JP2001294712A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the mechanical properties of a thermoplastic resin composition comprising a polyolefin resin and a polyvinyl chloride resin. SOLUTION: A block copolymer which comprises a polymer block (A) consisting of (meth)acrylic ester units and a polymer block (B) consisting of conjugated alkadiene units, of which at least a part of carbon-carbon double bonds may be hydrogenated into carbon-carbon saturated bonds, is incorporated into a thermoplastic resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing a polyolefin-based resin and a polyvinyl chloride-based resin, wherein the thermoplastic resin composition has improved mechanical properties.

[0002]

2. Description of the Related Art In general, a resin composition composed of a plurality of resins often has insufficient mechanical properties due to incompatibility among the resin components constituting the resin composition. . If a suitable compatibilizer is added during mixing of mutually incompatible resins, it is also possible to obtain a resin composition having significantly improved mechanical properties. In recent years, for this purpose, compatibilizing agents for compatibilizing different kinds of resins have begun to be developed. The use of a compatibilizer has also been proposed for a thermoplastic resin composition comprising a polyolefin-based resin and a polyvinyl chloride-based resin. For example, JP-A-6-190829 discloses that a composite comprising polyvinyl chloride and polypropylene is pulverized, and an ethylene-vinyl acetate random copolymer is used for 100 parts by weight of the pulverized product.
Ethylene-acrylate random copolymer or ethylene-methacrylate random copolymer 1
A method for regenerating a composite comprising polyvinyl chloride and polypropylene, which comprises adding and kneading 20 parts by weight, is described. JP-A-6-49280 discloses that a thermoplastic resin composition containing a modified vinyl chloride resin and an olefin resin contains ethylene-propylene-diene rubber (EPDM) and ethylene-vinyl acetate random as a modifier. For a polymer composition containing a polymer, a graft polymer modifier obtained by graft-polymerizing a functional group-containing monomer such as glycidyl methacrylate and other monomers such as methyl methacrylate and styrene has been proposed. ing.

[0003]

In a resin composition composed of a plurality of resins as described above, the mechanical properties may be improved to a high degree by adding an appropriate amount of an appropriate compatibilizer. If the amount of the compatibilizer in the resin composition is too large, other disadvantages such as a decrease in performance may occur. Therefore, as far as the compatibilizing agent can achieve the same effect of improving the mechanical properties, the addition amount can be as small as possible. Is required to be as high as possible. Japanese Unexamined Patent Publication No.
Modifiers selected from ethylene-vinyl acetate random copolymer, ethylene-acrylate random copolymer and ethylene-methacrylic ester random copolymer, used in the regeneration treatment method described in JP 190829 Therefore, it is difficult to say that the effect of improving the mechanical properties is still sufficient.For example, when a high degree of improvement in impact resistance is required, it is necessary to add a relatively large amount. The elastic modulus of the composition is significantly reduced. Further, the modifier described in JP-A-6-49280 is a very special graft copolymer composition obtained by a complicated production method and has poor versatility.

Accordingly, it is desired that a thermoplastic resin composition containing a polyolefin-based resin and a polyvinyl chloride-based resin provides an additive which has a high effect of improving mechanical properties and is excellent in versatility. . Thus, an object of the present invention is to provide a thermoplastic resin composition containing a polyolefin-based resin and a polyvinyl chloride-based resin, a highly versatile novel additive having an excellent effect of improving mechanical properties, Another object of the present invention is to provide a thermoplastic resin composition containing the novel additive.

[0005]

Means for Solving the Problems The present inventors diligently studied to solve the above-mentioned problems, and converted a specific block copolymer into a thermoplastic resin composition containing a polyolefin resin and a vinyl chloride resin. When added, the present inventors have found that a high effect of improving mechanical properties is exhibited even with a relatively small amount of addition, and that there is no inconvenience such as a decrease in melt formability. I came to.

