JP2804493B2 - Propylene-based polymer composition, molded product thereof, and bonding method - Google Patents

Description

The present invention relates to a method for adhering a molded product of a propylene-based polymer composition to a chlorinated polypropylene-based two-liquid mixed type adhesive without using a primer. More in detail,
Good adhesion (adhesiveness) without using a primer, chlorinated polypropylene-based two-liquid type adhesive and rigidity,
The present invention relates to a method for adhering a propylene-based polymer composition having excellent mechanical properties such as impact resistance to a molded article.

[Conventional technology]

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 used 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, the door lining which is a part of the interior material of the automobile will be described as an example.

The door lining is usually made of PVC leather, and this PVC leather is laminated with polypropylene foam, polyethylene foam, polyurethane foam, etc.However, PVC leather has low rigidity, so it cannot be used as it is. In order to increase the rigidity as a lining material, acrylonitrile-butadiene-styrene terpolymer resin (ABS resin) molded products, hardboard press molded products, and polypropylene mixed with filler such as wood powder It is used by adhering it through a resin board with an adhesive.

However, in recent years, with the intention of reducing the weight and cost of automobiles, polypropylene resin (propylene polymer) that is inexpensive and has good moldability instead of ABS resin, hardboard and polypropylene resin containing wood flour Is being used.

[Problems to be Solved by the Invention]

However, as described above, the propylene-based polymer is a chemically extremely high-molecular substance because it does not have a polar group in the molecule. ) Is undercoated with a primer that can be adhered to a propylene-based polymer, or is pretreated with plasma treatment, corona discharge treatment, ultraviolet irradiation treatment, etc., and then an adhesive is applied to adhere vinyl chloride leather. It is a reality. 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.

From these, some of the present inventors do not have these drawbacks, that is, do not require a pretreatment that requires a complicated operation, and have good adhesion with a chloroprene-based two-liquid mixed type adhesive. The propylene-based polymer not only has excellent moldability but also has the same mechanical properties (for example, impact resistance and rigidity) that the propylene-based polymer has, and the appearance of the molded product is also excellent. As a result of various searches for the composition, a graft polymer obtained by graft-polymerizing a copolymer of ethylene and vinyl acetate on a propylene-based polymer and an organic compound having an unsaturated bond containing a hydroxyl group on a propylene-based polymer It was found that a composition obtained by mixing coalescing agents and fillers solves all of these problems, and has previously proposed (Japanese Patent Application No. 62-176022, the same).
62-183600, 62-190287, 62-203014, 62
-201852 and 62-231171). Therefore, the present invention has an object of establishing a bonding method that exhibits almost the same effect even for a two-liquid mixed type adhesive containing chlorinated polypropylene as a main component, which could not be solved in these inventions. It is what

[Means for solving the problem]

According to the present invention, these problems are encountered in adhering a molded article of a propylene-based polymer composition and a two-component mixed type adhesive containing chlorinated polypropylene as a main component. However, (A) it is substantially insoluble in xylene at a temperature of 30° C., and its melt index [measured according to JIS K7210 under conditions of 14, hereinafter referred to as “MI (1)”] is 0.01 to 100 g.
Propylene homopolymer of /10 minutes and/or propylene-ethylene copolymer having a copolymerization ratio of ethylene of at most 5.0% by weight, (B) substantially soluble in xylene at a temperature of 30° C., and The ethylene-propylene random copolymer having an ethylene copolymerization ratio of 25 to 70% by weight, and the copolymerization ratio of (C) a vinyl-polymerizable ester are 5.0 to 5
A copolymer of 0% by weight of ethylene and a vinyl-polymerizable ester or a composition thereof and (D) a filler, which is a propylene homopolymer, a propylene-ethylene copolymer or an ethylene-propylene random copolymer. The MI (1) of the polymer is 0.05 to 80 g/10 minutes,
The composition ratio of the ethylene-propylene random copolymer in the total amount of these polymers is 5.0 to 35% by weight, propylene homopolymer, propylene-ethylene copolymer, ethylene-propylene random copolymer and ethylene. The composition ratio of the copolymer of ethylene and the vinyl-polymerizable ester in the total amount of the polymer substance consisting of the copolymer of the vinyl-polymerizable ester and ethylene is 5.0 to 35% by weight, and The monomer unit derived from the vinyl-polymerizable ester in the molecular substance is 2.5 to 10% by weight, and it is solved by setting the composition ratio of the filler to 40 parts by weight at most with respect to 100 parts by weight of the total amount of the polymeric substance. be able to. Hereinafter, the present invention will be specifically described.

