JP2001240638A - Hydrogenated diene based copolymer and polypropylene resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogenated diene polymer giving an excellent polypropylene resin composition having excellent rigidity and shock resistance, low in a brittle temperature and less in physical property deterioration due to the retention during injection molding when compounded as an elastomer component with an ethylene-α-olefin random copolymer. SOLUTION: A hydrogenated product of a block polymer consisting of a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound. In the hydrogenated product, the ratio of 1,2-vinyl bond to 3,4-vinyl bond in the polymer block mainly composed of a conjugated diene compound is 50-75% based on the total of the carbon-carbon double bonds in the polymer block, and the ratio of 1,2-vinyl bond to 3,4-vinyl bond in the polymer block mainly composed of a conjugated diene compound is gradually increasing or gradually decreasing by >=10% from the initial point to the terminal point or coupling part of the polymer block. Further, a polypropylene resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a hydrogenated diene-based polymer, a polypropylene resin, an ethylene-α-olefin random copolymer and a hydrogenated diene-based polymer. The present invention relates to a polypropylene resin composition having an excellent embrittlement temperature.

[0002]

2. Description of the Related Art A molded article of a polypropylene resin is rigid,
It has excellent heat resistance and is used for a wide range of applications.

However, polypropylene resin (PP
Resin) is usually crystalline, and has poor impact resistance, especially at low temperatures, and may be blended with polyethylene or polyisobutylene, polybutadiene, ethylene-α-olefin copolymer to improve impact resistance. And the like.

In order to improve the impact resistance, it is necessary to finely disperse the rubber-like substance in a PP resin.
In the case of a resin composition in which an ethylene-α-olefin copolymer is added to a resin, the phase separation between the PP resin and the ethylene-α-olefin copolymer proceeds due to heat stagnation during molding, and the dispersed particle size of the rubber is enlarged. There is a problem that impact resistance is greatly reduced.

In order to solve this problem, Japanese Patent Application Laid-Open No.
No. 9 proposes a method of blending a specific block copolymer having a polyethylene block with a crystalline polypropylene / ethylene-α-olefin copolymer to suppress an increase in the dispersion particle size of rubber. However, in the addition of the block copolymer, although the enlargement of the dispersed particle diameter of the rubber is suppressed, there is a problem that the surface hardness of the obtained polypropylene resin composition is reduced, and the effect of improving the brittle temperature is sufficient. It turns out that it is not.

In Japanese Patent Application Laid-Open No. 10-101888, a specific block copolymer having the above-mentioned polyethylene block is taken as a comparative example, and a specific styrene-butadiene-styrene triblock copolymer is added with a hydrogenated product. Methods for improving impact strength and flow mark have been proposed. Although it has been found that the composition has an excellent brittle temperature, the effect of suppressing the enlargement of the dispersed particle diameter of the rubber during heat retention is not always sufficient, and thus there is a problem that the impact resistance is reduced.

The present invention has been made on the background of the prior art.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a hydrogenated diene polymer having a specific structure and physical properties capable of providing a polypropylene resin composition having excellent impact resistance and the like. Is to do.

Another object of the present invention is to provide an excellent injection-molded article comprising a polypropylene resin, an ethylene-α-olefin random copolymer and a hydrogenated diene-based polymer of the present invention, which has the above-mentioned problems and is improved. To provide a polypropylene resin composition that can be used.

[0010] Still other objects and advantages of the present invention will become apparent from the following description.

[0011]

According to the present invention, the above objects and advantages of the present invention are firstly achieved by a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound. And the proportion of 1,2- and 3,4-vinyl bonds in the polymer block mainly composed of a conjugated diene compound is 50 to 75% based on the total carbon-carbon double bonds in the polymer block. 1,2- and 3,4 in a polymer block mainly composed of a conjugated diene compound
A hydrogenated product of a block polymer in which the ratio of vinyl bonds gradually increases or decreases by 10% or more from the starting point to the end point or the coupling portion of the polymer block, and at least one of the double bonds derived from the conjugated diene 80% is achieved with hydrogenated hydrogenated diene polymers.

The hydrogenated diene-based polymer of the present invention is preferably used for dynamic viscoelasticity measurement (tensile mode, measurement frequency 1 Hz,
Has a peak of loss tangent (tan delta, tan delta = storage modulus (E ') / loss modulus (E'')) observed at -40 ° C or lower and observed at a measured strain of 0.1%) Height is 0.75 or more.

According to the present invention, the above objects and advantages of the present invention are as follows: (A) a polypropylene resin; (B) an ethylene-α-olefin random copolymer; and (C) the water of the present invention. And the weight ratio of each component is (A) / ((B) +
(C)) = 95/5 to 60/40, and the weight ratio of the component (B) to the component (C) is (B) / (C) = 60/40.
９５95/5, which is achieved by a polypropylene resin composition.

[0014] The polypropylene resin composition of the present invention is preferably a hydrogenated diene-based polymer in which the component (C) has the above-mentioned properties relating to tan delta.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the hydrogenated diene polymer and the polypropylene resin composition of the present invention will be described in detail.