That is, the present invention firstly comprises a polyolefin resin (I), a polyvinyl chloride resin (II) and a block copolymer (III), wherein the block copolymer (III) comprises at least A polymer block (A) consisting of one kind of methacrylate unit or acrylate unit and at least one kind of conjugated alkadiene unit, wherein at least a part of carbon-carbon double bond is hydrogenated to obtain carbon-carbon saturated A thermoplastic resin composition, which is a block copolymer containing a polymer block (B) which may be converted into a bond. Further, the present invention secondly provides the above block copolymer (III)
An additive for a thermoplastic resin composition containing a polyolefin-based resin (I) and a polyvinyl chloride-based resin (II), comprising:

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The block copolymer (III) used in the present invention comprises the above polymer block (A) and the above polymer block (B). For the block arrangement of the block copolymer (III), for example, AB
Type diblock copolymer, ABA type triblock copolymer, BAB type triblock copolymer and the like. Among these, AB type diblock copolymers are preferred.

The polymer block (A) constituting the block copolymer (III) is a fragment of an addition polymer comprising at least one methacrylate unit or acrylate unit (hereinafter referred to as methacrylic acid and acrylic unit). The acid is sometimes collectively referred to as “(meth) acrylic acid”). In the polymer block (A), the main constituent unit may be at least one methacrylate unit, at least one acrylate unit, or both, and further, a constituent unit derived from a comonomer may be used. A small proportion may be contained. Examples of the methacrylate unit include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate And methacrylic acid esters such as 2-methoxyethyl methacrylate, glycidyl methacrylate, and 2-dimethylaminoethyl methacrylate. The acrylate unit includes, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, dodecyl acrylate, acrylic acid 2 And structural units derived from acrylates such as -ethylhexyl, 2-methoxyethyl acrylate, glycidyl acrylate, and 2-dimethylaminoethyl acrylate. Among these (meth) acrylate units, a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms is preferable, and a structural unit derived from methyl methacrylate is particularly preferable. preferable.

As a structural unit of the polymer block (A),
If necessary, a structural unit derived from a monomer copolymerizable with the (meth) acrylic acid ester may be contained. However, when the polymer block (A) contains a structural unit derived from a copolymerizable monomer, its content is not more than 45 mol% based on all the structural units constituting the polymer block (A). Preferably, 30 mol%
It is more preferably at most 10 mol%. Examples of the structural units that can be used in combination include, for example, structural units derived from nitrile monomers such as methacrylonitrile and acrylonitrile; and amide monomers such as methacrylamide and acrylamide. it can.

The number average molecular weight of the polymer block (A) is
Although the effect of improving the mechanical properties in the thermoplastic resin composition obtained to a certain degree is easily obtained, the effect is not so high when producing the block copolymer (III) and using the thermoplastic resin composition. , The handleability at the time of preparing is good. From these viewpoints, the number average molecular weight is preferably in the range of 2,000 to 1,000,000, and more preferably in the range of 5,000 to 500,000.

The polymer block (B) constituting the block copolymer (III) is a fragment of an addition polymer comprising at least one conjugated alkadiene unit. In the conjugated alkadiene unit of at least a part (or all) of the polymer block (B), the carbon-carbon double bond therein may be converted to a carbon-carbon saturated bond by hydrogenation. The polymer block (B) may be such that the main constituent unit is at least one kind of conjugated alkadiene unit (may be a constituent unit obtained by hydrogenating a conjugated alkadiene unit), and is further derived from a comonomer. A small proportion of a structural unit may be contained. Examples of the conjugated alkadiene unit include butadiene, isoprene, 2-methyl-1,3-pentadiene, and 3-methyl-
Structural unit derived from a conjugated alkadiene having 4 to 10 carbon atoms such as 1,3 pentadiene, 1,3-hexadiene, piperylene and 1,3-octadiene;
Structural units derived from a conjugated alkadiene are more preferably hydrogenated, and particularly preferred are a hydrogenated butadiene unit and a hydrogenated isoprene unit.

The conjugated alkadiene unit has a plurality of bonding forms. For example, 1,4 in butadiene units
There may be a structural unit in the form of a bond and a structural unit in the form of a 1,2-bond, and in the isoprene unit, a structural unit in the form of a 1,4-bond, a structural unit in the form of a 3,4-bond, and There may be structural units in the form of 1,2-bonds. When the conjugated alkadiene unit constituting the polymer block (B) is a butadiene unit (may be in a hydrogenated form) and / or an isoprene unit (may be in a hydrogenated form), The proportion of the structural units in the 4-bond form (including the structural units in the hydrogenated form) is as follows:
It is preferably within a range of 10% or more and less than 100% based on all conjugated alkadiene units (including constitutional units in a hydrogenated form).

