JPH06256439A - Propylene polymer composition - Google Patents

Abstract

PURPOSE:To obtain a polymer composition excellent in adhesion to a coating film of e.g. a urethane coating material and mechanical strengths by mixing a specified propylene polymer with a specified hydrogenated copolymer and modifying each polymer with a specified compound. CONSTITUTION:This polymer composition is prepared by mixing a propylene polymer (e.g. PP) having a melt flow rate of 0.05-15g/10min as measured at 230 deg.C under a load of 2.16kg with a hydrogenated aromatic vinyl compound/ conjugated diene compound copolymer (e.g. styrene/butadiene block copolymer) having a melt flow rate of 10-200g/10min as measured under the above conditions in a weight ratio of 99:1 to 10:90 and modifying each polymer with 0.1-20 pts.wt., per 100 pts.wt. total of the both, hydroxy ethylenically unsaturated compound (e.g. hydroxyethyl acrylate).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene-based polymer composition having excellent coating properties. More specifically, the present invention relates to a propylene-based polymer composition having high adhesion to paints such as urethane-based paints and amine-based paints even when they are not surface-treated with a primer or a solvent.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Propylene-based polymers are widely industrially manufactured because they have various properties such as mechanical properties, heat resistance, solvent resistance, oil resistance and chemical resistance. This propylene-based polymer is widely used as a raw material for manufacturing industrial parts such as automobiles and electric appliances and daily necessities.
However, the propylene-based polymer is highly safe because it has no polar group in the molecule and is chemically inactive, while it does not have a polar group, so it has good adhesion to other resins. is not. Therefore, for example, when coating with urethane-based paint, etc., use treatment by electrical treatment method such as corona discharge, mechanical surface roughening method, flame treatment method, oxygen treatment method or surface treatment method such as ozone treatment method. Then, it is necessary to perform a treatment for improving the affinity of the surface of the molded product with other resins.

In carrying out these surface treatments, the surface of the molded product is previously washed with a solvent such as alcohol or aromatic hydrocarbon, or is washed with a solvent vapor such as trichlene, perchlorethylene, pentachloroethylene or toluene. The method is generally adopted.

In order to carry out the above-mentioned methods, an apparatus for processing all is required, which is disadvantageous in terms of equipment and requires a considerable amount of time for processing these. In addition to the method of coating after performing the above-described pretreatment, a primer capable of adhering to a propylene-based polymer is undercoated on the molded product, and a urethane-based paint, an amine-based paint or the like is formed on the undercoat layer. Although a method of applying paint is also used, this method also requires an undercoating step and an overcoating step, which requires a long time for the coating step, and the coating film is formed to have a two-layer structure. There is a problem that the cost of goods becomes high.

As described above, with respect to the coating of the molded product made of the propylene-based polymer, the molded product itself is generally subjected to some treatment. Therefore, since the process of coating a molded article made of a propylene-based polymer that has been conventionally performed is complicated, development of a propylene-based polymer having excellent coatability has been earnestly desired.

An attempt to introduce a carboxyl group, an acid anhydride group, a hydroxyl group, and an amino group into a propylene-based polymer and an olefin-based elastomer for the purpose of improving the coating property of such a propylene-based polymer is disclosed in JP-A-58-217,349. 58-219,244
Nos. 54-124,048 and 62-127,332. Further, JP-A-60-101,130 and 63-39,95
No. 1 discloses that polyolefin is acid-modified aromatic vinyl-
A composition in which a conjugated diene compound copolymer hydrogenated material is added to improve impact resistance and paintability is shown.

However, these methods do not sufficiently improve the elastic modulus, impact resistance and paintability, and further improvement is demanded.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems in olefin resin compositions, and is a propylene polymer excellent in coating properties while maintaining properties such as mechanical strength. The purpose is to provide a composition.

[0009]

SUMMARY OF THE INVENTION The first modified olefin polymer composition of the present invention has a propylene polymer (a) and a melt flow rate of 1 when measured at a temperature of 230 ° C. and a load of 2.16 kg.
The aromatic vinyl compound-conjugated diene compound copolymer hydrogenated product (b), which is 0 to 200 g / 10 min, is 99: 1 to 10:
The propylene-based polymer (a), which is contained in a weight ratio of 90.
And the hydrogenated product (b) is modified with 0.1 to 20 parts by weight of a hydroxyl group-containing ethylenically unsaturated compound (c) based on 100 parts by weight of the total of the components (a) and (b). It is characterized by being.