First, as described above, the hydrogenated diene polymer of the present invention comprises a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound. The proportion of 1,2- and 3,4-vinyl bonds in the polymer block is from 50 to 50 based on the total carbon-carbon double bonds in the polymer block.
75%, and the ratio of 1,2- and 3,4-vinyl bonds in the polymer block mainly composed of a conjugated diene compound gradually increases or decreases by 10% or more from the starting point to the end point or the coupling portion of the polymer block. A hydrogenated diene polymer in which at least 80% of the double bonds derived from the conjugated diene are hydrogenated.

That is, the hydrogenated diene polymer of the present invention is a hydrogenated product of a diene copolymer having a high vinyl bond content. Hereinafter, the diene copolymer having a high vinyl bond content is also referred to as a “pre-hydrogenated polymer”.

The pre-hydrogenated polymer includes, for example, (1) a block copolymer composed of a polymer block of an aromatic vinyl compound and a polymer block of a conjugated diene compound, and (2) a polymer block of an aromatic vinyl compound. A block copolymer composed of a random copolymer block of a conjugated diene / aromatic vinyl compound; (3) a tapered block composed of a polymer block of a conjugated diene compound and an aromatic vinyl compound composed of an aromatic vinyl compound and a conjugated diene; Block copolymer consisting of (4) random copolymer block of conjugated diene / aromatic vinyl compound, block copolymer consisting of aromatic vinyl compound and conjugated diene, and block copolymer consisting of tapered block in which aromatic vinyl compound gradually increases It is.

The ratio of the conjugated diene compound and the aromatic vinyl compound constituting the pre-hydrogenated polymer is (conjugated diene compound /
Aromatic vinyl compound, weight ratio, the same applies hereinafter), although not particularly limited, preferably 96/4 to 60/40, more preferably 64/6 to 70/30, and most preferably 64/60/40.
6 to 80/20.

The copolymer of a conjugated diene compound and a vinyl aromatic compound can balance the rigidity of the vinyl aromatic compound with the elastomeric property of the conjugated diene by a polymerization method employed in the production thereof. Therefore, it can be suitably used as a polymer before hydrogenation.

The conjugated diene compound used in the pre-hydrogenated polymer includes, for example, 1,3-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene,
3-butyl-1,3-octadiene, chloroprene and the like. Among them, a hydrogenated diene polymer which can be used industrially and has excellent physical properties can be obtained.
3-Butadiene, isoprene and 1,3-pentadiene are preferred, and 1,3-butadiene and isoprene are particularly preferred.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, divinylbenzene, N, N-
Dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like can be mentioned. Of these, styrene and α-methylstyrene are preferred, and styrene is most preferred.

The pre-hydrogenated polymer may be a polymer in which a polymer molecular chain is extended or branched through a residue of the coupling agent by using a coupling agent.

The coupling agent used in this case includes, for example, diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, , 2-
Examples thereof include dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, and 1,2,4-benzene triisocyanate.

The vinyl bond content in the conjugated diene component in the polymer block mainly composed of conjugated diene in the pre-hydrogenated polymer, that is, the total content of 1,2- and 3,4-vinyl bonds is determined by the value of this block. 50-75%, preferably 55-75%, based on the total carbon-carbon double bonds therein.
%, More preferably 60 to 75%.

If the vinyl bond content in the conjugated diene component in the polymer block mainly composed of a conjugated diene compound in the pre-hydrogenated polymer is lower than 50%, the following (A) polypropylene resin and (B) ethylene-α- The function as a compatibilizer with the olefin random copolymer is low, and as a result,
It is not preferable because the impact strength of the injection-molded article is reduced and the embrittlement temperature is increased. On the other hand, if it is higher than 75%, the rigidity is undesirably reduced.

In the pre-hydrogenated polymer, 1,2- and 3,3-
The proportion of the 4-vinyl bond is preferably increased or decreased by 10% or more, more preferably from 15% or more, from the starting point to the end point or the coupling portion of the polymer block.

In the pre-hydrogenated polymer, 1,2- and 3,4-
(A) a polypropylene resin and (B) an ethylene-α-olefin random copolymer described below, since the ratio of vinyl bonds gradually increases or decreases by 10% or more from the start point to the end point or the coupling portion of the polymer block. (C) A hydrogenated diene polymer having excellent function as a compatibilizer is obtained. Further, by gradually increasing or decreasing by 15% or more, the function as a compatibilizer of the (A) polypropylene resin and the (B) ethylene-α-olefin random copolymer described later is further excellent (C) a hydrogenated diene system A polymer is obtained. Such a hydrogenated diene-based polymer gradually increasing or decreasing by 10% or more can be obtained by adiabatic polymerization.