The number average molecular weight of the polymer block (B) is
Although the effect of improving the mechanical properties in the thermoplastic resin composition obtained to a certain degree is easily obtained, the effect is not so high when producing the block copolymer (III) and using the thermoplastic resin composition. , The handleability at the time of preparing is good. From these viewpoints, the number average molecular weight is preferably in the range of 2,000 to 1,000,000, and more preferably in the range of 5,000 to 500,000.

In the polymer block (B), of the carbon-carbon double bonds derived from the conjugated alkadiene units in the polymer block, from the viewpoint of a compatibilizing effect on the polyolefin resin and the polyvinyl chloride resin. It is preferable that at least 60% or more of the above is converted to a carbon-carbon saturated bond by hydrogenation. In the same perspective,
The hydrogenation rate is more preferably 80% or more.
It is particularly preferably 0% or more (may be 100%). The hydrogenation rate can be controlled to an arbitrary value by selecting reaction conditions such as a reaction rate and a reaction time when the block polymer (III) is subjected to a hydrogenation reaction as described later. is there.

When the number average molecular weight of the block copolymer (III) is higher to some extent, the effect of improving the mechanical properties of the obtained thermoplastic resin composition is easily exerted, and it is difficult to bleed out from the thermoplastic resin composition. This is preferred. However, if the number average molecular weight is not too high, the handleability in producing the block copolymer (III) and preparing the thermoplastic resin composition using the same will be better. From these viewpoints, the number average molecular weight is 4,000
Preferably in the range of 0 to 2,000,000,
More preferably, it is in the range of 10,000 to 500,000.

The method for producing the block copolymer (III) is not particularly limited, and the (meth) acrylic acid ester and the conjugated alkadiene may be subjected to block copolymerization by any polymerization method, and if necessary, the conjugated alkadiene may be used. By performing hydrogenation of units, a desired block copolymer can be produced. However, since the compatibilizing effect on the polyolefin-based resin and the polyvinyl chloride-based resin is particularly prominently expressed, the polymerization method has a high block efficiency, and an undesired homopolymer having a structure corresponding to each polymer block is used. Hard to mix (that is, it is easy to obtain the specified block copolymer (III) with high purity)
It is preferable to use an anionic polymerization method. Anionic polymerization involves, for example, forming a living polymer of a polyconjugated alkadiene by polymerizing a conjugated alkadiene in the presence of a monofunctional initiator such as sec-butyllithium, and then converting the living polymer to, for example, a trialkylaluminum, Trialkylboron, formula: Al-OA
in the presence of a tertiary organoaluminum compound having a chemical structure represented by r (where Ar represents an aromatic ring) in the molecule, if necessary, ethers such as diethyl ether and dimethoxyethane; and tetramethylethylene diamine and the like. By contacting with a (meth) acrylate in the presence of a polar additive such as an amine, a poly (meth) acrylate block is formed at one end of the living polymer. In this case, the block copolymer obtained after the completion of the polymerization is an AB-type diblock copolymer.

It is also possible to prepare the block copolymer (III) by an anionic polymerization method using a bifunctional initiator. Examples of the bifunctional initiator include 1,4-dilithio-1,1,4,4-tetraphenylbutane, 1,3-
Examples include bifunctional alkali metal initiators such as bis (1-lithio-1,3-dimethylpentyl) benzene. In this case, first, a bifunctional living polymer of a polyconjugated alkadiene is formed by polymerizing a conjugated alkadiene in the presence of a bifunctional initiator, and then a (meth) acrylic acid ester is brought into contact with the polymer to polymerize it. By doing so, an ABA-type triblock copolymer is formed. When using a bifunctional initiator, usually,
Good results are often obtained when a mixed solvent composed of a polar solvent and a nonpolar solvent (for example, a mixture composed of cyclohexane and an ether such as diethyl ether) is used.

