-based polymer, a carboxylic acid-based compound, and It can be produced by treating (heating) the organic peroxide in the above mixing ratio. The heating temperature is the same as in the case of the modified propylene polymer (1).

(H) Composition ratio In the composition of the present invention, "a crystalline propylene-based polymer, an ethylene-carboxylic acid ester-based copolymer and a modified propylene-based polymer or these and an ethylene-based polymer, an ethylene-propylene-based rubber and a modified The composition ratio of the crystalline propylene-based polymer in the total amount of at least one polymer selected from the group consisting of the propylene-based polymer (2) (hereinafter referred to as “polymeric substance”) is 45% by weight or more. It is preferably 50% by weight or more.
When the composition ratio of the crystalline propylene-based polymer is less than 45% by weight, the mechanical strength of the obtained composition is not good.

The composition ratio of the modified propylene-based polymer (1) in the total amount of the polymer is 5.0 to 40% by weight, and 5.0 to 40% by weight.
30% by weight is preferable, and 5.0 to 30% by weight is particularly preferable. Composition ratio of modified propylene polymer is 5.0% by weight
If it is less than the range, the effect of improving the adhesiveness is poor. On the other hand, 40% by weight
If it exceeds the above range, it will become an economic problem.

Furthermore, the composition ratio of the ethylene-unsaturated carboxylic acid ester-based copolymer in the total amount of the polymer is 5.0 to 30.
% By weight, preferably 5.0-25% by weight, especially 10-25
Weight percent is preferred. When the composition ratio of the ethylene-unsaturated carboxylic acid ester copolymer is less than 5.0% by weight, the adhesiveness of the obtained composition with the adhesive is not good. Meanwhile, 30
If it exceeds the weight percentage, the mechanical strength (particularly rigidity) is poor.

When an ethylene-based polymer is blended, its composition ratio is at most 20% by weight, and particularly preferably 18% by weight or less, based on the total amount of the above polymers. If the composition ratio of the ethylene-based polymer in the total amount of the polymer exceeds 20% by weight, the adhesiveness of the resulting composition will decrease.

Further, when blending ethylene-propylene rubber,
Its composition ratio is at most 20 relative to the total amount of the polymer.
% By weight, particularly preferably 15% by weight or less. When the composition ratio of the ethylene-propylene copolymer rubber in the total amount of the polymer exceeds 20% by weight, the abrasion resistance of the obtained composition is good, but other mechanical properties (for example, rigidity) are not good.

When the ethylene-based polymer and the ethylene-propylene copolymer rubber are used in combination, the amount is preferably at most 30% by weight with respect to the total amount of the polymer.

When the modified propylene polymer (2) is blended,
The composition ratio is at most 100 parts by weight with respect to 100 parts by weight of the below-mentioned filler, preferably 10 to 80 parts by weight, and particularly preferably 15 to 75 parts by weight. Even if more than 100 parts by weight is blended with 100 parts by weight of the filler, the effect of improving the rigidity cannot be recognized depending on the amount used.

Further, the proportion of units derived from unsaturated carboxylic acid ester in these polymer substances is 2.5 to 10% by weight. When the proportion of the unit derived from the unsaturated carboxylic acid ester in the polymer substance is less than 2.5% by weight, the adhesiveness of the obtained composition is not good. On the other hand, if it exceeds 10% by weight, the mechanical strength (especially rigidity) of the composition is not good.

Further, the composition ratio of the filler to 100 parts by weight of the total amount of the polymer is 40 parts by weight at the most, preferably 0.5 to 40 parts by weight, and more preferably 1.0 to 35 parts by weight. The composition ratio of the filler is 4 with respect to 100 parts by weight of the total amount of polymer substances.
If it is blended in an amount of more than 0 parts by weight, not only the moldability is deteriorated but also the adhesiveness is lowered and the impact resistance is not good.

(J) Production of Composition To produce the composition of the present invention, the above-mentioned polymer substance or the polymer substance and the filler may be uniformly blended. At this time, if necessary, additives such as oxygen, light or heat stabilizers, flame retardants, processability improvers, lubricants, antistatic agents and pigments commonly used in olefin polymers are added. Of course, you can do that.

To obtain the composition, it may be dry blended using a mixer such as a tumbler, a ribbon blender and a Henschel mixer, or a batch type kneader (for example,
The kneading can be performed using a Banbury mixer) or a continuous kneading kneader (for example, an extruder), but the kneading can be continuously performed using the continuous mixer as described above. Further, by using these methods together (for example, after dry blending, kneading continuously), it is possible to mix more uniformly.

(K) Molding method The composition thus obtained is usually molded into pellets, and the desired molded article is molded by a molding method such as an injection molding method or an extrusion molding method that is generally performed in the field of each thermoplastic resin. Manufactured to.

Even when melt-kneading when producing the composition,
Even in the case of molding, the temperature is higher than the melting point of the polymer used, but it is a temperature at which no heat is applied. For these reasons, it is generally carried out at 180 to 280 ° C (preferably 200 to 260 ° C).