(A) Propylene homopolymer and propylene-ethylene copolymer The propylene homopolymer used in the present invention is obtained by homopolymerizing propylene. Further, the propylene-ethylene copolymer is obtained by copolymerizing propylene with 5.0% by weight (preferably 4.5% by weight or less) of ethylene. These polymers are substantially insoluble in xylene at a temperature of 30°C (soluble matter is usually 10% by weight or less, preferably
5.0% by weight or less).

MI (1) of propylene homopolymer and propylene-ethylene copolymer is 0.01 to 100 g/10 minutes, 0.01 to 80 g
/10 minutes is preferable, and 0.1 to 70 g/10 minutes is particularly preferable. When a propylene homopolymer or propylene-ethylene copolymer having MI (1) of less than 0.01 g/10 minutes is used, the kneading property is not good. On the other hand, when these polymers in excess of 100 g/10 min are used, the resulting composition has poor impact resistance.

(B) Ethylene-propylene random copolymer Further, the ethylene copolymerization ratio of the ethylene-propylene random copolymer used in the present invention is 25 to 70% by weight, preferably 25 to 65% by weight, and particularly 30 to 65
Weight percent is preferred. 25% by weight of ethylene copolymerization
The use of the ethylene-propylene random copolymer of <1> results in unsatisfactory impact resistance of the composition. On the other hand, an ethylene-propylene random copolymer having an ethylene copolymerization ratio of more than 70% by weight is not only difficult to manufacture, but also has problems in rigidity and heat resistance of the composition.

Furthermore, the MI of the ethylene-propylene random copolymer
(1) is usually 0.01 to 50 for the same reason as in the case of the above-mentioned propylene homopolymer or propylene-ethylene copolymer.
g/10 minutes, preferably 0.01-30 g/10 minutes, especially 0.05-
20g/10min is suitable.

Further, the ethylene-propylene random copolymer is
It is substantially soluble in xylene at a temperature of 30°C (insoluble content is generally 10% by weight or less, preferably 5.0% by weight or less).

These propylene homopolymers, propylene-ethylene copolymers and ethylene-propylene random copolymers are produced by homopolymerization or copolymerization, respectively, and are mixed in the composition ratios described below when producing the composition of the present invention. Alternatively, propylene homopolymer and/or propylene-ethylene copolymer may be prepared in advance, and ethylene and propylene may be mixed in the same polymerization vessel or in the presence of the catalyst system used for the production of these polymers and the polymer. It may be produced by so-called block copolymerization in which it is copolymerized in the polymerization vessel.

In any of the above cases, MI (1) of the total amount of propylene homopolymer and/or propylene-ethylene copolymer and ethylene-propylene random copolymer
Is 0.05-80g/10min, 0.1-80g/10min is desirable,
Especially, 0.1 to 70 g/10 minutes is preferable. When the MI(1) of the total amount of the propylene homopolymer and/or the propylene-ethylene copolymer and the ethylene-propylene random copolymer is less than 0.05/10 minutes, the kneading property is not good.
Moreover, the moldability of the obtained composition is not good. On the other hand, 80g/
If it exceeds 10 minutes, the mechanical properties of the composition, especially the impact resistance, are poor.

The ethylene content in the total amount of these polymers is 2.0 to 25% by weight as a monomer unit, preferably 3.0 to 25% by weight, and particularly preferably 5.0 to 25% by weight. If the ethylene content in the total amount of these polymers is less than 2.0% by weight as a monomer unit, there is a problem in impact resistance of the composition. On the other hand, if it exceeds 25% by weight, the rigidity and heat resistance are insufficient.

Further, the composition ratio of the ethylene-propylene random copolymer in the total amount of the propylene homopolymer and/or propylene-ethylene copolymer and the ethylene-propylene random copolymer is 5.0 to 35% by weight, and 5.0 to 35% by weight. 30% by weight is desirable, especially 7.0-30% by weight
Is preferred. When the composition ratio of the ethylene-propylene random copolymer in the total amount of these polymers is less than 5.0% by weight, the resulting composition has poor impact resistance.
On the other hand, if it exceeds 35% by weight, there are problems in rigidity and heat resistance of the composition.