When it is desired to obtain a block copolymer (III) in which at least a part of the conjugated alkadiene units in the polymer block (B) is hydrogenated, for example, the above-mentioned polymerization Obtained by the method, (meta)
Polymer block (A) comprising acrylate units
And a block copolymer having a polymer block comprising a conjugated alkadiene unit that has not been hydrogenated is subjected to a hydrogenation reaction. As a hydrogenation reaction method in that case, hydrogenation occurs to the conjugated alkadiene unit in the polymer block (B), but to the (meth) acrylate unit in the polymer block (A). As long as no significant hydrogenation occurs,
There is no particular limitation. In the hydrogenation reaction, the block copolymer before hydrogenation is prepared by adding a certain transition metal hydrogenation catalyst in a solvent inert to the hydrogenation reaction such as hexane, cyclohexane, toluene, or a mixed solvent of cyclohexane / diethyl ether. Is preferably carried out by contacting with hydrogen gas in the presence of hydrogen. For example, using a catalyst prepared from a trialkylaluminum and a soluble nickel salt such as nickel octoate, the temperature is raised from room temperature to 250 ° C.
The hydrogenation reaction can be carried out at a temperature in the range of ° C. and a hydrogen gas pressure in the range of normal pressure to 20 MPa. The hydrogenation rate in the conjugated alkadiene unit can be quantitatively analyzed by a nuclear magnetic resonance method or an infrared spectrum method.

Examples of the polyolefin resin usable in the present invention include high density polyethylene, medium density polyethylene, low density polyethylene, ethylene-1-butene copolymer, ethylene-1-octene copolymer, polypropylene and polybutene. , Polyisobutylene, polymethylpentene, polybutadiene, hydrogenated products of polybutadiene,
Polyisoprene, hydrogenated polyisoprene, copolymer of propylene and ethylene and / or 1-butene, ethylene-propylene-diene terpolymer having a diene component of 50% by weight or less, ethylene or propylene and 50% by weight By weight or less of a copolymer with vinyl acetate, alkyl methacrylate or alkyl acrylate, butadiene-isoprene copolymer, butadiene-
Examples include a hydrogenated product of an isoprene copolymer, a reactor alloy of propylene and an ethylene-propylene copolymer rubber, and a dynamically crosslinked product of polypropylene and an ethylene-propylene-diene terpolymer.

Examples of the polyvinyl chloride resin usable in the present invention include not only a vinyl chloride homopolymer but also vinyl chloride and other comonomers (for example, 30
Can be copolymerized with vinyl chloride such as ethylene, propylene, vinyl acetate, vinyl bromide, vinylidene chloride, vinyl ether, methacrylic ester, acrylate, methacrylamide, acrylamide, acrylonitrile, maleimide, etc. by weight% or less. And a chlorinated polyvinyl chloride resin.

In the thermoplastic resin composition of the present invention, when the content of the block copolymer (III) is too small, the content of the block copolymer (III) between the polyolefin resin (I) and the polyvinyl chloride resin (II) is reduced. When the compatibility improvement is small, the mechanical properties of the obtained thermoplastic resin composition become insufficient, and conversely, when the content of the block copolymer (III) is too large,
Since the tendency of excess block copolymer (III) to bleed out from the resin composition is apt to occur, the content of block copolymer (III) may be determined by appropriately evaluating the performance of the thermoplastic resin composition obtained. It is better to set it. However, in many cases, the content of the block copolymer (III) is 0.2 to 100 parts by weight based on the sum of the contents of the polyolefin resin (I) and the polyvinyl chloride resin (II).
It is preferably set within the range of 50 parts by weight,
It is more preferable to set within the range of ~ 20 parts by weight,
It is particularly preferable to set within the range of 0.5 to 10 parts by weight. Further, in the thermoplastic resin composition of the present invention, the content of the polyolefin-based resin (I) and the polyvinyl chloride-based resin (II) is not necessarily limited,
From the viewpoint that the compatibilizing effect of the block copolymer is remarkably exhibited, the weight ratio of (I) / (II) is 95/5 to 5/5.
It is preferably within the range of 5/95.

As described above, the thermoplastic resin composition of the present invention contains the polyolefin resin (I), the polyvinyl chloride resin (II) and the block copolymer (III) as essential components. May contain other optional components. Examples of the optional components include phenol-based, amine-based, sulfur-based, and phosphorus-based antioxidants; pigments; nucleating agents; thermal deterioration inhibitors; ultraviolet absorbers; antiblocking agents; Fillers such as silica, aluminum hydroxide, calcium carbonate, talc, mica, titanium oxide, carbon black and potassium titanate; engineering resins; general-purpose resins; block copolymers Other examples include compatibilizing agents for polymer alloys other than (III).