[Function] In the composition of the present invention, the grafted hydroxyl compound in the modified propylene polymer (1) gives a chemically active site rich in polar groups on the surface of the propylene polymer or a molded article thereof. As a result of the improved compatibility with the adhesive, it is considered that the effect of improving the adhesiveness can be obtained without using a primer. Furthermore, the modified propylene-based polymer (2) uniformly disperses in the composition and acts as an effect of improving the compatibility of the interface between the filler and the crystalline propylene-based polymer which is the main component. It is considered that the effect of improving the rigidity can be obtained.

[Examples and Comparative Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.

In Examples and Comparative Examples, the flexural modulus is ASTM
Measured according to D790, Izod impact strength is ASTM
Measured according to D256. The room temperature adhesiveness is a flat plate test piece prepared by injection molding (thickness 3 mm, 140 x 140 m
m, textured product) chloroprene-based two-liquid mixed type solvent type adhesive (Hitachi Chemical Polymer Co., Ltd., trade name Hypon XA32)
2-10) is sprayed, evenly applied to 100-150 g / m ² and dried at 80 ° C for 5 minutes, then preheated at 140 ° C for 3 minutes vinyl chloride resin (PVC) Of the sheet (which is laminated with propylene resin foam primer coated product) on the propylene resin foam surface, and using a heat press machine (50 ° C for flat test piece side, 150 ° C for PVC sheet side) ℃) Pressure is 1kg / cm
^It was crimped at ² for 30 seconds. Then, it was allowed to stand in a thermostatic chamber (temperature 23 ° C, relative humidity 65%) for 48 hours. 25 mm for the obtained test piece
After cutting to width and forcibly peeling the PVC sheet from the resin part of the test piece, the remaining adhesion part is 200m using a tensile tester.
It was determined by pulling in a reverse direction (180 degrees) to the PVC sheet at a speed of m / min and measuring the peel strength. further,
The heat-resistant adhesiveness was determined by leaving the test piece obtained by pressure bonding as described above for 300 hours in a thermostatic chamber adjusted to 80 ° C., pulling it at a temperature of 80 ° C. in the same manner as above, and measuring the peel strength. .

The crystalline propylene polymer, ethylene-unsaturated carboxylic acid ester copolymer, modified propylene polymer (1), ethylene polymer, ethylene-propylene rubber, modified used in Examples and Comparative Examples The physical properties of the propylene polymer (2) and the filler, the production method, and the like are shown below.

[(A) Crystalline propylene-based polymer] As a crystalline propylene-based polymer, MFR (1) is 10 g / 10
Of the ethylene-propylene block copolymer [hereinafter referred to as "PP
(A) ”], a propylene homopolymer having MFR (1) of 8.0 g / 10 minutes [hereinafter referred to as“ PP (B) ”] and MFR
(1) is 12 g / 10 minutes, and the ethylene copolymerization ratio is
A 2.0% by weight ethylene-propylene random copolymer [hereinafter referred to as "PP (C)"] was used.

[(B) Ethylene-unsaturated carboxylic acid ester-based copolymer] Further, as the ethylene-unsaturated carboxylic acid ester-based copolymer, MFR (2) is 45 g / 10 minutes, and the copolymerization ratio of methyl methacrylate is Is 35% by weight of ethylene-methacrylate copolymer [hereinafter referred to as "EMMA (a)"],
MFR (2) is 3.0 g / 10 minutes, and the copolymerization ratio of methyl methacrylate is 4.0 weight [hereinafter referred to as "EMMA (b)], and MFR (2) is 20 g. An ethylene-ethyl acrylate copolymer [hereinafter referred to as "EEA"] was used for 10 minutes and the copolymerization ratio of ethyl acrylate was 20% by weight.

[(C) Modified propylene-based polymer (1)] Further, as a modified propylene-based polymer (1), MFR
(1) is 0.05 g / 10 minutes and the ethylene copolymerization ratio is 18% by weight. 100 parts by weight of ethylene-propylene block copolymer, 4.0 parts by weight of 2-hydroxyethyl acrylate and 1.0 parts by weight of 2 2,2'-Bis (tertiary-butylperoxyisopropyl) benzene was previously dry blended for 5 minutes using a Henschel mixer. The obtained mixture was kneaded using an extruder with a vent (diameter 40 mm, cylinder temperature 160 to 200 ° C.) to prepare pellets [hereinafter, referred to as “modified PP (I)].

[(D) Ethylene Polymer] Further, MFR (2) is 1.0 g / 10 minutes and the density is 0.950 g.
/ cm ³ at a high density polyethylene [hereinafter referred to as "PE (1)"], MFR (2) is 7.1 g / 10 min, and a density 0.920g
/ cm ³ linear copolymer of ethylene and butene-1 [copolymerization ratio of butene-1 is 8.2% by weight, hereinafter "PE (2)
And a MFR (2) of 3.0 g / 10 minutes and a density of 0.920 g / cm ³ were used for high-pressure process low density polyethylene (hereinafter referred to as “PE (3)”).