(C) Ethylene-vinyl ester copolymer Further, in the present invention, a copolymer of ethylene and vinyl ester is used. In the present invention, the vinyl ester copolymerizable with ethylene contains a vinyl-polymerizable ester. Therefore, unless otherwise specified, a vinyl-polymerizable ester is referred to as a vinyl ester. The copolymerization ratio of vinyl ester in the ethylene-vinyl ester copolymer is 5.0 to 50% by weight, particularly 5.0 to 50% by weight.
40% by weight is preferred. Vinyl ester copolymerization ratio is 5.
The use of less than 0% by weight of ethylene-vinyl ester copolymer is not desirable because the effect of modification is not satisfactory. On the other hand, use of an ethylene-vinyl ester copolymer having a vinyl ester copolymerization ratio of more than 50% by weight is not preferable because not only the physical properties of the composition are deteriorated but also delamination occurs. The melt index of the ethylene-vinyl ester copolymer [measured according to JIS K7210 under conditions of 4, hereinafter referred to as “MI(2)”] is
Generally, it is 0.1 to 200 g/10 minutes, preferably 0.1 to 150 g/10 minutes, and particularly preferably 0.5 to 100 g/10 minutes. MI (2)
If an ethylene-vinyl ester copolymer having a viscosity of less than 0.01 g/10 minutes is used, the kneading property is not good. On the other hand, if an ethylene-vinyl ester copolymer exceeding 200 g/10 minutes is used, the mechanical strength of the composition will be poor.

The vinyl ester preferably has at most 20 carbon atoms (preferably 4 to 16 carbon atoms). Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, methyl methacrylate, ethyl acrylate and the like, with vinyl acetate being most suitable.

The propylene-based polymer composition of the present invention can be produced by mixing the above-mentioned propylene homopolymer and/or propylene-ethylene copolymer, but by adding a filler, the rigidity of the composition ( Bending elastic modulus) can be improved. This time
By blending the modified propylene-based polymer described below,
This effect can be further exerted. In addition, the impact resistance of the composition can be improved by blending the ethylene-propylene rubber and the ethylene polymer described below.

(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. It is roughly classified into salts and mixtures thereof. Representative 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. Further, in the fibrous form, it is desirable that the diameter is 1 to 500 μm (preferably 1 to 300 μm) and the length is 0.1 to 6 mm (preferably 0.1 to 5 mm). Further, it is preferable that the flat plate has a diameter of 30 μm or less (preferably 10 μm or less). 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.

Further, as the organic filler, wood powder, organic fiber, straw,
Examples include chaff and peanut.

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

The organic fibers include 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 cannot be unconditionally specified because they vary depending on the use and mixing conditions of the polypropylene composition finally obtained, but generally the average diameter range is 3 to 500 μm,
Those having an average length of 0.1 to 6 mm are suitable.

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

Further, from chaff and peanut, it is crushed and used like the above-mentioned wood powder.

(E) Modified propylene-based polymer This modified propylene-based polymer is a propylene-based polymer obtained by adding "α,β-unsaturated carboxylic acid and/or anhydride thereof" (hereinafter referred to as "carboxylic acid-based compound") and organic peroxide. It can be obtained by treating an oxide.

(1) Propylene-based polymer The propylene-based polymer used for producing the modified propylene-based polymer includes propylene homopolymer, block copolymer of ethylene and propylene, and propylene and carbon number at most. Examples thereof include block copolymers with 12 other α-olefins (the copolymerization ratio of α-olefins is at most 20% by weight). The MI (1) of this propylene-based polymer is usually 0.01 to 100 g/10 minutes from the viewpoint of moldability and mechanical properties of the obtained composition.
It is preferably -50 g/10 min, and more preferably 0.02-50 g/10 min.

(2) Carboxylic Acid Compound The carboxylic acid compound used for producing the modified propylene polymer of the present invention is an α,β-unsaturated carboxylic acid and its anhydride. The unsaturated carboxylic acid compound usually has at most 30 carbon atoms, and particularly preferably has 25 or less carbon atoms. 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,
Examples include citraconic acid and 3,6-endomethylene-1,2,3,6-tetrahydro-cis-phthalic acid. Further, the 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-cis- An example is phthalic anhydride.

(3) Organic peroxide Further, the organic peroxide is generally used as an initiator in radical polymerization and a cross-linking agent for the polymer, and one having a half-life of 1 minute or more of 100° C. or more is preferable.
Especially, those of 130° C. or higher are preferable. Above temperature is 1
If the temperature is less than 00°C, not only is it difficult to handle, but the effects of use are not so noticeable, which is not desirable.

(4) Usage ratio 100% in producing the modified olefin polymer.
The proportion of the carboxylic acid compound used relative to parts by weight of the propylene polymer is 0.01 to 10 parts by weight, preferably 0.02 to 10 parts by weight, and particularly preferably 0.02 to 7.0 parts by weight. If the proportion of the carboxylic acid compound used relative to 100 parts by weight of the propylene polymer is less than 0.01 parts by weight, the effect of improving the rigidity will be 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 to 100 parts by weight of the propylene-based polymer is 0.01 to 10 parts by weight, 0.01 to 7.
0 parts by weight is preferable, and 0.02 to 5.0 parts by weight is particularly preferable. When the mixing ratio of the organic peroxide with respect to 100 parts by weight of the propylene polymer is 0.01 parts by weight or less, not only the modification effect is low, but also the effect of improving the rigidity of the mixture is insufficient. On the other hand, when the amount exceeds 10 parts by weight, the excellent mechanical properties of the polymer in the future are deteriorated, and therefore it is not desirable in any case.