The thermoplastic resin composition of the present invention is, for example,
It can be produced by melt-kneading the polyolefin resin (I), the polyvinyl chloride resin (II), the block copolymer (III) and, if desired, any components at a predetermined ratio. The order of mixing the components at this time is not necessarily limited. For example, a method comprising simultaneously mixing the above components, after mixing the polyolefin resin (I) and the polyvinyl chloride resin (II), A method comprising mixing the block copolymer (III) is exemplified. In addition, as the polyolefin-based resin (I) and the polyvinyl chloride-based resin (II), it is also possible to use a collected product of a composite member composed of both. In the melt-kneading operation, a melt-kneader such as a single-screw extruder, a twin-screw extruder, a Brabender, a kneader, or a Banbury mixer, which is usually used when melt-kneading a thermoplastic resin material, can be used. The temperature of the melt-kneading is preferably in the range of 170 to 250 ° C, more preferably in the range of 180 to 230 ° C.

The thermoplastic resin composition of the present invention can be melt-molded and heat-processed, and is particularly excellent in melt-moldability. Therefore, any molding method such as injection molding, extrusion molding, blown film molding and blow molding can be used. Accordingly, various molded products can be manufactured smoothly. Good mechanical properties are exhibited in the obtained molded article. For these reasons, the thermoplastic resin composition of the present invention can be used for packaging materials, home appliances and
It is useful as a housing member for OA equipment, a material for various uses such as automobile parts, and the like.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, the number average molecular weight and the block efficiency were determined by gel permeation chromatography (hereinafter abbreviated as GPC) based on a standard polystyrene calibration curve.

Reference Example 1 (Synthesis example of polybutadiene-poly (methyl methacrylate) diblock copolymer) In a 1-liter autoclave whose inside was replaced with nitrogen, 690 ml of degassed and dehydrated toluene and 1.3 mol of toluene were added.
2.5 ml of a cyclohexane solution containing 1 / l sec-butyllithium were added. To this solution, 65.0 g of 1,3-butadiene was added, and polymerization was carried out at 35.0 ° C. for 3 hours. Next, a part of the produced polymer was sampled and analyzed. The analysis is performed by GPC and nuclear magnetic resonance absorption measurement (hereinafter abbreviated as NMR), and the number average molecular weight (hereinafter abbreviated as “Mn”), weight average molecular weight /
Number average molecular weight ratio (hereinafter abbreviated as “Mw / Mn”) and 1,4-bond amount (ratio of 1,3-butadiene unit in 1,4-bond form based on all 1,3-butadiene units) ). As a result, Mn = 15500, M
It was found that w / Mn = 1.01 and the amount of 1,4-bonds = 90.0%. After the above polymerization, the obtained reaction mixture was cooled to 0 ° C and 6.0 ml of 1,2-dimethoxyethane was added.
And 23.2 ml of a toluene solution containing 0.7 mol / l of isobutyl bis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, and 15
Stirred for minutes. Next, 65.0 g of methyl methacrylate was added to the obtained solution while vigorously stirring the solution.
After performing polymerization at 0 ° C. for 4 hours with stirring, the polymerization was stopped by adding about 1.0 ml of methanol.

A polymer was obtained by removing the solvent in the obtained reaction mixture under reduced pressure. GPC and N
As a result of analysis by MR, the polymer was a polybutadiene-polymethyl methacrylate diblock copolymer (a),
For the polymer, Mn = 35400, Mw / Mn =
1.03, the weight ratio of polybutadiene block / polymethyl methacrylate block was 47/53 (from NMR), and the block efficiency during polymerization was 100% (GP
C).

Reference Example 2 (Synthesis example of hydrogenated polybutadiene-polymethyl methacrylate diblock copolymer) In a 1-liter autoclave in which the inside was replaced with nitrogen,
100 g of the block copolymer (a) obtained in Reference Example 1
Was dissolved in 600 ml of degassed and dehydrated toluene, and the temperature was raised to 80 ° C. 12.0 ml of a hydrogenation catalyst composed of nickel octoate / triisobutylaluminum = 1/3 (molar ratio) was added thereto, and hydrogen gas was supplied into the system until the pressure reached 1 MPa. Allowed to react for hours. Then, the hydrogenation reaction was stopped by adding 1.5 ml of 30% by weight aqueous hydrogen peroxide and 5.2 g of citric acid. The obtained reaction mixture was washed three times with 1500 ml of distilled water, and the obtained polymer solution was poured into 4000 ml of methanol to coagulate the polymer. The coagulated product was collected and vacuum-dried at 60 ° C. for 10 hours to obtain a hydrogenated polymer.

