JPH11100479A - Thermoplastic resin composition and masterbatch containing the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent moldability and mechanical and thermal properties and useful in the fields of blow-molding, vacuum forming, extrusion molding, expansion molding, etc., by including a polymer of an alkyl (meth)acrylate and a thermoplastic resin. SOLUTION: The objective thermoplastic resin composition is produced by including (A) preferably 0.01-50 pts.wt. of a polymer composed of (a) an alkyl (meth)acrylate having a 2-30C alkyl group (e.g. ethyl acrylate and butyl acrylate) and optionally (b) a vinyl monomer (e.g. methyl acrylate, methyl methacrylate and styrene) and having a weight-average molecular weight of <600,000 and (B) 100 pts.wt. of a thermoplastic resin (e.g. polyolefin and polyethylene terephthalate). A polymerization solvent, a polymerization initiator, a chain transfer agent, etc., may be used as necessary in the production of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent moldability.

[0002]

2. Description of the Related Art Thermoplastic resins are used for various purposes. For example, when polyolefins are blow-molded, vacuum-formed, extruded, foamed, etc., various molding process defects often occur. It is generally well known.

[0003] It is known that the poor molding processability depends on the fluidity and melt tension of a molten resin. Thermoplastic resin with low balance between fluidity and melt tension causes poor molding processability such as poor thickness uniformity during blow molding, vacuum molding, drawdown during extrusion molding, and low expansion ratio during foam molding. Although easy, the thermoplastic resin having both high fluidity and high melt tension has excellent moldability.

However, for example, in the case of polyolefin,
It is well known that these two performances are simultaneously unsatisfactory.

When the molecular weight of the polyolefin is reduced,
Although the fluidity improves, the melt tension decreases. on the other hand,
When the molecular weight is increased, the melt tension is improved, but the fluidity is reduced. Even if the molecular weight distribution is varied or a blend of two or more polymers having different molecular weights is obtained, the fluidity and melt tension of the resulting blend can be obtained only as an average of the low molecular weight and the high molecular weight.

Acrylic polymers are often used as modifiers for various thermoplastic resins. Attempts have been made to improve the moldability of polyolefins by the addition of such polymers, as follows.

JP-A-51-24649 describes that the roll kneading property is improved by adding an acrylic polymer to a polyolefin. However, there is no description regarding fluidity and melt tension.

Japanese Patent Application Laid-Open No. 51-151791 discloses that the addition of a polymer consisting of a methacrylic acid ester and (meth) acrylic acid improves the kneading properties, extrusion foaming properties, vacuum moldability, and blow moldability of a polyolefin. JP-A-8-302098 describes that the weight-average molecular weight is 670,000 or more by adding an acrylic polymer.
It is stated that the melt strength of the polypropylene is improved. These are attempts to improve the melt tension of the polyolefin by adding an acrylic polymer having a high molecular weight. However, as described in JP-A-8-302098, flowability is reduced. The balance between fluidity and melt tension of the resulting polyolefin resin composition was insufficient.

[0009]

As described above, it is important to improve the balance between the fluidity and the melt tension particularly in the moldability of a thermoplastic resin such as polyolefin.
For example, there is a strong demand for the development of an additive that improves the flowability of polyolefin without lowering the melt tension.

For example, the fluidity of a polypropylene resin composition is measured by a melt flow rate (ASTM D1238, 2).
30 ° C., 2.16 kg), and the melt tension was measured using a capillary rheometer (barrel temperature: 190 ° C., nozzle:
L / D = 8 mm / 2.1 mm, extrusion speed 10 mm /
When the melt flow rate is 1.2 g / 10 min or more and the melt tension is 11 g or more, blow molding, vacuum molding, extrusion molding, foam molding, etc. In the above, poor molding processability is reduced, and if the melt flow rate is 2 g / 10 min or more, the poor molding processability can be substantially prevented.

An object of the present invention is to obtain a thermoplastic resin composition having both high fluidity and high melt tension and excellent moldability.