Preferred as these pre-hydrogenated polymers are (1) a block copolymer comprising a polymer block of an aromatic vinyl compound and a polymer block of a conjugated diene compound;
(2) A block copolymer comprising a polymer block of an aromatic vinyl compound and a random copolymer block of a conjugated diene / aromatic vinyl compound. Most preferred as the pre-hydrogenated polymer is (C-1) a polymer block of an aromatic vinyl compound at both ends and a polymer block of an intermediate conjugated diene compound, and one of the polymer blocks of the conjugated diene compound is included. The proportion of 2,3- and 3,4-vinyl bonds is between 50 and 7 based on the total carbon-carbon double bonds in this block.
5%, and the ratio of 1,2- and 3,4-vinyl bonds in the polymer block of the conjugated diene compound is 15% from the starting point of the polymer block toward the end point or the coupling portion.
The above-mentioned gradually increasing or decreasing block polymer, (C-
2) A polymer block of an aromatic vinyl compound at both ends and a random copolymer block of an intermediate conjugated diene / aromatic vinyl compound, wherein 1,2 in the random copolymer block of a conjugated diene / aromatic vinyl compound -And 3,4-
The proportion of vinyl bonds is 50-75% based on the total carbon-carbon double bonds in this block, and 1,2 in the conjugated diene / aromatic vinyl compound random copolymer block.
A block polymer in which the proportion of-and 3,4-vinyl bonds gradually increases or decreases by 15% or more from the starting point of the polymer block to the end point or the coupling portion.

As described above, the hydrogenated diene polymer (C) of the present invention is obtained by hydrogenating a pre-hydrogenated polymer, that is, a polymer mainly composed of a conjugated diene compound. From the viewpoint that the polymer functions as a compatibilizer for the (A) polypropylene resin and (B) the ethylene-α-olefin random copolymer, the conjugated diene component has a double bond of 80%.
Above, preferably 90% or more. If the degree of hydrogenation is lower than 80%, compatibility with both (A) the polypropylene resin and (B) the ethylene-α-olefin random copolymer becomes poor, and (A) the polypropylene resin and (B) ethylene-α- It is not preferable because the function of the olefin random copolymer as a compatibilizer is reduced.

The number-average molecular weight of the hydrogenated diene polymer (C) is preferably 10,000 to 700,000, more preferably 50,000 to 50,000 from the viewpoint of the balance between moldability and physical properties of the obtained polypropylene resin composition. 600,000, most preferably 60,000-35
It is ten thousand. If the molecular weight is lower than 10,000, the impact strength of the injection-molded article may decrease. If it is higher than 700,000, moldability may be poor.

As the hydrogenated diene polymer (C) of the present invention, those obtained by hydrogenating a blend of two or more pre-hydrogenated polymers are also suitably used. Further, a blend of two or more hydrogenated diene polymers is also suitably used as the hydrogenated diene polymer of the present invention.

The hydrogenated diene polymer (C) of the present invention may be modified with a functional group. For example, the hydrogenated diene polymer may be modified from an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group, an isocyanate group and an epoxy group. It may be modified with a compound having at least one functional group selected from the group consisting of:

It is preferable that the hydrogenated diene polymer (C) exhibits a specific dynamic viscoelasticity from the viewpoint of the physical properties of the polypropylene resin composition described later.

That is, (C) the hydrogenated diene polymer has a peak of loss tangent (tan delta) observed at -40 ° C. or lower in dynamic viscoelasticity measurement under the measurement conditions described below,
And it is preferable that the peak height is 0.75 or more.

When the tan delta peak does not exist at -40 ° C. or lower, the impact strength and the embrittlement temperature of the polypropylene resin composition to be described later are liable to be increased, which is not preferable.

When the tan delta peak height at -40 ° C. or lower is less than 0.75, the polypropylene resin composition described below tends to cause a decrease in impact strength and an increase in brittle temperature, which is not preferable. There is.

(C) Hydrogenated diene polymers are described, for example, in JP-A-3-72512, page 4, upper right column, lines 13 to 6.
It can be obtained by the method disclosed in the first line at the lower left of the page.

Next, the polypropylene resin (A) used in the present invention includes a homopolymer of propylene or a structural unit derived from an α-olefin other than propylene, preferably an α-olefin having 2 or 4 to 20 carbon atoms. Is contained in an amount of 10 mol% or less.

Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, and 4-methyl-1 -Pentene, 2-methyl-1
-Butene, 3-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene, 3-methyl-1-pentene, ethyl -1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3-
Methyl-1-hexene, dimethyl-1-hexene, 3,5,
5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, dimethyl-1-octene, ethyl-1-octene, methyl-1-nonene, vinylcyclopentane, vinylcyclohexane, vinylnorbornane, etc. No.

These α-olefins can be used alone or in combination of two or more.

The copolymer of propylene and these α-olefins may be a random copolymer or a block copolymer.

The polypropylene resin (A) used in the present invention is preferably a propylene / ethylene block copolymer, and particularly preferably a propylene / ethylene block copolymer having an ethylene content of 25% by weight or less.

(A) The melt flow rate (MFR) of the polypropylene resin is a value measured at 230 ° C. under a load of 2.16 kg according to ASTM-D1238.
Preferably from 0.1 to 300 g / 10 min, more preferably from 1 to 300 g / 10 min.
-200 g / 10 min, more preferably 10-150 g
/ 10 min, most preferably 30 to 120 g / 10 min.