The second modified olefin polymer composition of the present invention has a propylene polymer (a) and a melt flow rate of 10 measured at a temperature of 230 ° C. and a load of 2.16 kg.
-200 g / 10 min with aromatic vinyl compound-conjugated diene compound copolymer hydrogenated product (b), 99: 1 to 10: 9
The propylene polymer (a) and the hydrogenated product (b) are contained in a weight ratio of 0 to 0.1 parts by weight based on 100 parts by weight of the total of the components (a) and (b). To 20 parts by weight of a hydroxyl group-containing ethylenically unsaturated compound (c), a modified polymer composition [A], an unmodified propylene polymer (a-1) and / or an unmodified aromatic vinyl compound- Consisting of a hydrogenated product of a conjugated diene compound copolymer (b-1), an unmodified propylene-based polymer (a-1) and / or an unmodified aromatic vinyl compound-hydrogenated product of a conjugated diene compound copolymer (b-1)
Is contained in an amount of 1 to 500 parts by weight based on 100 parts by weight of the total of the components (a) and (b).

In the modified olefin polymer composition of the present invention, as described above, the propylene polymer (a) and the hydrogenated product (b) of the aromatic vinyl compound-conjugated diene compound copolymer are hydroxyl group-containing ethylene. Since it is modified with a polyunsaturated compound (c), it adheres well to coatings such as urethane paints and melamine paints, and the above paints are applied without surface treatment on the surface to be coated as in the past. Even then, the coating film exhibits good adhesion. Moreover, even by improving the coatability in this way, the characteristics that the propylene-based polymer essentially has,
In particular, mechanical properties do not deteriorate.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Next, the propylene polymer composition of the present invention will be specifically described. [Propylene-based Polymer (a)] The propylene-based polymer (a) constituting the propylene-based polymer composition of the present invention is a homopolymer of propylene or a copolymer of propylene and another α-olefin. . Examples of α-olefins copolymerized with propylene include ethylene, 1-butene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene. , 4-methyl-1-pentene, 3,3-
Dimethyl-1-butene, 1-heptene, methyl-1-hexene,
Dimethyl-1-pentene, trimethyl-1-butene, ethyl-1
-Pentene, 1-octene, methyl-1-pentene, dimethyl
-1-hexene, trimethyl-1-pentene, ethyl-1-hexene, methylethyl-1-pentene, diethyl-1-butene,
Propyl-1-pentene, 1-decene, methyl-1-nonene, dimethyl-1-octene, trimethyl-1-heptene, ethyl-1
-Octene, methylethyl-1-heptene, diethyl-1-hexene, 1-dodecene, hexadodecene and the like can be mentioned. These monomers may form a random copolymer with propylene, or may form a block copolymer. Particularly in the present invention, a propylene-based polymer
(a) Propylene homopolymer, ethylene content 2
A crystalline propylene-ethylene block copolymer having a content of -40 mol% and a crystalline propylene-ethylene random copolymer having an ethylene content of 0.5-10 mol% are preferred.

The melt flow rate (MFR) of the propylene polymer (a) measured at a temperature of 230 ° C. and a load of 2.16 kg is usually in the range of 0.05 to 15 g / 10 minutes, and the MFR is Those in the range of 0.1 to 5 g / 10 minutes are preferably used. By using a propylene-based polymer having such an MFR, good physical properties and moldability can be secured.

The density of the propylene polymer (a) is usually within the range of 0.89 to 0.92 g / cm ³ . [Hydrogenated product of aromatic vinyl compound-conjugated diene compound copolymer (b)] Aromatic vinyl compound-conjugated diene compound which constitutes the modified propylene polymer of the present invention together with the above-mentioned propylene polymer (a) The hydrogenated product (b) of the block copolymer is a block containing at least one polymer block A mainly containing an aromatic vinyl compound and at least one polymer block B mainly containing a conjugated diene compound. Hydrogenated product of copolymer, containing at least one, preferably at least two, polymer block mainly composed of aromatic vinyl compound and at least one polymer block mainly composed of conjugated diene compound It is preferably a hydrogenated product of a block copolymer.

Here, the polymer block A containing an aromatic vinyl compound as a main component is composed of an aromatic vinyl compound and a conjugated diene compound, usually 100/0 to 51/49, preferably 100/0 to 70/30. When the polymer block A is a copolymer block in which the aromatic vinyl compound and the conjugated diene compound are copolymer blocks, the conjugated diene compound is randomly, It is distributed in a partial block shape or any combination thereof.

The polymer block B containing a conjugated diene compound as a main component is such that the aromatic vinyl compound and the conjugated diene compound are usually 0/100 to 49/51, preferably 0/100 to 30/70. When it is a polymer block copolymerized at a weight ratio within the range, and this copolymer block B is a copolymer of a conjugated diene compound and an aromatic vinyl compound,
The aromatic vinyl compound is randomly, partially block-shaped or distributed in any combination thereof in this block.

The aromatic vinyl compound-conjugated diene compound block copolymer comprises a repeating unit derived from an aromatic vinyl compound and a repeating unit derived from a conjugated diene compound, usually 10/90 to 65/35. The weight ratio is preferably in the range of 20/80 to 50/50. By using a copolymer having a content of repeating units derived from an aromatic vinyl compound of 10% by weight or more, it is possible to secure the rigidity of the modified olefin-based polymer composition of the present invention, and the aromatic vinyl compound. By using a copolymer having a content of repeating units derived from the compound of 65% by weight or less, the effect of improving the impact resistance of the olefin polymer composition of the present invention is sufficiently exhibited.