(5) Method for producing modified propylene-based polymer To produce the modified propylene-based polymer of the present invention, the above propylene-based polymer, carboxylic acid-based compound and organic peroxide are treated at the above mixing ratio (heating). ) Can be manufactured. At this time, the treatment may be carried out while mixing the propylene polymer, the carboxylic acid compound and the organic peroxide, but these may be mixed in advance by dry blending or at a relatively low temperature (the carboxylic acid compound does not react. It is obtained by kneading at a temperature) and 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 polymer and the carboxylic acid 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 ℃).

Typical examples of the organic peroxides, mixing methods and treating methods are described in detail in JP-A-58-154732.

(F) Ethylene-propylene rubber Further, the ethylene-propylene rubber used in the present invention contains ethylene-propylene copolymer rubber obtained by copolymerizing ethylene and propylene and ethylene and propylene as main components, and 1 ,4-Pentadiene, 1,5-hexadiene and 3,3-dimethyl-1,5-
Contains only one double bond such as 1,4-hexadiene and 6-methyl-1,5-heptadiene, which is a linear or branched diolefin having two double bonds at the end, such as hexadiene. Copolymerize small amounts (generally less than 10% by weight) of straight or branched chain diolefins or monomers such as cyclic diene hydrocarbons such as bicyclo[2,2,1]-heptene-2 and its derivatives. It is a multi-component copolymer rubber obtained by the above. The weight ratio of ethylene monomer units to propylene monomer units of these copolymer rubbers and multi-component copolymer rubbers is usually 30:70 to 80:20.
Those of 40:60 to 75:25 are particularly preferable. These ethylene-propylene rubbers are produced by copolymerization or multi-copolymerization of propylene or ethylene, propylene and the above-mentioned monomers with a catalyst system ethylene obtained from a transition metal compound and an organic aluminum compound.

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 will be improved, but not only the impact improving effect will be low, but layer delamination may occur during gate cutting of the molded product. , It may cause trouble. On the other hand, when the amount of the mixture exceeds 140, not only the dispersion at the time of kneading becomes difficult, but even if a uniform composition is obtained, flow marks, weld lines, etc. are conspicuous on the surface of the molded product. Therefore, a product having a good appearance cannot be obtained.

(G) Ethylene Polymer The density of the ethylene polymer used in the present invention is
And a 0.900 g / cm ³ or more, preferably has a 0.900~0.975g / cm ^3, are preferred, especially those 0.910~0.970g / cm ^3.

The ethylene-based polymer, ethylene homopolymer,
Examples thereof include 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.

MI (2) of the ethylene polymer is at least 0.1 g/10
Min, 0.1 to 50 g/10 min is desirable, especially
It is preferably 0.5 to 10 g/10 minutes. MI (2) is 0.1g/10
If less than a minute is used, the dispersibility is poor and it is difficult to obtain a uniform composition. Even if a uniform composition is obtained, the adhesiveness is slightly improved and the appearance of the formed product is small. not good.

(H) Composition Ratio In the composition of the present invention, propylene homopolymer, propylene-ethylene random copolymer and ethylene-
The composition ratio of ethylene-propylene random copolymer in the total amount of propylene random copolymer is 5.0 to 35.
% By weight, preferably 5.0 to 30% by weight, and more preferably 7.0 to 30% by weight. The composition ratio of the ethylene-propylene random copolymer in the total amount of these polymers is 5.0.
If it is less than wt %, the resulting composition has poor impact resistance. On the other hand, if it exceeds 35% by weight, the composition has poor rigidity.

In addition, the ethylene-vinyl ester copolymer occupies in the total amount of the polymer substance consisting of the propylene homopolymer, the propylene-ethylene copolymer, the ethylene-propylene random copolymer and the ethylene-vinyl ester copolymer in the composition. The composition ratio of the polymer is 5.0 to 35% by weight, 5.0
-30% by weight is preferable, and 7.0-30% by weight is particularly preferable. When the composition ratio of the ethylene-vinyl ester copolymer in these polymer substances is less than 5.0% by weight,
The adhesiveness of the resulting composition with the adhesive (two-component mixed type chlorinated polypropylene) is not good. On the other hand, if it exceeds 35% by weight, the mechanical properties (especially rigidity) of the composition are not good.