When the MFR is in the above range, the polypropylene resin composition of the present invention is excellent in fluidity and easy to form a large molded product. If the melt flow rate is higher than the above, the polypropylene resin composition tends to have poor impact strength.

The (A) polypropylene resin used in the present invention is crystalline and has a distinct melting point. As a value measured by the DSC method, the melting point is 140 ° C. or higher, particularly 15 ° C.
The temperature is preferably 5 ° C. or higher from the viewpoint of heat resistance.

The polypropylene resin (A) used in the present invention can be produced by using an ordinary stereoregular catalyst, and is commercially available.

Next, the ethylene-α-olefin random copolymer (B) used in the present invention is composed of a structural unit derived from ethylene, a structural unit derived from α-olefin, and a copolymer which is optionally copolymerized. It consists of a proportion of structural units derived from non-conjugated dienes.

Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene and 4-methyl-1 -Pentene, 2-methyl-
1-butene, 3-methyl-1-butene, 3-methyl-1
-Butene, 3,3-dimethyl-1-butene, diethyl-1
-Butene, trimethyl-1-butene, 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl- 1-pentene, 3-methyl-1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, dimethyl-
Examples thereof include 1-octene, ethyl-1-octene, methyl-1-nonene, vinylcyclopentane, vinylcyclohexane, and vinylnorbornane. Of these, 1-butene, 1-butene
Hexene and 1-octene are preferred, and 1-butene and 1-octene are particularly preferred.

These α-olefins can be used alone or in combination of two or more.

The weight ratio of the structural units derived from ethylene to the structural units derived from α-olefin in the ethylene-α-olefin random copolymer of the present invention is not particularly limited, but the weight ratio of ethylene / α-olefin is not limited. Preferably 8
0/20 to 20/80, more preferably 75/25 to
25/75.

In the ethylene-α-olefin random copolymer (B), the non-conjugated diene optionally copolymerized is not particularly limited. Specific examples of the non-conjugated diene include 5-ethylidene-2-norbornene, dicyclopentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene,
-Methyl-1,4-hexadiene, 5-methyl-1,4-
Examples thereof include hexadiene, 1,7-octadiene, 1,8-nonadiene, 7-methyl-1,6-octadiene, 1,9-decadiene, 5-vinyl-2-norbornene, and 2,5-norbornadiene.

(B) When the catalyst system described below used for producing the ethylene-α-olefin random copolymer is a metallocene-based catalyst, α such as 1,7-octadiene and 1,9-decadiene are used. , ω-diene can also be used.

These non-conjugated dienes can be used alone or in combination of two or more.

The injection molded article obtained from the polypropylene resin composition of the present invention by using the above-mentioned (B) ethylene-α-olefin random copolymer has excellent impact resistance, low-temperature embrittlement, and heat resistance. , The rigidity is balanced to a high level.

The melting point of the ethylene-α-olefin random copolymer of the present invention is not particularly limited, but is preferably 80 ° C. or less, more preferably 60 ° C. or less. Here, the melting point is a temperature at which a main endothermic peak is measured by the DSC method.

The polymerization catalyst used for producing the ethylene-α-olefin random copolymer of the present invention includes, for example, at least one transition metal compound selected from V, Ti, Zr and Hf, and an organometallic compound. An olefin polymerization catalyst consisting of Particularly preferred examples of such an olefin polymerization catalyst include a vanadium-based catalyst comprising a vanadium compound and an organoaluminum compound, a metal compound having a cyclopentadienyl group and an aluminoxane compound, or an ionic compound which reacts with the metal compound. A metallocene-based catalyst comprising an ionic compound forming a complex can be exemplified.

Next, as the component (C) in the polypropylene resin composition of the present invention, the aforementioned hydrogenated diene-based polymer can be suitably used. Particularly preferably, the pre-hydrogenated polymer comprises (C-1) a polymer block of an aromatic vinyl compound at both terminals and a polymer block of an intermediate conjugated diene compound, and one of the polymer blocks of the conjugated diene compound is present. The proportion of 2,2- and 3,4-vinyl bonds is 50-75% based on the total carbon-carbon double bonds in this block, and the 1,2- and 3,3-vinyl bonds in the polymer block of the conjugated diene compound. A block polymer in which the proportion of 4-vinyl bonds gradually increases or decreases by 15% or more from the starting point to the end point or the coupling portion of the polymer block, or (C-
2) A polymer block of an aromatic vinyl compound at both ends and a random copolymer block of an intermediate conjugated diene / aromatic vinyl compound, wherein 1,2 in the random copolymer block of a conjugated diene / aromatic vinyl compound -And 3,4-
The proportion of vinyl bonds is 50-75% based on the total carbon-carbon double bonds in this block, and 1,2 in the conjugated diene / aromatic vinyl compound random copolymer block.
The above-mentioned hydrogenated diene polymer, which is a block polymer in which the proportion of-and 3,4-vinyl bonds gradually increases or decreases by 15% or more from the starting point of the polymer block to the end point or the coupling portion.