[(E) Ethylene-Propylene Rubber] Further, as an ethylene-propylene rubber, an ethylene-propylene rubber having a Mooney viscosity [ML _{1 + 4} (100 ° C.)] of 60 and a propylene copolymerization ratio of 27% by weight. Propylene copolymer rubber [hereinafter referred to as "EPR"] and Mooney viscosity [ML
_{1 + 4} (100 ° C.)] is 36, the propylene copolymerization ratio is 36% by weight, and the ethylidene norbornene copolymerization ratio is 6.0% by weight.
Ethylidene norbornene terpolymer rubber [hereinafter referred to as "EPDM"
Is used].

[(F) Modified propylene-based polymer (2)] Further, as the modified propylene-based polymer (2), MFR
(1) was added to 100 parts by weight of propylene homopolymer of 0.6 g / 10 min.
0.70 part by weight of maleic anhydride and 0.4 part by weight of benzoyl peroxide were dry blended in advance for 5 minutes using a Henschel mixer. Pellets were manufactured by kneading the obtained mixture with an extruder (diameter 40 mm, cylinder temperature 180 to 230 ° C) [hereinafter referred to as "modified.
PP (II) ”] was used.

[(G) Filler] Further, as the filler, talc having an average particle size of 2.0 μm and an aspect ratio of 5.5, and an average particle size of 7.0 μm
And mica with an aspect ratio of 30 and wood flour (45
Mesh pass) and jute (average diameter 20 μm 3 average fiber length 3 mm) were used.

Examples 1 to 13 and Comparative Examples 1 to 9 Crystalline propylene-based polymers (hereinafter referred to as "PP"), whose blending amounts and types are shown in Table 1, ethylene-unsaturated carboxylic acid ester-based copolymers Polymer [hereinafter referred to as "copolymer"], ethylene-based polymer [hereinafter referred to as "PE"], ethylene-propylene rubber [hereinafter referred to as "rubber"], filler, and compounding amount in Table 1. The modified propylene polymer (1) [modified PP (I)] and the modified propylene polymer (2) [modified PP (II)] shown were mixed for 5 minutes using a super mixer. The resulting mixture was mixed with a vented twin-screw extruder (cylinder temperature 180-200
Pellets (composition) were produced while kneading at 0 ° C and a diameter of 30 mm). Each pellet was manufactured into a flat plate, a sample for flexural modulus measurement, and a sample for Izod impact strength measurement by using a 5 ounce injection molding machine. The Izod impact strength (measurement temperature: 23 ° C.) and flexural modulus of each of the obtained test pieces were measured, and room temperature adhesiveness and heat resistant adhesiveness were measured. The results are shown in Table 2.

In the columns of "room temperature adhesiveness" and "heat resistant adhesiveness" in Table 2, "material destruction" means that the propylene-based resin foam is destroyed.

[Effect of the Invention] The propylene polymer composition of the present invention exhibits the following effects (features).

(1) It has excellent mechanical strength such as rigidity (flexural modulus) and impact resistance.

(2) Good workability and moldability.

(3) The appearance of the molded product is excellent.

(4) Adhesiveness with the adhesive is good, and not only the pretreatment (primer coating, plasma treatment, corona discharge treatment, ultraviolet irradiation) step of the adhesive surface can be omitted, but also the adhesive trouble is reduced. Is expected, and the adhesiveness after heat aging is excellent.

The propylene-based polymer composition of the present invention can be used in various fields in order to exert the above effects. Typical examples are automotive parts such as door liners, instrument panels, and various linings.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location C08L 23:08 23:26 51:06) (72) Inventor Hide Umemura Chidori Kawasaki-ku, Kawasaki-shi, Kanagawa Machi 3-2 Kawasaki Plastic Research Laboratory, Showa Denko KK (56) Reference JP-A-63-254148 (JP, A) JP-A-59-184247 (JP, A) JP-A-62-209150 (JP, A)

Claims (1)

[Claims] 1. A melt flow index of (A) is 0.01 to.
100 g / 10 minutes of crystalline propylene polymer, (B) unsaturated carboxylic acid ester copolymerization ratio of 5.0 to 5
0% by weight of ethylene-unsaturated carboxylic acid ester-based copolymer and (C) 100 parts by weight of (1) propylene-based copolymer (2) having at least one unsaturated bond in the molecule and having a hydroxyl group A modified propylene polymer obtained by treating 0.01 to 10 parts by weight of an organic compound containing (3) and 0.01 to 10 parts by weight of an organic peroxide, or a composition comprising these and (D) a filler. Yes, crystalline propylene-based polymer,
The composition ratio in the total amount of the polymer material composed of the ethylene unsaturated carboxylic acid ester copolymer and the modified propylene polymer is 5.0 to 30% by weight of the ethylene-unsaturated carboxylic acid ester copolymer. , And the modified propylene-based polymer is 5.0 to 40% by weight, but the crystalline propylene-based polymer is at least 45% by weight, and the unit derived from the unsaturated carboxylic acid ester in these polymer substances is 2.5. A propylene-based polymer composition, wherein the composition ratio of the filler is at most 40 parts by weight with respect to 100 parts by weight of the total amount of the polymer.