The total amount of monomer units derived from vinyl ester and monomer units derived from unsaturated carboxylic acid ester in these polymer substances is 2.5 to 10% by weight. The ratio of units derived from vinyl ester in the polymer is 2.
If it is less than 5% by weight, the adhesiveness of the resulting 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.

Furthermore, the composition ratio of the filler to the total amount of 100 parts by weight of these polymer substances is at most 40 parts by weight, 0.1
-40 parts by weight is preferable, and 1.0-35 parts by weight is particularly preferable. If the composition ratio of the filler exceeds 40 parts by weight with respect to 100 parts by weight of the total amount of the polymer substance, not only the moldability is poor, but also the adhesiveness is deteriorated and the impact resistance 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.

Furthermore, when an ethylene-propylene rubber is compounded, its composition ratio is at most 20% by weight, and particularly preferably 15% by weight or less, based on the total amount of the above-mentioned polymer. When the composition ratio of the ethylene-propylene rubber in the total amount of the polymer exceeds 20% by weight, the resulting composition has good impact resistance, but other mechanical strength (for example, rigidity) is good. Absent.

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

The composition ratio of the modified propylene-based polymer is 10 to 100 parts by weight with respect to 100 parts by weight of the filler described below, and 10 to 80 parts by weight.
Parts by weight are desirable, especially 15 to 75 parts by weight are preferred. When the composition ratio of the modified propylene-based polymer is less than 10 parts by weight with respect to 100 parts by weight, the rigidity of the obtained composition is not good. On the other hand, even if the amount is more than 100 parts by weight, the effect of improving the rigidity is not recognized depending on the amount used.

(J) Production of composition To produce the composition of the present invention, the propylene homopolymer and/or the propylene-ethylene copolymer and the ethylene-vinyl ester copolymer, or the above-mentioned filling depending on the purpose of use, is used. The agent, the modified propylene polymer, the ethylene-propylene copolymer and the ethylene polymer may be mixed so as to be uniform. This time
As described above, the propylene homopolymer and/or the propylene-ethylene copolymer and the ethylene-propylene random copolymer may be produced by so-called block copolymerization, or those produced separately in advance may be mixed at this stage. Good. If necessary, additives such as oxygen, light or heat stabilizers, flame retardants, processability improvers, lubricants, antistatic agents and pigments commonly used in olefin polymers may be 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, Banbury mixer) or a continuous kneader (for example, Although it can be kneaded using an extruder, it can also be kneaded continuously using a continuous mixer as described above. Further, by using these methods together (for example, after dry blending, kneading continuously), it is possible to further uniformly mix.

(K) Molding method The composition thus obtained is usually molded into pellets, and the desired molded product is formed 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 in.

The temperature is higher than the melting point of the polymer to be used, but not to be thermally decomposed, in the case of melt-kneading and in the case of molding the above-mentioned composition. From these, generally 180 ~ 280 ℃ (suitably 200 ~ 260 ℃)
Will be implemented in.

(L) Adhesive The adhesive used in the present invention is a two-liquid mixed type containing chlorinated polypropylene as a main component, and is generally used by dissolving it in an organic solvent that dissolves each of chlorinated polypropylene and an isocyanate compound. It The chlorine content of the chlorinated polypropylene is usually 5.0 to 40% by weight (preferably 7.0 to 35% by weight). Also, the starting material polypropylene is amorphous and its molecular weight is generally 50
It is 0 to 200,000 (preferably 1,000 to 100,000).
Further, as the organic solvent, aromatic hydrocarbons (eg, toluene, xylene), ketones (eg, methyl ethyl ketone), aliphatic or alicyclic hydrocarbons (eg, hexene, cyclohexene) and chlorinated hydrocarbons ( For example, trichloroethylene, tetrachloroethylene, chlorocyclohexane) may be mentioned. In addition, the content of non-volatile substances dissolved in organic solvents is usually
15-30% by weight. The organic solvent may be used alone or as a mixed solution. The viscosity of the solution in which the adhesive is dissolved is usually 100 to 2,000 centipoise at 23° C. from the viewpoint of handling.