These (A) polypropylene resin and (B)
Polypropylene resin excellent in impact resistance, embrittlement temperature, heat resistance and rigidity by using hydrogenated diene-based polymer (C) which has excellent function as compatibilizer of ethylene-α-olefin random copolymer In addition to the fact that the composition is obtained, even when the residence time of the molten resin changes due to a change in the molding cycle during injection molding, etc., (B) the ethylene-α-olefin random copolymer is contained in the polypropylene resin composition. Since it is difficult to re-agglomerate, a polypropylene resin composition having an extremely small change in impact resistance can be obtained.

In the polypropylene resin composition of the present invention, the weight ratio of the above components is (A) / ((B) + (C)) = 95.
/ 5 to 60/40. Where (B) component and (C)
The weight ratio of the components is (B) / (C) = 60 / 40-95 /
5, preferably (B) / (C) = 70/30 to 90/1
0. Here, (A) a polypropylene resin and (B) an ethylene-α-olefin random copolymer and (C)
The total amount with the hydrogenated diene polymer is 100 parts by weight.

The above components (A), (B) and (C)
From the polypropylene resin composition of the present invention containing the components, a polypropylene resin composition having excellent rigidity, heat resistance, impact resistance, and embrittlement temperature can be obtained.

The polypropylene resin composition of the present invention includes:
In order to reduce costs, improve printability, and improve the balance of physical properties, other polymers different from the components (A), (B) and (C) are blended within a range that does not impair the achievement of the object of the present invention. Can be. Other polymers that can be blended, for example, various polyethylene, polybutene, polyhexene, polyolefins such as polymethylpentene,
Olefin copolymers other than the components (A) and (B), styrene-butadiene block copolymers (SB
S) and a styrene-isoprene block copolymer. Further, various modified polymers obtained by grafting maleic anhydride to various polymers such as a polyolefin resin, ethylene-propylene rubber, and ethylene butene rubber may be added. These modified polymers may be effective for improving coating properties and printability in some cases.

The amount of the other polymer different from the components (A), (B) and (C) is 100 parts by weight in total of the components (A), (B) and (C). It is preferably 20 parts by weight or less based on parts.

The polypropylene resin composition of the present invention includes:
You may mix | blend an inorganic filler as needed. The compounding amount of the inorganic filler is the above-mentioned (A) component, (B) component and (C)
The amount is preferably 40 parts by weight or less, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the total amount of the components.

Examples of the inorganic filler used include natural silicates or silicates such as talc, kaolinite, calcined clay, virophilite, sericite, wollastonite, precipitated calcium carbonate, heavy calcium carbonate, and the like.
Carbonates such as magnesium carbonate; hydroxides such as aluminum hydroxide and magnesium hydroxide; oxides such as zinc oxide, zinc white and magnesium oxide; synthetic silica such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, and silicic anhydride Powdery fillers represented by silicates, flake-like fillers such as mica, basic magnesium sulfate whiskers, calcium titanate whiskers, aluminum borate whiskers, sebiolite, PMF (Processed)
Fibrous fillers such as Mineral Fiber, zonotolite, potassium titanate, and elestadite, and balun fillers such as glass balun and fly ash balun. These can be used alone or in combination of two or more.

Among them, talc is preferably used from the viewpoints of improving the rigidity, surface hardness, heat deformation temperature and dispersibility of the component (B) of the molded product. Particularly, talc having an average particle size of 0.01 to 10 μm is preferably used. Formulation is preferred. When talc is compounded, the amount is preferably 40 parts by weight or less, more preferably 5 to 30 parts by weight, per 100 parts by weight of the total of the components (A), (B) and (C).

The polypropylene resin composition of the present invention includes:
Heat stabilizers, nucleating agents, ultraviolet absorbers, lubricants, antistatic agents,
Flame retardants, pigments, dyes, phenol-based, sulfur-based, phosphorus-based antioxidants, dispersants, copper damage inhibitors, neutralizers, foaming agents, plasticizers, foam inhibitors, crosslinking agents, peroxides, etc. An additive such as a flowability improver, a light resistance stabilizer such as HALS, and a weld strength improver may be added within a range that does not impair the achievement of the object of the present invention. The amount of additives is (A) component, (B)
2 per 100 parts by weight of the total amount of component and component (C)
It is preferably at most part by weight.

The polypropylene resin composition of the present invention is prepared by charging the above-mentioned components into, for example, a Henschel mixer, a V-type blender, a tumbler blender, a ribbon blender, etc., and then mixing them. Kneader,
It is obtained by melt-kneading with a Banbury mixer or the like.

[0069]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the scope of the present invention is not limited by the examples. Note that “parts” and “%” are based on weight unless otherwise specified. The polypropylene resin, ethylene-α-olefin random copolymer, (C) hydrogenated diene polymer and filler used in the following Examples and Comparative Examples are as follows.