[0012]

The gist of the present invention is to provide an alkyl (meth) acrylate (a-1) having an alkyl group having 2 to 30 carbon atoms as a component and having a weight average molecular weight of less than 600,000. A thermoplastic resin composition comprising the coalesced (A) and the thermoplastic resin (B) and a master batch containing the same.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, an alkyl (meth) acrylate having an alkyl group having 2 to 30 carbon atoms (a-
1) is an alkyl (meth) acrylate containing a linear or branched alkyl group having 2 to 30 carbon atoms, and includes ethyl acrylate, butyl acrylate, 2-methylbutyl acrylate, and 3-methylbutyl. Acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, tridecyl acrylate, cetyl acrylate, stearyl acrylate, eicosyl acrylate, ethyl methacrylate, butyl methacrylate, 2-methylbutyl methacrylate, 3- Methyl butyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decylmeth Examples thereof include acrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, and eicosyl methacrylate. One or two or more of these can be used, and the molding processability and cost of the obtained thermoplastic resin composition can be used. Considering ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate,
Stearyl acrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, and stearyl methacrylate are preferred.

The polymer (A) according to the present invention comprises (a-1)
In addition, a vinyl monomer (a-2) exemplified below can be included as needed. The vinyl monomer (a-2) according to the present invention is an organic substance having at least one polymerizable unsaturated bond, and is an aromatic substance such as methyl acrylate, methyl methacrylate, styrene, α-methyl styrene, and vinyl toluene. Alkenyl compounds; acrylonitrile,
Vinyl cyanide compounds such as methacrylonitrile; α-olefins such as ethylene and propylene; glycidyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, polyalkylene glycol (meth) acrylate Vinyl monomers having an epoxy group such as glycidyl ether of glycidyl ether, glycidyl ether of polyalkylene glycol (meth) acrylate and diglycidyl itaconate; functionalities such as amino group, hydroxy group, mercapto group, halogen group and halogenated carbonyl group Examples thereof include vinyl monomers containing a group, and one or more of these can be used. The method for industrially producing the obtained polymer (A) and the thermoplastic resin composition, and the obtained thermoplastic resin The fluidity of the resin, in consideration of cost and the like, methyl acrylate, methyl methacrylate, styrene, alpha-methyl styrene, acrylonitrile is preferred.

Further, other copolymer components of the polymer (A) include (meth) such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. A vinyl monomer such as a compound having two or more polymerizable functional groups such as acrylate, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, etc., in total of (a-1) and (a-2) 100 weight Less than 5 parts by weight per part can be used. If it is used in an amount of 5 parts by weight or more, the fluidity of the obtained thermoplastic resin composition decreases.

The structure of the polymer (A) is not particularly limited, and examples thereof include a branched type such as a linear type, a comb type, a star type, a dendrimer type and a cascade type.

The weight average molecular weight of the polymer (A) is as follows:
Although not particularly limited, in consideration of the moldability of the obtained resin composition, the weight average molecular weight is less than 600,000,
Less than 400,000 is more preferred, and less than 100,000 is even more preferred.

The method for producing the polymer (A) is not particularly limited, and it is generally known in the system of bulk, solution, emulsification, suspension, etc., such as radical polymerization, anion polymerization and cationic polymerization. Can be exemplified.

In producing the polymer (A), a polymerization initiator, a polymerization catalyst, a chain transfer agent, a molecular weight regulator, an organic solvent,
Commonly known polymerization additives such as a dispersion medium, an emulsifier, and a dispersant can be used.

As the polymerization initiator for radical polymerization, te
Examples of the redox initiator include a peroxide such as rt-butyl hydroperoxide and cumene hydroperoxide, an azo initiator such as azobisisobutyronitrile or an oxidizing agent, and a redox initiator obtained by combining a reducing agent. Examples thereof include a sulfoxylate initiator obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetate, Rongalid, and hydroperoxide.

Examples of the emulsifier include nonionic, anionic and cationic emulsifiers.

Examples of the chain transfer agent include n-octyl mercaptan and tert-dodecyl mercaptan.