(M) Adhesion method In order to apply an adhesive to the surface of the molded article obtained as described above, generally 100 to 200 g/m ² (as a solvent containing an adhesive, the same applies hereinafter) is uniformly applied. Apply. As a coating method, a method generally used in industry may be applied, and typical methods include an air spray method, a roll coating method, a dip coating method, and a brush coating method. As an air spray method, a robot is used. May be used. After coating, the organic solvent may be evaporated almost completely. At this time, if it is rapidly dried, bubbles may be generated in the film, or the film may not be uniformly formed. For that purpose, crosslinking, adhesion and drying can be carried out simultaneously by first drying at a relatively low temperature (for example 50 to 90°C) and then raising the temperature (130 to 150°C). Alternatively, the adherend surfaces may be attached to each other and then pressure-bonded under a low pressure using a press.

[Action]

In the composition of the present invention, the ethylene-vinyl ester copolymer uniformly dispersed in the composition swells with the solvent of the adhesive, so that the adhesive component diffuses into the ethylene-vinyl ester copolymer, It is considered to have a compatibilizing effect.

[Examples and Comparative Examples]

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

In the examples and comparative examples, the flexural modulus is AS
Measured according to TM D790, Izod impact strength is AST
It was measured according to MD256. In addition, room temperature adhesiveness is measured by flat plate test piece (thickness 3mm, 140×14
Chlorinated polypropylene two-liquid mixed type solvent adhesive (0 mm, textured product) (chlorine with a chlorination degree of about 29% by weight obtained by chlorinating amorphous polypropylene with an average molecular weight of about 8,600) Sprayed with an organic mixture of the same volume of toluene and methyl ethyl ketone containing approximately 27% by weight of non-volatile components such as epoxidized polypropylene and isocyanate compounds, and uniformly coating it to 100-150 g/m ² . After drying at 80℃ for 5 minutes,
A vinyl chloride resin (PVC) sheet heated at 0°C for 3 minutes (laminated with a propylene-based resin foam primer coat product) is laminated to the propylene-based resin foam surface, and a heating press is used. (Plate test piece side 50℃, PVC sheet side 150℃) Pressure is 1kg/cm ² 3
It was crimped for 0 seconds. Next, a temperature-controlled room (temperature 23℃, relative humidity 6
5%) and left for 48 hours. The obtained test piece was cut into a width of 25 mm, the PVC sheet was forcibly peeled from the resin portion of the test piece, and the remaining adhered portion was applied to the PVC sheet at a speed of 200 mm/min using a tensile tester. Pull in the opposite direction (180 degrees),
It was determined by measuring the peel strength. Furthermore, the heat-resistant adhesiveness is obtained 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. I asked.

The physical properties of the propylene-based polymer, ethylene-based copolymer, ethylene-propylene-based rubber, ethylene-based polymer, modified propylene-based polymer and filler used in Examples and Comparative Examples are shown below.

[Propylene polymer ((A) propylene homopolymer, (B) ethylene-propylene random copolymer)]

As a propylene-based polymer, Ziegler
Only propylene was polymerized without solvent using Natta catalyst. Then, ethylene was supplied to this polymerization vessel to produce a random copolymer of ethylene and propylene. The resulting propylene-based polymer contains 82% by weight of a propylene homopolymer (insoluble in xylene at a temperature of 30° C.) and has an ethylene copolymerization ratio of 45% by weight. An ethylene-propylene random copolymer (30 Soluble in xylene at a temperature of °C). The MI (1) of this propylene-based polymer [hereinafter referred to as "PP (A)"] is 10
It was g/10 minutes. Further, only propylene was polymerized in the same manner as PP(A), and then random copolymerization of ethylene and propylene was carried out to produce a propylene polymer [hereinafter referred to as "PP(B)"]. This PP (B) contains 75% by weight of a propylene homopolymer (insoluble in xylene at a temperature of 30° C.) and has an ethylene copolymerization ratio of 50.
It was a composition with an ethylene-propylene random copolymer (soluble in xylene at a temperature of 30° C.) that was wt %. The MI (1) of this PP (B) was 8.0 g/10 minutes.
For comparison, a composition with an ethylene-propylene random copolymer containing 87% by weight of a propylene homopolymer (insoluble in xylene) and having an ethylene copolymerization ratio of 40% by weight [MI (1) of composition] 15 g/10 minutes, hereinafter referred to as “PP(C)”, propylene homopolymer having MI (1) of 10 g/10 minutes [hereinafter referred to as “PP(D)]”, MI (1) 12 g/ An ethylene-propylene random copolymer having an ethylene copolymerization ratio of 2.0% by weight for 10 minutes [hereinafter referred to as "PP(E)"
Was used].