Examples of the aromatic vinyl compound forming the copolymer include styrene, α-methylstyrene, p-methylstyrene, alkylstyrene such as p-tert-butylstyrene, paramethoxystyrene and vinylnaphthalene. These can be used alone or in combination. Of these, styrene is particularly preferable. Examples of the conjugated diene compound include butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene and 4,5-diethyl-1,3-octadiene. it can. These can be used alone or in combination. Of these, butadiene and / or isoprene are preferred.

The number average molecular weight of this aromatic vinyl compound-conjugated diene compound block copolymer measured by gel permeation chromatography is usually in the range of 20,000 to 500,000, and the molecular weight distribution (weight The ratio of average molecular weight to number average molecular weight) is usually in the range of 1.01-10. The molecular structure of the aromatic vinyl compound-conjugated diene compound block copolymer may be linear, branched, radial, or a combination thereof.

Further, when butadiene or isoprene is used as the conjugated diene compound in the aromatic vinyl compound-conjugated diene compound block copolymer,
The microstructure of the conjugated diene is preferably such that the 1,2 bond content is in the range of 5 to 80% or the 3,4 bond content is in the range of 5 to 80%.
It is particularly preferable that it is within the range.

When the aromatic vinyl compound-conjugated diene compound block copolymer contains two or more polymer blocks mainly containing an aromatic vinyl compound,
Each block may have the same structure, or may have different structures such as the content of the monomer component, the distribution in their molecular chains, the molecular weight of the block, and the microstructure.

The aromatic vinyl compound-conjugated diene compound block copolymer can be obtained, for example, by polymerizing the above-mentioned monomers by a catalyst such as an alkyllithium and an alkylsodium by an anionic polymerization method. However, the present invention is not limited to this method, and any known method can be used within the above range.

Aromatic vinyl compound used in the present invention-
The hydrogenated product of the conjugated diene compound block copolymer is the above aromatic vinyl compound-conjugated diene compound block copolymer product, for example, platinum, a supported catalyst such as palladium, organic cobalt, a nickel compound, or these. It is obtained by hydrogenation in the presence of a known hydrogenation catalyst such as a complex of the compound with another organometallic compound.

Hydrogenation is preferably carried out to the extent that at least 80%, preferably 90% or more of the conjugated diene moieties are hydrogenated. However, the proportion of hydrogenated aromatic vinyl moieties is preferably 20% or less, and more preferably 5% or less.

If the hydrogenation ratio of the conjugated diene portion is less than 80%, the propylene-based polymer (a) and the block copolymer (b) will be due to the double bond of the conjugated diene contained in the block copolymer. ) Tends to be less compatible with
As a result, the impact resistance of the resulting composition may decrease.

The degree of unsaturation of the conjugated diene portion of the block copolymer (b) can be measured by instrumental analysis using infrared absorption analysis, nuclear magnetic resonance, etc., or titration analysis by iodometric titration. Regarding the hydrogenated product (b) of the aromatic vinyl compound-conjugated diene compound block copolymer used here, the MFR measured at a temperature of 230 ° C. and a load of 2.16 kg was 10 to 2
It should be in the range of 00 g / 10 minutes. Furthermore, the block copolymer (b) having an MFR within the range of 20 to 5 g / 120 minutes is preferably used. M like this
By using the hydrogenated product (b) of the aromatic vinyl compound-conjugated diene compound block copolymer having FR, good physical properties, moldability and paintability can be secured.

The density of the hydrogenated product of such an aromatic vinyl compound-conjugated diene compound block copolymer is usually in the range of 0.89 to 0.95 g / cm ³ . The propylene-based polymer (a) and the hydrogenated product (b) of the aromatic vinyl compound-conjugated diene compound copolymer are 99: 1 to 10: 9.
It is blended in a weight ratio of 0. The blending weight ratio [(a) :( b)] of both is preferably 90:10 to 20:80, and more preferably 85:15 to 30:70.

[Hydroxyl group-containing ethylenically unsaturated compound
(c)] The modified olefin polymer composition of the present invention is a propylene-based polymer (a) and a hydrogenated product of an aromatic vinyl compound-conjugated diene compound copolymer (b) are hydroxyl group-containing ethylenic compounds. It is a composition modified with an unsaturated compound (c).

Here, a hydroxyl group-containing ethylenically unsaturated compound
Specific examples of (c) include hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-
Hydroxy-3-phenoxy-propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetra Mention is made of (meth) acrylic acid esters having a hydroxyl group such as methylolethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate and 2- (6-hydroxyhexanoyloxy) ethyl acrylate. You can

These hydroxyl group-containing ethylenically unsaturated compounds (c) can be used alone or in combination. Among such hydroxyl group-containing ethylenically unsaturated compounds (c), particularly in the present invention, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate may be used. preferable.