(A) Polypropylene resin PP1: BC06C, manufactured by Nippon Polychem Co., Ltd.
MFR = 60 (g / 10 minutes) (B) Ethylene-α-olefin random copolymer (B-1): ethylene-butene-diene random copolymer Mooney viscosity (ML _{1 + 4} , 100 ° C.) = 88, Density = 0.
86, butene content = 32 wt%, diene content = 4 wt% (B-2): ENGAGE818 manufactured by Dupont Dow
0 Mooney viscosity (ML _{1 + 4} , 100 ° C.) = 49, density = 0.86
g / cm ³ ethylene-octene random copolymer (C) Hydrogenated diene polymer A hydrogenated diene polymer having the structure shown in Table 1 was synthesized and used. Various data in Table 1 are values measured as follows.

It was measured by infrared analysis based on the absorption of a phenyl group having a bound vinyl aromatic compound content of 679 cm ^-1 . The vinyl bond content of the conjugated diene was calculated by the Hampton method using infrared analysis. Using hydrogenation ratio ethylene tetrachloride as a solvent, 100MHz, ¹ H-N
It was calculated from the MR spectrum. The weight-average molecular weight of the hydrogenated diene polymer was determined in terms of polystyrene by gel permeation chromatography (GPC) at 135 ° C. using trichlorobenzene as a solvent. The tan delta polymer was melt-kneaded with an open roll at 180 ° C. for 3 minutes, and sheeted out to about 1.5 mm. This sheet 1
After using a 20 × 130 × 2 (mm) press mold and pressurizing with a hot press (200 ° C.) at 10 MPa for 3 minutes,
After cooling at 15 MPa for 5 minutes between the pressure plates cooled to 5 ° C., a 2 mm sheet was obtained. At this time, two rolled sheets were pressed so that the grain was perpendicular to each other and then pressed. The obtained 2 mm sheet is 100 × 70 × 1 (mm)
With a hot press (200 ° C)
After pressurizing at 3 MPa for 3 minutes, the mixture was cooled at 25 MPa for 5 minutes between pressurizing plates to obtain a 1 mm sheet.

The obtained 1 mm thick sheet was punched into a 5 mm width and used for measurement. The measurement conditions are as follows. Apparatus: Rheometrics RSA-II Measurement temperature range: -90 ° C to 150 ° C (held at -90 ° C for 5 minutes) Heating rate: 3 ° C / min Measurement frequency: 1 Hz Mode: Tension Measurement strain: 0.1%

Example 1 (Synthesis of C-1) In a 10-liter autoclave, 5 kg of degassed and dehydrated cyclohexane and 40 g of styrene were charged, and 100 g of tetrahydrofuran and 0.6 g of n-butyllithium were added. Adiabatic polymerization from 50 ° C. was performed for 30 minutes. After the temperature of the reaction solution was adjusted to 10 ° C., 900 g of 1,3-butadiene and 40 g of styrene were added to perform adiabatic polymerization. The residual monomer was measured by gas chromatography, and after the conversion reached almost 100%, 20 g of styrene was further added to carry out polymerization.

After completion of the reaction, the living Li was measured and found to be 4.8 mmol. 0.26 g of 4-hydroxy-4-methyl-2-pentanone was added to the system, and the mixture was stirred for 10 minutes. From the change in the color of the polymer solution, it was confirmed that there was no living polymer terminal lithium as a living anion. did.

Next, 4-hydroxy-4-methyl-2-pentanone 0.8 dissolved in 20 ml of cyclohexane.
A reaction product obtained by previously reacting 2 g and 0.96 g of n-butyllithium in a nitrogen atmosphere for 10 minutes was charged, and 0.47 g of bis (cyclopentadienyl) titanium dichloride and 1.36 g dissolved in 10 ml of toluene were charged. Was mixed in advance in a nitrogen atmosphere, and the mixture was stirred in an autoclave. Hydrogen gas is supplied at a pressure of 0.8 MPa, and 90
The hydrogenation reaction was performed at 1.5 ° C. for 1.5 hours. The hydrogenated polymer thus obtained had a degree of hydrogenation of 99%, a weight average molecular weight of 290,000 and a bound styrene content of 10.0%.

1,2 of the butadiene portion of the polymer before hydrogenation
-The vinyl bond content was 70%. The 1,2-vinyl bond content measured at the start of the 1,3-butadiene block polymerization was 80%, the 1,2-vinyl bond content measured after the polymerization was completed, and the 1,2-vinyl bond content at the start of the polymerization. The 1,2-butadiene block had a 1,2-vinyl bond content of 60% at the end of the polymerization calculated from the above, and the difference between the 1,2-vinyl bond contents of both molecular terminals calculated therefrom was 20%. Was.

Example 2 (Synthesis of C-2): 45 g of tetrahydrofuran and 0.65 g of n-butyllithium
Polymerization was carried out in the same manner as in Example 1 except that the polymerization was carried out. Then
A hydrogenation reaction was performed in the same manner as in Example 1. The hydrogenated polymer obtained had a hydrogenation rate of 98% and a weight average molecular weight of 23.
The bound styrene content was 10.1%.