As the polymerization solvent, toluene, benzene,
Examples thereof include dioxane, dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like.

Examples of the production method by radical polymerization in a bulk or solution system include an alkyl (meth) acrylate (a-1) and a vinyl monomer (a-
2) A method of polymerizing a monomer by heating a mixture comprising a polymerization solvent, a polymerization initiator, a chain transfer agent and the like can be exemplified.

The polymer (A) can be separated and recovered by pouring the solution of the polymer (A) obtained by the solution polymerization into a liquid in which the polymer (A) is not dissolved.

Examples of the emulsion-type radical polymerization include a mixture comprising water, an emulsifier, an alkyl methacrylate (a-1) and, if necessary, a vinyl monomer (a-2), a polymerization initiator and a chain transfer agent. If necessary, homogenize using a homomixer that atomizes by shearing force due to high-speed rotation or a homogenizer that atomizes by jetting power from a high-pressure generator, etc. And a method for polymerizing the monomer.

The polymerization can be carried out in one stage or in two or more stages. As an example of the two-stage polymerization, in the emulsion-type radical polymerization, after the alkyl (meth) acrylate (a-1) and, if necessary, the vinyl monomer (a-2) are polymerized in the first stage, the two-stage polymerization is carried out. A method in which the vinyl monomer (a-2) is supplied into the polymerization system and polymerized can be exemplified.

As a method for supplying the monomers in the first and second stages, there is a method for supplying them all at once or in small amounts.

Further, the polymer (A) in the form of a latex obtained by emulsion polymerization is poured into an aqueous solution of a coagulant, whereby the polymer (A) can be separated and recovered. Examples of the coagulant include metal salts such as calcium chloride, calcium acetate and aluminum sulfate.

When an alkyl (meth) acrylate (a-1) having an alkyl group having 2 to 30 carbon atoms is a monomer (for example, lauryl methacrylate) which gives a polymer having a glass transition temperature of room temperature or lower, For example, as the ratio of (a-1) in the polymer (A) obtained by one-step polymerization is increased, the fluidity of the obtained thermoplastic resin composition is increased, but the glass transition temperature of the polymer (A) is increased. The temperature may be lower than room temperature. For example, the polymer (A) 1
When (a-1) is used in an amount of 40 parts by weight or more with respect to 00 parts by weight, the obtained polymer (A) has poor handling properties, so that the production of the polymer (A) of the present invention and the thermoplastic resin composition is It is not preferable depending on the production conditions.

When the polymer (A) is produced in one step, (a-1) 30 to 1 to 100 parts by weight of the polymer (A) is used.
00 parts by weight and 70 to 0 parts by weight of (a-2), more preferably 60 to 100 parts by weight of (a-1), and (a-2) 4
0 to 0 parts by weight is preferable from the viewpoint of fluidity of the obtained thermoplastic resin composition.

In the polymer (A) obtained by the two-stage polymerization, (a-
20 to 85 parts by weight of a first-stage polymer containing 1) by weight of 50% by weight or more, more preferably 75% by weight or more, and 15 to 85 parts by weight of a second-stage polymer containing 50% by weight or more of (a-2) In the case of using, the obtained thermoplastic resin composition has high fluidity, and the obtained polymer (A) can be recovered as a powder, which is preferable.

The polymer (A) of the present invention may be used alone or
It can be used as a mixture of more than one species.

The thermoplastic resin (B) of the present invention is generally known thermoplastic resins and elastomers.
Polyolefin; Polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate; polystyrene, high-impact polystyrene, acrylonitrile-
Styrene copolymers, styrene-butadiene copolymers, styrene-butadiene block copolymers, acrylonitrile-styrene-butadiene copolymers and other styrene resins and elastomers, polycarbonate, 6-nylon,
6,6-nylon, polyarylate, polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polyether ketone, polyether ether ketone, polysulfone, polyether sulfone, polyamideimide, polyetherimide, polymethyl methacrylate, polyacetal, polyvinyl chloride And the like, and one or more of these can be used. In view of the moldability, mechanical properties, cost, and the like of the obtained thermoplastic resin composition, polyolefins; polyethylene terephthalate, polybutylene terephthalate ,
Polyesters such as polyethylene naphthalate and polybutylene naphthalate, polymethyl methacrylate and polycarbonate are preferred, and polyolefins, polymethyl methacrylate and polycarbonate are more preferred.