In this modification, the hydroxyl group-containing ethylenically unsaturated compound (c) is mixed with the propylene polymer (a) and the aromatic vinyl compound-conjugated diene compound block copolymer.
It is necessary to modify the total amount of (b) with respect to 100 parts by weight in an amount within the range of 0.1 to 20 parts by weight, and further, this amount is within the range of 0.3 to 10 parts by weight. Is preferred.

By modifying with the above-mentioned amount of the hydroxyl group-containing ethylenically unsaturated compound (c), the graft amount of the hydroxyl group-containing ethylenically unsaturated compound (c) in the resulting composition (monomer conversion) Is usually 0.1 to 20 parts by weight, preferably 0.5 to 8 parts by weight, based on the weight of the composition.

[Other compounding agents] The propylene polymer (a) and the hydrogenated product (b) of the aromatic vinyl compound-conjugated diene compound copolymer are modified with a hydroxyl group-containing ethylenically unsaturated compound (c). In this case, in addition to the above-mentioned hydroxyl group-containing ethylenically unsaturated compound (c), styrene within a range that does not impair the characteristics of the composition of the present invention, it is possible to use a polymerizable aromatic compound such as α-methylstyrene in combination. it can.

The polymerizable aromatic compound is usually used in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the propylene polymer (a) and the aromatic vinyl compound-conjugated diene compound block copolymer (b). 20 parts by weight, preferably 0.3-10
Used in an amount within the range of parts by weight.

Further, in the modification with the hydroxyl group-containing ethylenically unsaturated compound (c), it is preferable to use a radical initiator. Here, as the radical initiator,
Usually, an organic peroxide or an azo compound is used.

Specific examples of the organic peroxide used here include 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane and 1,1-bis (t- Butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valalate, 2,2-bis (t-butylperoxy) Peroxyketals such as butane, di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide,
α, α'-bis (t-butylperoxy-m-isopropyl) benzene, (2,5-dimethyl-2,5-bis (t-butylperoxy)
Dialkyl peroxides such as hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl Peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide,
Diacyl peroxides such as 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexano Ate, t-butylperoxylaurylate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxy Maleic acid, t-butylperoxyisopropyl carbonate, peroxyesters such as cumylperoxyoctate, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
Hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide can be mentioned.

Of these, preferred is 1,1-bis (t
-Butylperoxy) -3,5,5-trimethylcyclohexane, di-t-butylperoxide, dicumyl peroxide, (2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2 , 5-Dimethyl-2,5-bis (t-butylperoxy)
Hexin-3.

Examples of the azo compound include azoisobutyronitrile. Such radical initiators can be used alone or in combination. The radical initiator is usually 0.01 to 1 relative to 100 parts by weight of the total of the propylene polymer (a) and the aromatic vinyl compound-conjugated diene compound block copolymer (b).
It is used in an amount of 0 parts by weight, preferably 0.05-5 parts by weight.

A filler may be added to the modified olefin polymer composition of the present invention. Specific examples used here include light calcium carbonate, heavy calcium carbonate, basic calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, kaolin, clay, pyroferrite, sericite, talc. , Calcium silicate (wollastonite, zonotolite, petal-like calcium silicate), diatomaceous earth, aluminum silicate, silicic anhydride, hydrous silicic acid, mica,
Magnesium silicate (asbestos, PFM (Processed M
ineral Fiber), sepiolite), potassium titanate,
Erestadite, plaster, glass balun, silica balun, fly ash balun, silas balun, carbon balun, phenolic resin, urea resin, styrene resin, organic resin balun such as saran resin, silica, alumina,
Barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, graphite, glass fiber (chopped strand, roping, milled glass fiber, glass flake, etc.), cut fiber, rock fiber,
Microfiber, carbon fiber, aromatic polyamide fiber,
Examples thereof include potassium titanate fiber, coumarone indene resin, petroleum resin and the like.

Further, a colorant may be added to the composition of the present invention. Specific examples of the colorant include carbon black, titanium oxide, zinc white, red iron oxide, ultramarine blue,
Examples include dark blue, azo pigments, nitroso pigments, lake pigments and phthalocyanine pigments.

Further, the composition of the present invention includes a known heat stabilizer such as a phenol stabilizer, a sulfite stabilizer, a phenylalkane stabilizer, a phosphite stabilizer or an amine stabilizer, and an aging stabilizer. It is also possible to add a lubricant such as an inhibitor, a weather resistance stabilizer, an antistatic agent, metal soap and wax.

In addition to the above-mentioned compounding agents, other thermoplastic resins, softening agents, plasticizers, flame retardants, and electrical property improving agents may be added as long as the physical properties and coating properties of the composition are not impaired. It can be blended as needed.

[Production of Propylene-Based Polymer Composition] The propylene-based polymer composition of the present invention is a propylene-based polymer.
It is obtained by graft-modifying the hydrogenated product (a) and the hydrogenated product (b) of the aromatic vinyl compound-conjugated diene compound block copolymer with the hydroxyl group-containing ethylenically unsaturated compound (c).