[(C) Ethylene Copolymer]

Also, as an ethylene-based copolymer, MI (2) is 30 g/10
Of ethylene-vinyl acetate copolymer [hereinafter referred to as "EVA (a)"
Ethylene-vinyl acetate copolymer [hereinafter referred to as "EVA (b)"] having MI (2) of 21 g/10 minutes and a vinyl acetate copolymerization ratio of 20% by weight, and MI ( 2)
An ethylene-vinyl acetate copolymer having a weight ratio of 7.2 g/10 minutes and a vinyl acetate copolymerization ratio of 4% by weight [hereinafter referred to as "EVA
(A)]], MI (2) is 45 g/10 minutes, and the copolymerization ratio of methyl methacrylate is 35% by weight (hereinafter referred to as "EMMA").
An ethylene-ethyl acrylate copolymer [hereinafter referred to as "EEA"] having an MI (2) of 20 g/10 minutes and a copolymerization ratio of ethyl acrylate of 20% by weight was used.

[(D) Filler]

Further, as a filler, the average particle size is 2.0 μm,
Talc with an aspect ratio of 5.5 and an average particle size of 7.0μ
m, mica with an aspect ratio of 30, wood flour (45 mesh pass) and jute (average particle size 20μ)
m, average fiber length 3 mm).

[(E) Modified propylene-based polymer]

As a modified propylene-based polymer, MI (1) was 0.
0.70 parts by weight of maleic anhydride and 0.4 parts by weight of benzoyl peroxide were preliminarily dry-blended with 100 parts by weight of 6 g/10 min propylene homopolymer for 5 minutes using a Henschel mixer. Pellets produced by kneading the obtained mixture with an extruder (diameter 40 mm, cylinder temperature 180-230°C) [hereinafter referred to as "modified PP"
Was used].

[(G) Ethylene polymer]

Furthermore, MI (2) is 1.0 g/10 minutes and density is 0.9.
50g/cm ³ high density polyethylene [hereinafter “PE (1)”
And MI (2) of 7.1 g/10 min and a density of 0.920 g/cm ³ a linear copolymer of ethylene and butene-1 [copolymerization ratio of butene-1 8.2 wt. %, below "PE
(2)”] is used.

[(F) Ethylene-propylene rubber]

Further, as the ethylene-propylene rubber, an Mooney viscosity [ML ₁₊₄ (100° C.)] of 60, and a copolymerization ratio of propylene of 37% by weight are ethylene-propylene copolymer rubber [hereinafter referred to as “EPR” Say) 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"
Was used].

Examples 1 to 9 and Comparative Examples 1 to 8 Propylene-based polymers, ethylene-based copolymers, and fillers whose amounts and types are shown in Table 1 were mixed for 5 minutes using a super mixer. The resulting mixture was vented to a twin-screw extruder (cylinder temperature 180-2
Pellets (composition) were produced while kneading using 00° C. and a diameter of 30 mm). Each pellet was manufactured into a flat plate, a bending elastic modulus measuring sample, and an Izod impact strength measuring sample using a 5 ounce injection molding machine. The Izod impact strength (measurement temperature: 23° C.) and flexural modulus of each of the obtained specimens 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 was destroyed.

Examples 10 to 17 PP(A) and modified propylene-based polymers whose respective blending amounts are shown in Table 3 and ethylene-based copolymers and ethylene-based polymers whose respective types and blending amounts are shown in Table 3 Dry blending of [hereinafter referred to as “PE”], ethylene-propylene rubber [hereinafter referred to as “rubber”] and filler was performed in the same manner as in Example 1. The obtained mixture was kneaded in the same manner as in Example 1 to produce pellets (composition). A flat plate, a test piece for measuring flexural modulus and a test piece for measuring Izod impact strength of each pellet were manufactured using an injection molding machine in the same manner as in Example 1. The Izod impact strength and flexural modulus of each of the obtained specimens were measured, and room temperature adhesiveness and heat resistant adhesiveness were measured. The results are shown in Table 4.

[Advantages of the Invention] The bonding method of the present invention and the propylene-based polymer composition used in the bonding method or a molded product thereof exhibit 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) Adhesion with an 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 method of the present invention can be used in various fields to exert the effects described above. Typical examples are automobile parts such as door liners, instrument panels, and various linings.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hide Umemura 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Akira Kawasaki Plastics Research Laboratory (56) Reference JP-A-62-277449 (JP, A) JP-A 60-32842 (JP, A) JP-A 64-45445 (JP, A) JP-A 59-138252 (JP, A) JP-A 52-138539 (JP, A) (58) Fields investigated (Int.Cl. ⁶ , DB name) C08L 23/10 C08L 23/08 C09J 123/10 C09J 5/00

Claims (3)