The polyolefin is a polymer of a vinyl monomer containing an α-olefin as a main component.

The α-olefin is an α-olefin having 2 to 10 carbon atoms.
-Means olefin, ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3,3-dimethylpentene-1, 3-methylhexene- 1,4-methylhexene-1,4,4-dimethylhexene-1,5-methylhexene-1, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexylbutene-1, vinylcyclopropane, vinylcyclohexane,
Examples thereof include 2-vinylbicyclo [2.2.1] heptane, heptene-1, octene-1 and the like, and one or more of these can be used. Considering the balance with ethylene, propylene is preferred.

Further, if necessary, 4-methyl-1,4-hexadiene, 5
-Methyl-1,4-hexadiene, 7-methyl-1,6-
Non-conjugated dienes such as octadiene and 1,9-decadiene;
One or two or more vinyl monomers such as vinyl acetate, acrylic acid, methacrylic acid, alkyl (meth) acrylate, aromatic vinyl, and maleic anhydride are combined with 5
It can be used to be 0% by weight or less.

A functional group can be introduced into the polyolefin as needed. As a method for introducing a functional group, a polyolefin is melt-kneaded with an α, β-unsaturated carboxylic acid such as maleic anhydride and the like, an anhydride thereof, and an organic peroxide by an extruder to obtain a carboxylic acid group and the anhydride thereof. Examples of the method include a method for obtaining a polyolefin having a basic group.

The thermoplastic resin composition according to the present invention can be obtained by mixing the polymer (A) and the thermoplastic resin (B).

The polymer (A) is a thermoplastic resin (B) 10
It is preferable to add 0.01 to 100 parts by weight with respect to 0 parts by weight. More preferably, 0.01 to
50 parts by weight.

The ratio of the polymer (A) is increased in advance, and the polymer (A) and the thermoplastic resin (B) are mixed to obtain a master batch. The desired composition can also be obtained by mixing the batch and the thermoplastic resin (B).

Further, in the thermoplastic resin composition of the present invention, if necessary, various additives such as generally known various additive stabilizers and reinforcing agents can be used.

As a method for mixing the polymer (A) with the thermoplastic resin (B), a known and known compounding and kneading method can be used. For example, a Henschel mixer, a Banbury mixer, a single screw extruder, A twin screw extruder, two rolls or the like can be used.

The obtained resin composition can be applied to any of the usual known molding methods, for example, injection molding, hollow molding, extrusion molding, foam molding, vacuum molding, compression molding, calendar molding, etc., to produce various molded products. it can.

Hereinafter, the present invention will be described with reference to examples. In Reference Examples, Examples and Comparative Examples, “parts” and “%” are “parts by weight” and “% by weight” unless otherwise specified.
Means

[0046]

EXAMPLES Various physical properties in Examples and Comparative Examples were measured by the following methods.

(1) Solid Content The weight of the polymerized latex after drying at 170 ° C. for 30 minutes was measured and determined.

(2) Weight average particle diameter The weight average particle diameter was measured by a dynamic light scattering method using DLS-700 manufactured by Otsuka Electronics Co., Ltd.

(2) Weight Average Molecular Weight (Mw) The weight average molecular weight of the obtained polymer was measured by gel permeation chromatography (GPC) in terms of chloroform and polymethyl methacrylate as eluent.

(3) Melt flow rate (MFR) Measured according to ASTM D1238.

However, in the case of the polypropylene resin composition, the temperature is 230 ° C. and the load is 2.16 kg; in the case of the polymethyl methacrylate resin composition, the temperature is 230 ° C. and the load is 3.8 kg;
In the case of the polycarbonate resin composition, the measurement was performed at a temperature of 280 ° C. and a load of 2.16 kg.