That is, the composition of the present invention is made uniform by employing a mixing method which is generally used in the field of propylene-based polymers so that the above components are in the range of the above composition ratio. It can be produced by mixing, usually the propylene-based polymer (a), a hydrogenated product of an aromatic vinyl compound-conjugated diene compound (b), for example, in the presence of a radical initiator, a hydroxyl group-containing It is produced by melt-kneading with the ethylenically unsaturated compound (c).

When producing the composition of the present invention, all the composition components may be blended and mixed at the same time, or a part of the composition components may be mixed in advance to produce a so-called masterbatch. You may mix this masterbatch and the remaining composition component.

The above components are preferably kneaded in a non-open type apparatus, preferably in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature is a temperature at which the half-life of the radical initiator used is 1 minute, usually 150 to 28.
0 ° C, preferably 170-240 ° C, kneading time is usually 1
-20 minutes, preferably 1-10 minutes.

As a kneading device, a mixing roll or an intensive mixer (eg, Banbury mixer, kneader, single-screw or twin-screw extruder) can be used. Of these apparatuses, it is particularly preferable to use a non-open type apparatus and knead in an inert gas atmosphere.

The composition thus obtained is usually molded into pellets and manufactured into a desired molded product by a molding method such as an injection molding method or an extrusion molding method which is generally used in the field of each thermoplastic resin. To be done.

[Second Modified Olefin Polymer Composition]
The modified olefin polymer composition (first) of the present invention comprises the propylene polymer (a) and the aromatic vinyl compound-conjugated diene compound block copolymer hydrogenated product (b) as described above. Although it is a composition graft-modified with the contained ethylenically unsaturated compound (c), in the present invention, the first modified olefin polymer composition (hereinafter, for convenience, this is referred to as "modified polymer composition" Hydrogenated products of unmodified propylene polymer (a-1) and / or unmodified aromatic vinyl compound-conjugated diene compound copolymer (b-1)
Can be blended (the second modified olefin polymer composition).

Here, the unmodified propylene polymer (a-1)
Is a homopolymer of propylene similar to the propylene polymer (a) used in preparing the above-mentioned first modified olefin polymer composition or a copolymer of propylene and another α-olefin. Can be used.

That is, the unmodified propylene-based polymer that can be used here is a homopolymer of propylene or a copolymer of propylene and another α-olefin. Examples of the α-olefin copolymerized with propylene include the α-olefins mentioned in the description of the propylene polymer (a). Further, among these, a propylene homopolymer, a crystalline propylene-ethylene block copolymer having an ethylene content of 2 to 40 mol%,
Crystalline propylene having an ethylene content of 0.5 to 10 mol%
Ethylene random copolymers are preferred.

However, the unmodified propylene polymer (a-1) used here has a higher melt flow rate (temperature 230 ° C., load 2.16 k) than the above-mentioned propylene polymer (a).
Melt flow rate (MFR) measured by g can also be used, and the melt flow rate of the unmodified propylene-based polymer (a-1) that can be used here is usually from 0.05 to Within the range of 150 g / 10 minutes, preferably 1
Within the range of ~ 70 g / 10 minutes.

The density of this propylene polymer (a) is usually in the range of 0.89 to 0.92 g / cm ³ . The hydrogenated product (b-1) of the unmodified aromatic vinyl compound-conjugated diene compound copolymer contained in the second composition of the present invention is
It is a copolymer having the same composition as the hydrogenated product (b) of the aromatic vinyl compound-conjugated diene compound copolymer forming the first composition.

However, the hydrogenated product (b-1) of the unmodified aromatic vinyl compound-conjugated diene compound block copolymer used herein is the hydrogenated product (b-1) used in the preparation of the first composition. Hydrogenates with lower melt flow rates than b-1) can be used. That is, the MFR of the hydrogenated product (b-1) measured at a temperature of 230 ° C. and a load of 2.16 kg is usually in the range of 0.1 to 100 g / 10 min, preferably 0.5 to 70 g / 10 min. Within range.

The density of the hydrogenated product (b-1) of this unmodified aromatic vinyl compound-conjugated diene compound copolymer is
It is usually in the range of 0.89 to 0.95 g / cm ³ . Unmodified propylene-based polymer having such properties (a-1) and unmodified aromatic vinyl compound-hydrogenated product of a conjugated diene compound copolymer (b-1) may be used alone, Both may be used in combination.

In the second resin composition, the unmodified propylene polymer (a-1) and the hydrogenated product (b-1) of the unmodified aromatic vinyl compound-conjugated diene compound copolymer are the above-mentioned The resin composition is blended in an amount of 1 to 500 parts by weight, preferably 1 to 300 parts by weight, based on 100 parts by weight of the component (a) and the component (b) in total.