Before the hydrogenation, one of the butadiene moieties of the polymer
The 2-vinyl bond content was 64%. Also, 1,3-
The 1,2-vinyl bond content measured at the start of the butadiene block polymerization is 74%, and the polymerization end time calculated from the 1,2-vinyl bond content measured after the polymerization and the 1,2-vinyl bond content at the start of the polymerization. The 1,2-butadiene block had a 1,2-vinyl bond content of 53%, and the difference between the 1,2-vinyl bond contents at both molecular terminals calculated therefrom was 21%.

Example 3 (Synthesis of C-3) In a 10-liter autoclave, 5 kg of degassed and dehydrated cyclohexane and 40 g of styrene were charged, and 100 g of tetrahydrofuran and 0.6 g of n-butyllithium were added. Adiabatic polymerization from 50 ° C. was performed for 30 minutes. After the temperature of the reaction solution was adjusted to 10 ° C., 940 g of 1,3-butadiene was added to perform adiabatic polymerization. The residual monomer was measured by gas chromatography, and after the conversion reached almost 100%, 20 g of styrene was further added to carry out polymerization. Next, a hydrogenation reaction was performed in the same manner as in Example 1. The hydrogenated polymer thus obtained had a degree of hydrogenation of 96%, a weight average molecular weight of 270,000 and a bound styrene content of 5.9%.

The 1,1 butadiene portion of the polymer before hydrogenation
The 2-vinyl bond content was 70%. Also, 1,3-
The 1,2-vinyl bond content measured at the start of the butadiene block polymerization is 81%, and the polymerization end time calculated from the 1,2-vinyl bond content measured after the polymerization and the 1,2-vinyl bond content at the start of the polymerization. The 1,2-vinyl bond content of the 1,3-butadiene block was 59%, and the difference between the 1,2-vinyl bond contents of both molecular terminals calculated therefrom was 22%.

Example 4 (Synthesis of C-4) 5 kg of degassed and dehydrated cyclohexane and 90 g of styrene were charged into an autoclave having a capacity of 10 liters, and 40 g of tetrahydrofuran and 0.9 g of n-butyllithium were added. Adiabatic polymerization from 50 ° C. was performed for 30 minutes. After the temperature of the reaction solution was adjusted to 10 ° C., 820 g of 1,3-butadiene was added to perform adiabatic polymerization. The residual monomer was measured by gas chromatography, and after the conversion reached almost 100%, 90 g of styrene was further added to carry out polymerization. Next, a hydrogenation reaction was performed in the same manner as in Example 1. The hydrogenated polymer thus obtained had a degree of hydrogenation of 99%, a weight average molecular weight of 140,000 and a bound styrene content of 18.0%.

The 1,1 butadiene portion of the polymer before hydrogenation
The 2-vinyl bond content was 60%. Also, 1,3-
The 1,2-vinyl bond content measured at the start of the butadiene block polymerization is 71%, and the polymerization end time calculated from the 1,2-vinyl bond content measured after the polymerization and the 1,2-vinyl bond content at the start of the polymerization. The 1,2-vinyl bond content of the 1,3-butadiene block was 51%, and the difference between the 1,2-vinyl bond contents at both molecular terminals calculated therefrom was 20%.

Comparative Example 1 (Synthesis of C-5): 5 kg of degassed and dehydrated cyclohexane and 90 g of styrene were charged into an autoclave having an internal volume of 10 liters, and 40 g of tetrahydrofuran and 0.9 g of n-butyllithium were added. Polymerization was carried out at 50 ° C. After 30 minutes, 820 g of 1,3-butadiene was added, and polymerization was carried out at 50 ° C. isothermally. The residual monomer was measured by gas chromatography, and the conversion was almost 1
After the content became 00%, 90 g of styrene was further added to carry out polymerization. Next, a hydrogenation reaction was performed in the same manner as in Example 1. The hydrogenated polymer thus obtained had a degree of hydrogenation of 99%, a weight average molecular weight of 140,000 and a bound styrene content of 17.9%.

The butadiene portion of the polymer before hydrogenation
The 2-vinyl bond content was 60%. Also, 1,3-
The 1,2-vinyl bond content measured at the start of the butadiene block polymerization is 60%, and the polymerization end time calculated from the 1,2-vinyl bond content measured after the polymerization and the 1,2-vinyl bond content at the start of the polymerization. The 1,2-butadiene block had a 1,2-vinyl bond content of 60%, and the difference between the 1,2-vinyl bond contents at both molecular terminals calculated therefrom was 0%.

Comparative Example 2 (Synthesis of C-6): 200 g of tetrahydrofuran and 0.6 g of n-butyllithium
Polymerization was carried out in the same manner as in Example 1 except that the polymerization was carried out. Then
A hydrogenation reaction was performed in the same manner as in Example 1. The hydrogenated polymer obtained had a hydrogenation rate of 99% and a weight average molecular weight of 30.
The bound styrene content was 10.0%.