(4) Melt tension The obtained resin composition was subjected to a nozzle: L / D using a capillary rheometer (Capillograph manufactured by Toyo Seiki Co., Ltd.).
= 8 mm / 2.1 mm, the extrusion speed was 10 mm / min, and the winding speed was 4 m / min.

However, the measurement temperature was 190 ° C. for the polypropylene resin composition and 230 ° C. for the polymethyl methacrylate resin composition.

(5) Izod Impact Strength (Izd.) A temperature of 23 ° C. and a humidity of 50% according to ASTM D256.
It was measured under conditions of RH and notch.

A test piece was obtained by molding the obtained resin composition using an injection molding machine (IS-100 manufactured by Toshiba Machine Co., Ltd.).

However, the thickness of the test piece was 6.4 mm for the polypropylene resin composition and the polymethyl methacrylate resin composition, and 3.2 mm for the polycarbonate resin composition.

(6) Flexural modulus According to ASTM D790, a temperature of 23 ° C. and a humidity of 50%
Measured at RH.

A test piece was obtained by molding the obtained resin composition using an injection molding machine (IS-100 manufactured by Toshiba Machine Co., Ltd.).

(7) Heat distortion temperature (HDT) Measured according to ASTM D648.

Test pieces were obtained by molding the obtained resin composition using an injection molding machine (IS-100 manufactured by Toshiba Machine Co., Ltd.).

However, the load was 4.6 kg for the polypropylene resin composition and 18.6 k for the polymethyl methacrylate resin composition and the polycarbonate resin composition.
g.

Reference Example 1 Lauryl methacrylate 70
Parts, 30 parts of methyl methacrylate, 0.5 part of cumene hydroperoxide, and 1.0 part of n-octyl mercaptan, and an emulsifier aqueous solution (Latemul AS manufactured by Kao Corporation)
K) 2.8 parts (0.7 parts in terms of solid content) and 147 parts of distilled water were added, and the mixture was stirred at 10,000 rpm for 2 minutes using a homomixer, and then pressure was 200 kg / cm using a homogenizer.
^The emulsion was forcibly emulsified twice with 2 to obtain a stable premixed emulsion. This emulsion was charged into a separable flask equipped with a condenser and a stirrer and placed in a water bath under a nitrogen atmosphere.
C. and then a mixture of 0.0004 parts of ferrous sulfate, 0.0012 parts of disodium ethylenediaminetetraacetate, 0.48 parts of Rongalite and 3 parts of distilled water was added to start radical polymerization, and then for 2 hours The mixture was stirred to complete the polymerization. The weight average particle diameter of the obtained emulsion is 300
nm, solid content was 39.1%. The emulsion was poured into methanol, and the resulting precipitate was dried to obtain an oily polymer P-1. The weight average molecular weight was 30,000.

Reference Example 2 A separable flask equipped with a stirrer, a condenser, and a thermometer was charged with 100 parts of lauryl methacrylate, 200 parts of toluene, and 0.1 part of azobisisobutyronitrile. After blowing in nitrogen gas for 30 minutes, the contents were heated to 60 ° C. in a water bath under a nitrogen atmosphere, and
Stir for 6 hours. The content was poured into methanol, and the resulting precipitate was dried to obtain an oily polymer P-2. The weight average molecular weight was 360,000.

Reference Example 3 Lauryl methacrylate 70
Parts, a mixture of 0.4 parts of cumene hydroperoxide and 0.7 parts of n-octyl mercaptan, 2.8 parts of an aqueous emulsifier (Latemul ASK manufactured by Kao Corporation) (0.7 parts of solid content), distilled water 147 parts was added, and the mixture was stirred at 10,000 rpm for 2 minutes using a homomixer, and then forcedly emulsified twice at a pressure of 200 kg / cm ² using a homogenizer to obtain a stable premixed emulsion. This emulsion was charged into a separable flask equipped with a condenser and a stirrer, and heated to 60 ° C. in a water bath under a nitrogen atmosphere, and then ferrous sulfate 0.0004 parts, ethylenediaminetetraacetic acid disodium salt 0.0012 parts, A mixture of 0.48 parts of Rongalite and 3 parts of distilled water was added to initiate radical polymerization,
Thereafter, the temperature was maintained for 2 hours to complete the first-stage polymerization. A small amount of the content was collected, poured into methanol, and the weight average molecular weight of the resulting precipitate was measured to be 20,000.