Various additives such as a filler may be added to the second resin composition, as in the first resin composition. The second resin composition of the present invention is produced by first producing a modified polymer composition corresponding to the first composition, and then adding a predetermined amount of unmodified propylene-based polymer to the modified polymer composition.
It can be produced by blending (a-1) and / or the hydrogenated product (b-1) of the unmodified aromatic vinyl compound-conjugated diene compound copolymer and melt-kneading.

The melt-kneading conditions at this time are basically the first.
The composition is similar to that of the above composition, and the kneading temperature is usually 150 to 28.
It is 0 ° C. and the melting time is 1 to 10 minutes. In this melt-kneading, a mixing roll and an intensive mixer (eg, Banbury mixer, kneader, single-screw or twin-screw extruder) used when preparing the first composition can be used. Of these apparatuses, it is particularly preferable to use a non-open type apparatus and knead in an inert gas atmosphere.

Like the first composition, the composition thus obtained is usually molded into pellets, and the injection molding method, the extrusion molding method, etc., which are generally performed in the field of each thermoplastic resin. A desired molded product is manufactured by the molding method of.

If necessary, other thermoplastic resins may be added to the first and second compositions of the present invention. Specific examples of other thermoplastic resins used here include high-density polyethylene, medium-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene,
Examples thereof include poly-1-butene and propylene-1-butene copolymers.

A molded article formed from the first and second propylene-based polymer compositions of the present invention is a urethane-based paint,
Excellent coatability for amino paints. Urethane-based paints are paints that generally form a coating film by reacting a polyisocyanate and a polyol compound, and there are one-pack type and two-pack type, and there are also powder paints using a block-type isocyanate. The polymer composition of the present invention has good affinity with any of these urethane-based paints. Further, amine-based paints include melamine-based paints, benzoguanamine-based paints, and urea-based paints, which are paints that form a coating film by the reaction between a methylol group formed by addition condensation of an amino group and formaldehyde and a hydroxyl group of alcohol, and these are: Further, it is used as a mixture with an oil-modified alkyd resin, an oil-free alkyd resin, an oil varnish, an acrylic resin, an epoxy resin and an epoxy ester resin having plasticity.

A coating method using, for example, a urethane resin-based paint among the above-mentioned paints will be described by way of example. A molded product formed from the first and second propylene-based polymer compositions of the present invention. Are washed at least once with water and with a general industrial detergent, further washed with water, and then dried by heating. That is, when coating a molded product formed from the polymer composition of the present invention, it is not always necessary to carry out steam cleaning using a chlorine-based solvent, which has been conventionally performed. A urethane resin coating film can be formed by applying a urethane-based paint to the thus-dried molded body and heating it as necessary. The coating film formed in this way has very good adhesion to the molded product, although it is not washed (surface treated) with chlorine-based solvent vapor.

The propylene-based polymer composition of the present invention thus obtained is excellent in moldability and can be molded by an apparatus used for usual thermoplastics, and extrusion molding, calender molding, injection molding. Suitable for molding etc.

Utilizing the above characteristics, the polymer composition of the present invention can be used for automobile parts, motorcycle parts, electric equipment parts, daily necessities, civil engineering building materials, general industrial materials, office information equipment, packaging materials, sports. It can be widely used for applications to which painting is applied such as tools and medical tools.

[0065]

The first propylene-based polymer composition of the present invention comprises a specific propylene-based polymer (a) and a hydrogenated product (b) of an aromatic vinyl compound-conjugated diene compound copolymer. Since it has a structure modified with the hydroxyl group-containing ethylenically unsaturated compound (c), it has very good adhesion to the coating film of urethane paint or amine paint. Therefore, even if the coating material is directly applied without performing the pretreatment for coating the surface of the molded product and the primer treatment as in the conventional case, the adhesion between the formed coating film and the molded product is good. . Therefore, by using the polymer composition of the present invention, it becomes possible to omit a complicated pretreatment step in coating. Further, such improved coating properties do not impair the excellent characteristics inherent in the resin forming the composition.

Further, the second propylene polymer composition of the present invention has good coatability as in the case of the first composition described above, and further has better mechanical strength such as flexural modulus. .

[0067]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Various properties of the propylene polymer composition used in the present invention were measured as follows. (1) Bending elastic modulus Using a test piece having a thickness of 1/8 inch, ASTM D-7
90. (2) Coating test ○ Preparation of test piece The following paint was applied to a square plate molded by a 50-ton injection molding machine. The surface of the square plate was blown with air before applying the following coating material. -Coating A melamine-based paint and a two-component urethane-based paint were applied with an air gun to a dry film thickness of 60 µm. The baking was performed at 120 ° C. for 30 minutes and 100 ° C. for 30 minutes, respectively.・ Cross-cut test In accordance with the cross-cut test method described in JIS K5400, a cross-cut test piece is prepared, and cellophane adhesive tape (Nichiban Co., Ltd., trade name Cellotape) is attached to the test piece. After that, this was rapidly pulled in the direction of 90 ° to be peeled off, and the number of crosses was counted and used as an index of adhesion.・ Peeling strength test A coating film was prepared on a substrate, a 1 cm width was cut with a cutter blade until the blade reached the substrate, the edge was peeled off, and the edge of the peeled coating film was 50 mm. The peel strength was measured by pulling in a direction of 180 ° at a speed of / min until the coating film peeled.