(57) [Claims] 1. When bonding a molded product of a propylene-based polymer composition and a two-component mixed type adhesive containing chlorinated polypropylene as a main component, the propylene-based polymer composition is (A) 30° C. Propylene homopolymer which is substantially insoluble in xylene at a temperature of, and has a melt index of 0.01 to 100 g/10 minutes and/or a copolymerization ratio of ethylene of at most 5.0% by weight, a propylene-ethylene copolymer, (B) an ethylene-propylene random copolymer substantially soluble in xylene at a temperature of 30° C. and having an ethylene copolymerization ratio of 25 to 70% by weight; and (C) a copolymer of a vinyl polymerizable ester. Polymerization ratio is 5.0 to 5
A copolymer of 0% by weight of ethylene and a vinyl-polymerizable ester or a composition thereof and (D) a filler, which is a propylene homopolymer, a propylene-ethylene copolymer or an ethylene-propylene random copolymer. Polymer melt index is 0.05-80g/10
The composition ratio of the ethylene-propylene random copolymer in the total amount of these polymers is 5.0 to 35% by weight, and the propylene homopolymer, the propylene-ethylene copolymer, the ethylene-propylene random copolymer. The composition ratio of the copolymer of ethylene and vinyl-polymerizable ester in the total amount of the polymer and the polymer substance consisting of the copolymer of ethylene and vinyl-polymerizable ester is 5.
0 to 35% by weight, and the monomer units derived from the vinyl polymerizable ester in these polymeric substances are 2.5 to 1
0% by weight, and the total amount of these polymeric substances is 100
A bonding method characterized in that the composition ratio of the filler to 40 parts by weight is at most 40 parts by weight. 2. (A) It is substantially insoluble in xylene at a temperature of 30° C. and has a melt index of 0.01 to 100 g/1.
Propylene homopolymer having 0 minutes and/or propylene-ethylene copolymer having a copolymerization ratio of ethylene of at most 5.0% by weight, (B) substantially soluble in xylene at a temperature of 30° C., and ethylene. Ethylene-propylene random copolymer having a copolymerization ratio of 25 to 70% by weight, and (C) a vinyl polymerizable ester copolymerization ratio of 5.0 to 5
A copolymer comprising 0% by weight of ethylene and a vinyl-polymerizable ester, or a composition thereof and (D) a filler, wherein the propylene homopolymer, propylene-ethylene copolymer and ethylene-propylene The melt index of the random copolymer is 0.05 to 80 g/10 minutes, the composition ratio of the ethylene-propylene random copolymer in the total amount of these polymers is 5.0 to 35% by weight, and the propylene homopolymer is A copolymer of ethylene and a vinyl-polymerizable ester in the total amount of the polymer substance consisting of a propylene-ethylene copolymer, an ethylene-propylene random copolymer and a copolymer of ethylene and a vinyl-polymerizable ester. The composition ratio of the polymer is 5.0 to 35% by weight,
And the monomer unit derived from the vinyl polymerizable ester in these polymer substances is 2.5 to 10% by weight, and the composition ratio of the filler to the total amount of these polymer substances is 100 parts by weight is at most 40 parts by weight. And a propylene-based polymer composition. 3. A molded article comprising a propylene-based polymer composition in which a two-component mixed type adhesive containing chlorinated polypropylene as a main component is used, wherein the propylene-based polymer composition comprises (A) 30 Propylene homopolymer having a melt index of 0.01 to 100 g/10 minutes and/or a copolymerization ratio of ethylene of at most 5.0% by weight, which is substantially insoluble in xylene at a temperature of °C. (B) an ethylene-propylene random copolymer which is substantially soluble in xylene at a temperature of 30° C. and has an ethylene copolymerization ratio of 25 to 70% by weight, and (C) a vinyl polymerizable ester. Copolymerization ratio is 5.0 to 5
A copolymer comprising 0% by weight of ethylene and a vinyl-polymerizable ester, or a composition thereof and (D) a filler, wherein the propylene homopolymer, propylene-ethylene copolymer and ethylene-propylene The melt index of the random copolymer is 0.05 to 80 g/10 minutes, the composition ratio of the ethylene-propylene random copolymer in the total amount of these polymers is 5.0 to 35% by weight, and the propylene homopolymer is A copolymer of ethylene and a vinyl-polymerizable ester in the total amount of the polymer substance consisting of a propylene-ethylene copolymer, an ethylene-propylene random copolymer and a copolymer of ethylene and a vinyl-polymerizable ester. The composition ratio of the polymer is 5.0 to 35% by weight,
And the monomer unit derived from the vinyl polymerizable ester in these polymer substances is 2.5 to 10% by weight, and the composition ratio of the filler to the total amount of these polymer substances is 100 parts by weight is at most 40 parts by weight. A propylene-based molded product characterized by being a part.