Subsequently, a mixture of 30 parts of methyl methacrylate, 0.2 part of cumene hydroperoxide and 0.3 part of n-octyl mercaptan was added dropwise over 15 minutes, and then 2 parts
After stirring for an hour, the second stage polymerization was performed. The solid content of the obtained emulsion was 39.1%. This emulsion was poured into an aqueous calcium chloride solution, and the resulting precipitate was dried to obtain a powdery polymer P-3. Weight average molecular weight is 2
It was 10,000.

Reference Example 4 The same procedure as in Reference Example 3 was carried out except that the first-stage monomer was changed to 49 parts of lauryl methacrylate and 21 parts of methyl methacrylate to obtain a powdery polymer P-4. Obtained. The solid content of the obtained emulsion is 3
The weight average molecular weight was 20,000 after the first-stage polymerization and 20,000 after the second-stage polymerization.

Reference Example 5 A separable flask equipped with a stirrer, a condenser, and a thermometer was charged with 100 parts of lauryl methacrylate and 0.03 part of azobisisobutyronitrile as a polymerization initiator. After blowing nitrogen gas for 30 minutes, the contents were heated to 60 ° C.
Stirred for hours. The content was poured into methanol, and the resulting precipitate was dried to obtain a polymer P-5. The weight average molecular weight was 1.5 million.

Reference Example 6 Methyl methacrylate 100
Parts, a mixture of 0.5 parts of cumene hydroperoxide and 7.7 parts of n-octyl mercaptan, 2.8 parts of an aqueous emulsifier (Latemul ASK manufactured by Kao Corporation) (0.7 parts in terms of solid content), distilled water After 147 parts were added and the mixture was stirred at 10,000 rpm for 2 minutes using a homomixer, the mixture was forcedly emulsified twice at a pressure of 200 kg / cm ² using a homogenizer to obtain a stable premixed emulsion. This emulsion,
The mixture was charged into a separable flask equipped with a condenser and a stirrer, and heated to 60 ° C. in a water bath under a nitrogen atmosphere. And a mixed solution of 3 parts of distilled water was added to start radical polymerization, and then maintained for 2 hours to complete the polymerization. The solid content of the obtained emulsion was 37.5%. This emulsion was poured into an aqueous solution of calcium chloride, and the resulting precipitate was dried to obtain a polymer P-6. The weight average molecular weight was 6000.

Reference Example 7 A butyl acrylate 70 was placed in a separable flask equipped with a cooling tube and a stirring device.
Parts, 0.14 part of cumene hydroperoxide, 0.7 part of n-octyl mercaptan, 0.7 part of sodium dodecylbenzenesulfonate, and 194 parts of distilled water, and heated to 60 ° C. in a water bath under a nitrogen atmosphere. Ferrous sulfate 0.
0004 parts, ethylenediaminetetraacetic acid disodium salt 0.0012 parts, Rongalit 0.48 parts, distilled water 6
The radical polymerization was started by dissolving in the solution. Thereafter, the mixture was stirred for 2 hours to complete the first-stage polymerization. The weight average molecular weight of the polymer was 40,000.

Subsequently, a mixture of 30 parts of methyl methacrylate, 0.06 part of cumene hydroperoxide, and 0.3 part of n-octyl mercaptan was added dropwise for 50 minutes, followed by stirring for 2 hours to carry out the second stage polymerization. Was. The solid content of the obtained emulsion was 33.1%. This emulsion was poured into an aqueous solution of calcium chloride, and the resulting precipitate was dried to obtain a polymer P-7. The weight average molecular weight was 40,000.