[0069]

Example 1 Propylene homopolymer (MFR = 0.2 g /
10 minutes, hereinafter referred to as "PP-1") 80 parts by weight, styrene-butadiene block copolymer hydrogenated product (MFR
= 80 g / 10 minutes, molecular weight distribution = 1.15, styrene content 30
% By weight, hereinafter referred to as “SEBS-1”) 20 parts by weight,
2 parts by weight of hydroxyethyl acrylate (hereinafter referred to as "HEA") and 2,5-dimethyl-2,5-di- (tert-
Butyl peroxy) hexyne-3 (hereinafter referred to as "PO") 0.06 parts by weight was added to a twin-screw extruder (screw diameter 30 m
m, L / D = 42), and the cylinder temperature is 230 ° C.
And melt-kneaded to produce a propylene-based polymer composition. This composition was supplied to an injection molding machine to mold each test piece.

The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 1.

[0071]

Example 2 In Example 1, as shown in Table 1, P
70 parts by weight of P-1 and 30 parts of SEBS-1
A propylene-based polymer composition was produced in the same manner, except that the amount of parts by weight, HEA was changed to 1.5 parts by weight, and the amount of PO was changed to 0.05 parts by weight.

This composition was fed to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 1.

[0073]

Example 3 In Example 1, as shown in Table 1, P
60 parts by weight of P-1 and 40 parts by weight of SEBS-1
A propylene-based polymer composition was produced in the same manner except that the amount of parts by weight, HEA was changed to 1.5 parts by weight, and the amount of PO was changed to 0.04 parts by weight.

This composition was fed to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 1.

[0075]

Comparative Example 1 Instead of PP-1 in Example 3, a high melt flow rate propylene homopolymer (MFR = 2) was used.
A modified polymer composition was produced in the same manner except that 0 g / 10 min, hereinafter referred to as "PP-2") was used and the amount of PO was changed to 0.05 part by weight.

This composition was supplied to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 1.

[0077]

COMPARATIVE EXAMPLE 2 In Example 3, instead of SEBS-1, hydrogenated product of styrene-butadiene block copolymer having low melt flow rate (MFR 4 g / 10 min, styrene content 30% by weight, described as SEBS-2). Use).
Further, a modified polymer composition was prepared in the same manner except that the amount of PO was changed to 0.05 part by weight.

This composition was fed to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 1.

[0079]

Comparative Example 3 Instead of SEBS-1 in Example 3,
Ethylene-propylene random copolymer (EPR, MF
R = 4 g / 10 minutes), and further add PO in an amount of 0.0
A modified polymer composition was prepared in the same manner except that the amount was changed to 5 parts by weight.

The composition was supplied to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 1.

[0081]

Example 4 In Example 1, as shown in Table 1, P
50 parts by weight of P-1 and 50 parts by weight of SEBS-1
A propylene-based polymer composition was produced in the same manner, except that the weight part, the HEA content of 1 part by weight, and the PO content of 0.06 parts by weight were changed.

This composition was fed to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 1.

[0083]

Fifth Embodiment In the first embodiment, as shown in Table 1, S
Instead of EBS-1, hydrogenated styrene-isoprene block copolymer (SEPS, MFR = 90 g / 10 min,
A propylene-based polymer composition was produced in the same manner as in Example 1 except that the same amount was used (molecular weight distribution: 1.05, styrene amount: 30% by weight) and the HEA content was changed to 0.5 part by weight.

This composition was fed to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 1.

[0085]

Example 6 In Example 1, as shown in Table 1, S
Instead of EBS-1, hydrogenated styrene-isoprene block copolymer (SEPS, MFR = 90 g / 10 min,
(Molecular weight distribution 1.05, Styrene amount 30% by weight) are used in the same amount, 20 parts by weight of talc is mixed, HEA content is changed to 0.8 part by weight, PO content is 0.04 part by weight. A propylene-based polymer composition was produced in the same manner as in Example 1 except that

This composition was fed to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 1.

[0087]

[Table 1]

[0088]

Example 7 First, as shown in Table 2, 50 parts by weight of PP-1, 50 parts by weight of SEPS, 3 parts by weight of HEA, and 0.1 parts by weight of PO were blended. Melt kneading was carried out under the same conditions as in 1 to produce a propylene polymer composition (pellets).

Then, 20 parts by weight of an unmodified propylene homopolymer having a high melt flow rate (MFR = 20 g / 10 minutes, "PP-2") in an amount shown in Table 2 was blended with the pellets, and the biaxial screw was used. Extruder (screw diameter 30 mm, L / D =
42) was used, the cylinder temperature was set to 190 ° C., and the mixture was melt-kneaded to produce a composition.

This composition was fed to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 2.