When the obtained polymer was subjected to NMR measurement, it was found that 95% of the carbon-carbon double bonds contained in the original polybutadiene block were hydrogenated and converted to carbon-carbon saturated bonds. It was confirmed that the product-poly (methyl methacrylate) diblock copolymer (b) was produced.

Reference Example 3 (Synthesis example of hydrogenated polybutadiene-polymethyl methacrylate diblock copolymer) In Reference Example 1, the weight ratio of polybutadiene block / polymethyl methacrylate block in the resulting polymer was 3 / 1, except that the polymerization reaction was carried out by changing the amounts of 1,3-butadiene and methyl methacrylate used so as to obtain a polymerization reaction operation of Reference Examples 1 and 2.
By performing a hydrogenation reaction operation and a post-treatment operation, a block efficiency of 100% and a hydrogenation reaction rate of 95%
Thus, a polybutadiene hydrogenated product-polymethyl methacrylate diblock copolymer (c) was obtained.

Reference Example 4 (Synthesis example of hydrogenated polybutadiene-polymethyl methacrylate diblock copolymer) In Reference Example 1, the weight ratio of polybutadiene block / polymethyl methacrylate block in the resulting polymer was 1 The polymerization reaction operation was carried out in the same manner as in Reference Examples 1 and 2 except that the polymerization reaction was carried out by changing the amounts of 1,3-butadiene and methyl methacrylate to be / 3.
By performing a hydrogenation reaction operation and a post-treatment operation, a block efficiency of 100% and a hydrogenation reaction rate of 95%
Thus, a polybutadiene hydrogenated product-polymethyl methacrylate diblock copolymer (c) was obtained.

Reference Example 5 (Synthesis example of hydrogenated polybutadiene-n-butyl diblock copolymer of polyacrylate) In the same manner as in Reference Example 1, 65.0 g of 1,3-butadiene was polymerized. Cool to 30 ° C, 0.7m
46.4 ml of a toluene solution containing ol / l isobutyl bis (2,6-di-tert-butyl-4-methylphenoxy) aluminum was added and stirred for 15 minutes.
While the solution was vigorously stirred, 65.0 g of n-butyl acrylate was added, polymerization was carried out at −30 ° C. for 4 hours with stirring, and then the polymerization was stopped by adding about 1.0 ml of methanol. The polymer was obtained by removing the solvent in the obtained reaction mixture under reduced pressure. A block efficiency of 90% and a hydrogenation reaction rate of 95 were obtained in the same manner as in Reference Example 2 except that the polymer thus obtained was used.
% To obtain a hydrogenated polybutadiene-n-butyl polyacrylate block copolymer (e).

Reference Example 6 (Synthesis example of hydrogenated polybutadiene-poly (methyl methacrylate) diblock copolymer) In Reference Example 1, cyclohexane / n was used instead of toluene as a solvent in the polymerization of 1,3-butadiene.
Hexane (volume ratio = 97/3) mixed solvent (480 ml) was added thereto, and 1,2-diethoxyethane (0.23 ml) was added thereto.
1,3-butadiene is polymerized in a solvent system to which toluene is added, and then toluene 21 is polymerized before polymerization of methyl methacrylate.
A polybutadiene hydrogenated product having a block efficiency of 100%, a hydrogenation reaction rate of 95%, and a 1,4-bond amount of 40% in a polybutadiene block was prepared in the same manner as in Reference Examples 1 and 2 except that 0 ml was added. A poly (methyl methacrylate) diblock copolymer (f) was obtained.