Reference Example 8 In the composition of the first stage, butyl acrylate was 50 parts, cumene hydroperoxide was 0.1 part, and n-octyl mercaptan was 0.5 part.
The same operation as in Reference Example 7 was performed except that the second-stage composition was changed to 50 parts of methyl methacrylate, 0.1 part of cumene hydroperoxide, and 0.5 part of n-octyl mercaptan, and the dripping time was changed to 80 minutes. Polymer P-8 was obtained. The solid content after the second stage polymerization was 33.2%, and the weight average molecular weight was 30,000 after the first stage polymerization and 40,000 after the second stage polymerization.

Reference Example 9 Reference Example 7 was repeated except that n-octyl mercaptan was changed to 0.1 part in the first-stage composition.
The same operation as described above was carried out to obtain a polymer P-9.

The solid content after the second stage polymerization was 33.1%, and the weight average molecular weight was 170,000 after the first stage polymerization and 12% after the second stage polymerization.
It was 10,000.

Reference Example 10 A polymer P-10 was obtained in the same manner as in Reference Example 7, except that the first-stage monomer was changed to 49 parts of butyl acrylate and 21 parts of methyl methacrylate.

The solid content after the second stage polymerization was 33.1%, and the weight average molecular weight was 30,000 after the first stage polymerization and 40,000 after the second stage polymerization.

Reference Example 11 A polymer P-11 was obtained in the same manner as in Reference Example 7, except that 5 parts of allyl methacrylate was added to the first-stage composition.

The solid content after the second stage polymerization was 33.1%.

(Examples 1 and 2) A small kneader (manufactured by Brabender) was prepared by mixing polypropylene (EA9 manufactured by Nippon Polychem Co., Ltd.) and the polymers obtained in Reference Examples 1 and 2 in the proportions shown in Table 1. Was melt-kneaded at a barrel temperature of 200 ° C. and a screw rotation speed of 80 rpm for 2 minutes. Table 1 shows the results of measuring various physical properties of the obtained resin composition.

[0079]

[Table 1]

Comparative Examples 1 to 3 Table 2 shows the results of measuring various physical properties of several types of polypropylene (manufactured by Nippon Polychem Co., Ltd.).

[0081]

[Table 2]

(Examples 3 and 4) Polypropylene (EA9, manufactured by Nippon Polychem Co., Ltd.) and the polymers obtained in Reference Examples 3 and 4 were blended in the proportions shown in Table 2 and mixed in a twin screw extruder (WERNE).
Using R &PFLEIDERER's ZSK30)
Extrusion was performed at a barrel temperature of 200 ° C. and a screw rotation speed of 200 rpm. Table 3 shows the results of measuring various physical properties of the obtained resin composition.

[0083]

[Table 3]

Comparative Examples 4 to 6 Polypropylene (EA9 manufactured by Nippon Polychem Co., Ltd.) and polypropylene (Viscol 660-P manufactured by Sanyo Chemical Industries, Ltd., weight average molecular weight 3)
000) or the polylauryl methacrylate prepared in Reference Example 5 and the polymethyl methacrylate prepared in Reference Example 6 were blended in the proportions shown in Table 4, using a small kneader (manufactured by Brabender) at a barrel temperature of 200 ° C. The mixture was melt-kneaded at a screw rotation speed of 80 rpm for 2 minutes. Table 4 shows the measurement results of various physical properties of the obtained resin composition.

[0085]

[Table 4]

(Examples 5 to 8 and Comparative Example 7) Polypropylene (EA9 manufactured by Nippon Polychem Co., Ltd.) and Reference Examples 7 to
11 was blended in the ratio shown in Table 5, and a twin-screw extruder (ZSK manufactured by Werner & Pfleiderer) was used.
Using 30), the product was extruded at a barrel temperature of 200 ° C. and a screw rotation speed of 200 rpm. Table 5 shows the results of measuring various physical properties of the obtained resin composition.