Before the hydrogenation, one of the butadiene moieties of the polymer
The 2-vinyl bond content was 80%. Also, 1,3-
The 1,2-vinyl bond content measured at the start of the butadiene block polymerization is 91%, and the polymerization end time calculated from the 1,2-vinyl bond content measured after the polymerization and the 1,2-vinyl bond content at the start of the polymerization. The 1,2-vinyl bond content of the 1,3-butadiene block was 69%, and the difference between the 1,2-vinyl bond contents of both molecular terminals calculated therefrom was 22%.

[0087]

[Table 1]

(C) Filler Talc: Measurement and evaluation of physical properties of the composition LMS200 manufactured by Fuji Talc Co., Ltd. are as follows.

(1) Preparation of Test Piece A test piece was prepared from the polypropylene resin composition by using an injection molding machine at an injection temperature of 220 ° C. and a mold temperature of 40 ° C., and the physical properties were evaluated. (2) Impact resistance Measured at 23 ° C. using a post-notched specimen in accordance with JIS K7110. (3) Hardness In accordance with JIS K7202, the hardness was measured at 23 ° C. on an R scale. (4) Embrittlement temperature Measured in accordance with JIS K7216. (5) Retention stability The molding cycle of injection molding was performed in 35 seconds and 635 seconds.
The impact resistance was evaluated in the same manner as in (2), and the retention stability index was calculated by the following equation. The higher the retention stability index, the smaller the decrease in impact resistance due to the retention of the molten resin in the injection molding machine, which is preferable. Retention stability index = (impact strength when molding cycle is 35 seconds / impact strength when molding cycle is 635 seconds) × 100

Examples 5 to 9 and Comparative Examples 3 to 7 The components shown in Table 2 were mixed with a Henschel mixer.
Using a twin screw extruder (PCM-45, manufactured by Ikegai Iron and Steel Company),
The mixture was melt-kneaded at a temperature of 150 to 200 ° C. to obtain a polypropylene resin composition, and the obtained composition was evaluated for impact resistance, hardness and brittleness temperature by the methods described above.
Table 2 shows the results.

[0091]

[Table 2]

The following is clear from the results shown in Table 2.

Each of the compositions of Examples 5 to 9 had a temperature of 23 ° C.
Has high IZOD impact strength, low embrittlement temperature, high Rockwell hardness, and good physical property balance. Further, the retention stability index is high, and the physical properties of the injection molded product are stable even when the retention time changes, which is preferable.

On the other hand, the compositions of Comparative Examples 3 to 7
Impact strength because a hydrogenated diene-based polymer was used or did not use a hydrogenated diene-based polymer outside the scope of the present invention,
The brittle temperature is not sufficiently improved, and the retention stability index is low and not good.

[0095]

The polypropylene resin composition comprising the hydrogenated diene polymer of the present invention and an ethylene-α-olefin random copolymer as an elastomer component is excellent in rigidity and impact resistance and has a brittle temperature. An excellent composition that is low and has little physical property deterioration due to stagnation during injection molding can be obtained.

The hydrogenated diene polymer and polypropylene resin composition of the present invention can be used for interior and exterior parts of automobiles, stationery products, materials for civil engineering and construction, sanitary fields, parts for AV and home appliances,
It is useful for various uses such as miscellaneous goods.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masafumi Shimakage 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation (72) Inventor Akihiko Morikawa 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR F-term in stock (reference) 4J002 BB052 BB121 BB141 BB151 BB152 BP013 BP021 FD010 4J026 HA05 HA06 HA07 HA08 HA14 HA15 HA16 HA18 HA26 HA32 HA39 HB05 HB06 HB07 HB08 HB14 HB15 HB16 HB18 HB26 HB32BB ABBB ABB HB08 AB AQ12P AS01Q AS02Q AS03Q AS04Q AS07Q BA31P CA04 CA16 CA25 DA49 GC02 HA03

Claims (4)

[Claims] 1. A polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound, wherein 1,2- and 3,4 in the polymer block mainly composed of a conjugated diene compound. The percentage of vinyl bonds is 5 based on the total carbon-carbon double bonds in the polymer block;
0 to 75%, and the proportion of 1,2- and 3,4-vinyl bonds in the polymer block mainly composed of a conjugated diene compound is 10% or more from the starting point to the end point or the coupling portion of the polymer block. A hydrogenated product of a gradually increasing or decreasing block polymer, wherein at least 80% of the double bond derived from the conjugated diene is hydrogenated. 2. Loss tangent (t) observed in dynamic viscoelasticity measurement (tensile mode, measurement frequency 1 Hz, measurement strain 0.1%)
The hydrogenated diene-based polymer according to claim 1, which has an (an delta) peak at -40 ° C or lower, and has a peak height of 0.75 or higher. 3. A (A) polypropylene resin, (B) an ethylene-α-olefin random copolymer, and (C) a hydrogenated diene polymer according to claim 1, wherein the weight ratio of each component is (A) / ((B) +
(C)) = 95/5 to 60/40, and the weight ratio of the component (B) to the component (C) is (B) / (C) = 60/40.
To 95/5. 4. The polypropylene resin composition according to claim 3, wherein the component (C) is the hydrogenated diene polymer according to claim 2.