Examples 1 to 6 Polyvinyl chloride resin ("Sunplane (FA70HB)", manufactured by Mitsubishi Chemical MKV Co., Ltd.), ethylene-1-octene copolymer resin as a polyolefin resin (manufactured by Dow Chemical Company, "Engage") EG8452 "), the block copolymers (a) to (e) obtained in Reference Examples 1 to 5 as compatibilizers, and Irganox 1010 (manufactured by Ciba Geigy) as an antioxidant, respectively, in Table 1 below. As shown in the figure, the polyolefin resin and the compatibilizer are premixed in a proportion such that the total weight of the polyolefin resin and the compatibilizer is 30 parts by weight and the antioxidant is 0.1 part by weight based on 70 parts by weight of the polyvinyl chloride resin. After that, the mixture was melt-kneaded at 210 ° C. using a twin-screw extruder to produce thermoplastic resin composition pellets. An injection molded article was prepared using the pellets, and the molded article was evaluated for mechanical properties such as yield strength, tensile strength at break and tensile elongation at break according to JIS K7113. In addition, using the obtained pellet, a capillary rheometer (manufactured by Yasuda Seiki Seisakusho, Model 805)
2 "), the melt viscosity under the condition of a shear rate of 24.3 s ^-1 was measured. In addition, break the injection molded product,
The average particle size of the polyvinyl chloride-based resin phase dispersed and distributed in the polyolefin-based resin phase was measured based on the scanning electron microscope observation of the fracture surface. It can be evaluated that the smaller the average particle size, the better the compatibility. The obtained measurement results are shown in Table 2 below.

Example 7 In the above-mentioned Example 1, a reactor alloy (manufactured by Montelu Sd. Sunrise Co., Ltd.) of polypropylene and ethylene-propylene copolymer rubber instead of ethylene-1-octene copolymer resin as the polyolefin resin was used. Cataloy (KS353P) "), and using the block copolymer (f) obtained in Reference Example 6 in place of the block copolymer (a) obtained in Reference Example 1 as a block copolymer. Except for the above, pellets of the thermoplastic resin composition were obtained in the same manner. Further, the obtained thermoplastic resin composition was dispersed and distributed in mechanical properties (yield strength, tensile rupture strength and tensile rupture elongation), melt viscosity and polyolefin resin phase in the same manner as in Example 1. The average particle diameter of the polyvinyl chloride resin phase used was measured. The measurement results obtained are shown in Table 2 below.

Comparative Example 1 In Example 1, an ethylene-ethyl acrylate random copolymer (weight ratio of ethylene units / ethyl acrylate units: 75/25; M) was used in place of the block copolymer.
FR: 1.6), except that pellets of the thermoplastic resin composition were obtained in the same manner. Further, the obtained thermoplastic resin composition was dispersed and distributed in mechanical properties (yield strength, tensile rupture strength and tensile rupture elongation), melt viscosity and polyolefin resin phase in the same manner as in Example 1. The average particle diameter of the polyvinyl chloride resin phase used was measured. The measurement results obtained are shown in Table 2 below.

Comparative Example 2 In Example 1, a polyvinyl chloride resin (manufactured by Mitsubishi Chemical MKV Co., Ltd., “Sunplane (FA70H)
B))) 70 parts by weight of an ethylene-1-octene copolymer resin as a polyolefin resin (manufactured by Dow Chemical Company,
“Engage EG8452”) The pellets of the thermoplastic resin composition were prepared in the same manner except that 30 parts by weight and only 0.1 part by weight of Irganox 1010 as an antioxidant were used (the block copolymer was not used). Obtained. Also,
About the obtained thermoplastic resin composition, similarly to Example 1, mechanical properties (yield strength, tensile rupture strength and tensile rupture elongation), melt viscosity, and distribution in the polyolefin resin phase are distributed. The average particle size of the polyvinyl chloride resin phase was measured. The measurement results obtained are shown in Table 2 below.

Comparative Example 3 In Example 7 described above, a polyvinyl chloride resin (manufactured by Mitsubishi Chemical MKV, "Sunplane (FA70H)
B) ") 70 parts by weight, 30 parts by weight of a reactor alloy of polypropylene as a polyolefin resin and ethylene-propylene copolymer rubber (" Cataalloy (KS353P) ", manufactured by Montell S. D. Sunrise Co., Ltd.) and an antioxidant The Irganox 1010
In the same manner, except that only 0.1 part by weight of was used (the block copolymer was not used), pellets of the thermoplastic resin composition were obtained. Further, the obtained thermoplastic resin composition was dispersed and distributed in mechanical properties (yield strength, tensile rupture strength and tensile rupture elongation), melt viscosity and polyolefin resin phase in the same manner as in Example 1. The average particle diameter of the polyvinyl chloride resin phase used was measured. The measurement results obtained are shown in Table 2 below.