[0087]

[Table 5]

(Example 9 and Comparative Example 8) Polymethyl methacrylate (suspension polymerized product) and the polymer obtained in Reference Example 8 were mixed at the ratio shown in Table 6 and mixed in a twin-screw extruder (WERNE).
Using R &PFLEIDERER's ZSK30)
Extrusion was performed at a barrel temperature of 230 ° C. and a screw rotation speed of 200 rpm. Table 6 shows the results of measuring various physical properties of the obtained resin composition.

[0089]

[Table 6]

(Example 10 and Comparative Example 9) Polycarbonate (Panlite L1225 manufactured by Teijin Chemicals Ltd.)
The polymer obtained in Reference Example 8 was blended in the ratio shown in Table 7, and a twin screw extruder (ZS manufactured by WERNER & PFLEIDERER) was used.
Using K30), the mixture was extruded at a barrel temperature of 280 ° C. and a screw rotation speed of 200 rpm. Table 7 shows the results of measuring various physical properties of the obtained resin composition.

[0091]

[Table 7]

The following is clear from the examples and comparative examples.

(1) As in Examples 1 and 2, the polypropylene resin composition of the present invention containing a polymer composed of lauryl methacrylate has a melt flow rate of 1.2.
Since the melt tension is at least g / 10 min and the melt tension is at least 11 g, molding defects in blow molding, vacuum molding, extrusion molding, foam molding and the like are unlikely to occur, and the molding processability is excellent. Further, the impact strength, the elastic modulus, and the heat deformation temperature are almost the same as those of the polypropylene alone of Comparative Example 1, and the original performance of the polypropylene is not impaired.

(2) As in Comparative Examples 1 to 3, commercially available polypropylene has low melt flow rate and one of melt tension, and is inferior in moldability.

(3) As in Examples 3 and 4, the polypropylene resin composition of the present invention containing a two-stage polymer composed of lauryl methacrylate has a melt flow rate of 1.2 g / 10 min or more and a melt tension of 11 g. As described above, the moldability is excellent, and the original performance of polypropylene is not impaired.

(4) As in Comparative Examples 4 to 6, the flowability of the polypropylene resin composition to which polypropylene (weight average molecular weight: 3000), polylauryl methacrylate (weight average molecular weight: 1.5 million), and polymethyl methacrylate were added It is about the same as polypropylene alone, has a low balance with the melt tension, and is inferior in moldability.

(5) As in Examples 5 to 8, the polypropylene resin composition of the present invention containing a polymer comprising butyl acrylate had a melt flow rate of 1.2 g / 10
Since the melt tension is 11 g or more, the moldability is excellent.

In particular, as in Examples 5 and 6, the first-stage polymer had a weight average molecular weight of less than 120,000 and an MMA content of 21.
When the amount is less than part by weight, the obtained thermoplastic resin composition exhibits a melt flow rate of 2 g / 10 minutes or more, can substantially prevent molding defects, and has a good molded appearance.

(6) As in Comparative Example 7, when butyl acrylate is copolymerized with allyl methacrylate, the resulting resin composition has poor fluidity.

(7) As in Example 9, the polymethyl methacrylate resin composition of the present invention is more excellent in fluidity than the polymethyl methacrylate alone of Comparative Example 8.

(8) As in Example 10, the polycarbonate resin composition of the present invention is superior in fluidity to the polycarbonate alone of Comparative Example 9.

[0102]

According to the present invention, fluidity can be drastically improved without impairing the inherent performance of the thermoplastic resin.

The thermoplastic resin composition of the present invention is excellent in moldability, mechanical properties and thermal properties, and has great industrial value especially in the fields of blow molding, vacuum molding, extrusion molding and foam molding. It is.

Claims (2)

[Claims] 1. A polymer (A) comprising an alkyl (meth) acrylate (a-1) having an alkyl group having 2 to 30 carbon atoms and having a weight average molecular weight of less than 600,000, and a thermoplastic resin (B) A) a thermoplastic resin composition comprising: 2. A polymer (A) having an alkyl (meth) acrylate (a-1) having an alkyl group having 2 to 30 carbon atoms and having a weight average molecular weight of less than 600,000 and a thermoplastic resin (B). A) Masterbatch for thermoplastic resin.