[0091]

Example 8 First, as shown in Table 2, 80 parts by weight of PP-1, 20 parts by weight of SEPS, 3 parts by weight of HEA, and 0.08 parts by weight of PO were blended. Melt kneading was carried out under the same conditions as in 1 to produce a propylene polymer composition (pellets).

Next, the pellets were mixed with 20 parts by weight of SEPS and 10 parts by weight of talc in the amounts shown in Table 2, and then mixed in a twin-screw extruder (screw diameter of 30 mm, L / D = 4).
Using 2), a cylinder temperature was set to 190 ° C. and melt kneading was performed to produce a composition.

This composition was fed to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 2.

[0094]

[Comparative Example 4] As shown in Table 2, a twin-screw extruder (screw diameter: 30 mm, L: 100 parts by weight of PP-1, 1.5 parts by weight of HEA, and 0.05 parts by weight of PO) was used. / D = 4
2), the temperature of the cylinder was set to 230 ° C., and the mixture was melt-kneaded to obtain a graft-modified propylene homopolymer.

As shown in Table 1, 50 parts by weight of SEPS was added to this graft-modified propylene homopolymer,
A twin screw extruder (screw diameter 30 mm, L / D = 42) was melt-kneaded at a cylinder set temperature of 190 ° C. to produce a composition.

This composition was fed to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 2.

[0097]

Comparative Example 5 As shown in Table 2, a twin-screw extruder (screw diameter 30 mm, L / D = 42) was used in an amount of 100 parts by weight of SEPS, 1.5 parts by weight of HEA, and 0.05 parts by weight of PO. ) Was melt-kneaded at a cylinder setting temperature of 250 ° C. to produce a graft-modified SEPS.

Next, as shown in Table 2, 150 parts by weight of PP-2 and 50 parts by weight of talc were blended with this graft-modified SEPS, and a twin-screw extruder (screw diameter 30 mm,
L / D = 42) was used, the cylinder temperature was set to 190 ° C., and the mixture was melt-kneaded to prepare a composition.

This composition was fed to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 2.

[0100]

Comparative Example 6 A propylene-based polymer composition was prepared by melt-kneading under the same conditions as in Example 7 except that SEPS-2: 50 parts by weight was used in place of SEPS: 50 parts by weight. (Pellet) was manufactured.

Next, 20 parts by weight of an unmodified propylene homopolymer having a high melt flow rate (MFR = 20 g / 10 minutes, "PP-2") in an amount shown in Table 2 was blended with the pellets, and the resulting mixture was biaxially mixed. Extruder (screw diameter 30 mm, L / D =
42) was used, the cylinder temperature was set to 190 ° C., and the mixture was melt-kneaded to produce a composition.

This composition was supplied to an injection molding machine to mold each test piece. The bending elastic modulus and the coating test were measured using the obtained test pieces, and the results are shown in Table 2.

[0103]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nagamiko Ito 3 Chikusaigan, Ichihara-shi, Chiba Mitsui Sekiyu Kagaku Kogyo Co., Ltd. (72) Seiichiro Saito 3 Chikusaigan, Ichihara-shi, Chiba Mitsui Petrochemical Gaku Kogyo Co., Ltd. (72) Inagaki Hajime 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd.

Claims (2)

[Claims] 1. A propylene-based polymer (a) having a melt flow rate of 0.05 to 15 g / 10 minutes measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg and a melt flow rate measured under the same conditions of 10 To 200 g / 10 minutes of the aromatic vinyl compound-conjugated diene compound copolymer hydrogenated product (b) in a weight ratio of 99: 1 to 10:90, and the propylene polymer (a) And the hydrogenated product (b) and the component (a)
A propylene-based polymer composition characterized by being modified with 0.1 to 20 parts by weight of a hydroxyl group-containing ethylenically unsaturated compound (c) with respect to a total of 100 parts by weight of the component (b). 2. A propylene polymer (a) having a melt flow rate of 0.05 to 15 g / 10 minutes measured under a temperature of 230 ° C. and a load of 2.16 kg and a melt flow rate measured under the same conditions of 10 To 200 g / 10 minutes of the aromatic vinyl compound-conjugated diene compound copolymer hydrogenated product (b) in a weight ratio of 99: 1 to 10:90, and the propylene polymer (a) And the hydrogenated product (b) and the component (a)
A modified polymer composition modified with 0.1 to 20 parts by weight of a hydroxyl group-containing ethylenically unsaturated compound (c) per 100 parts by weight of the component (b), and an unmodified propylene-based polymer (a-1) and / or a hydrogenated product of an unmodified aromatic vinyl compound-conjugated diene compound copolymer (b-1), and the unmodified propylene-based polymer (a-1) and / or The hydrogenated product (b-1) of the modified aromatic vinyl compound-conjugated diene compound copolymer has a total of 10 of the components (a) and (b).
A propylene-based polymer composition, which is contained in an amount of 1 to 500 parts by weight with respect to 0 parts by weight.