[0039]

[Table 1]

[0040]

[Table 2]

The measurement results of the thermoplastic resin compositions according to the present invention of Examples 1 to 6 shown in Table 2 above and Comparative Examples different from the present invention in that the block copolymer (III) was not added. Comparative example 2 with the measurement result of the thermoplastic resin composition; and the measurement result of the thermoplastic resin composition according to the present invention of Example 7 and the present invention in that the block copolymer (III) is not added. By comparison with the different measurement results of the thermoplastic resin composition of Comparative Example 3, in the thermoplastic resin composition of the present invention containing the specific block copolymer (III),
Mechanical properties (tensile rupture strength, tensile rupture elongation and yield strength) as compared to the case where the block copolymer (III) is not contained (a thermoplastic resin composition comprising a polyolefin resin and a polyvinyl chloride resin) It can be seen that the compatibility between the polyolefin resin and the polyvinyl chloride resin is greatly improved. Further, the thermoplastic resin composition of the present invention has the same melt viscosity as that of the thermoplastic resin composition different from the present invention in that it does not contain the block copolymer (III). It can be seen that good melt moldability is maintained irrespective of the addition of the coalescence (III).

The results of the measurements of the thermoplastic resin compositions according to the present invention of Examples 1 to 6 shown in Table 2 above and the point that another copolymer was used instead of the block copolymer (III) were used. The specific block copolymer (II) was compared with the measurement result of the thermoplastic resin composition of Comparative Example 1 different from the present invention.
In the thermoplastic resin composition of the present invention containing (I), the mechanical properties (tensile rupture strength, tensile rupture elongation and yield strength) of the thermoplastic resin composition containing other modifiers It can be seen that the compatibility between at least one) and the polyolefin-based resin and the polyvinyl chloride-based resin are all significantly improved.

[0043]

The polyolefin resin (I) of the present invention,
Thermoplastic resin compositions composed of polyvinyl chloride resin (II) and a specific block copolymer (III) have excellent mechanical properties, melt moldability, etc., and are useful as materials for molded articles for various applications. is there.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazunari Ishiura 41 Miyukigaoka, Tsukuba, Ibaraki Pref. Kuraray Co., Ltd. (72) Inventor Kazuhiko Maekawa 2045, Sazu, Kurashiki-shi, Okayama Pref. (reference) 4J002 AC03W AC06W AC11W BB03W BB04W BB04X BB05W BB06W BB06X BB07X BB08W BB08X BB09X BB12W BB15W BB17W BD03X BD10X BD11X BG10X BG12X BH02X BP03Y FD010 FD070 GG02 GN00 GQ00 4J026 HA14 HA15 HA16 HA26 HA39 HB12 HB19 HB25 HB32 HB42 HB44 HB45 HB50 HE01 HE02

Claims (3)

[Claims] 1. A composition comprising a polyolefin resin (I), a polyvinyl chloride resin (II) and a block copolymer (III), wherein the block copolymer (III) comprises at least 1
A polymer block (A) comprising at least one methacrylate unit or an acrylate unit and at least one conjugated alkadiene unit, wherein at least a part of the carbon-carbon double bond is hydrogenated to form a carbon-carbon saturated bond. A thermoplastic resin composition, which is a block copolymer containing a polymer block (B) which may be converted into a polymer. 2. The content of the block copolymer (III) is as follows:
0.2 to 5 based on 100 parts by weight of the sum of the contents of the polyolefin resin (I) and the polyvinyl chloride resin (II)
The thermoplastic resin composition according to claim 1, wherein the amount is within a range of 0 parts by weight. 3. A polymer block (A) comprising at least one methacrylate unit or acrylate unit and at least one conjugated alkadiene unit, wherein at least a part of the carbon-carbon double bond is hydrogenated. A polyolefin-based resin (I) and a polyvinyl chloride-based resin, comprising a block copolymer (III) containing a polymer block (B) which may have been converted to a carbon-carbon saturated bond. An additive for a thermoplastic resin composition containing (II).