JPS62153330A - Copolymer containing dispersed complex gel - Google Patents

Abstract

PURPOSE:To obtain the title copolymer excellent in heat resistance, impact strength and moldability and useful as a resin material for a large molding of a complicated shape wherein the dispersed phase comprises a specified complex gel. CONSTITUTION:A dispersed gel phase is formed by bulk- or solution- copolymerizing a styrene monomer (a) with an acrylonitrile monomer (b) in the presence of a rubber-like polymer (A). Components (a) and (b) and a maleimide monomer (c) of the formula (wherein R is H, a 1-15 C alkyl, a cyanoalkyl or an aromatic residue) are bulk- or solution-polymerized in the presence of the above dispersed gel phase to form a continuous phase. In this way, a dispersed complex gel-containing copolymer comprising a complex gel comprising 30-70 wt. % component A and 70-30 wt. % total of a copolymer of components (a) and (b) and a copolymer of components (a), (b) and (c).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a copolymer with excellent heat resistance, impact strength, and moldability. The copolymer of the present invention can be used, for example, as a molding material for material parts for electrical equipment, electronic equipment, automobiles, and the like.

[Conventional technology]

Many attempts have been made to improve heat resistance through copolymerization of vinyl polymers, but the general tendency is that improving heat resistance results in a decrease in impact resistance, which poses five problems. For example, Japanese Patent Laid-Open No. 58-12904
3. JP-A-58-206657 and the like propose a resin composition in which a copolymer of NTft maleimide and a vinyl monomer and a graft copolymer are blended under specific conditions. In such compositions.

The performance balance of heat resistance and isot impact strength of the resin is maintained better than that of conventional resins (ABS) made of copolymers and graft copolymers of styrene monomers and acrylonitrile monomers. However, such conventional resins still have room for improvement, especially in terms of practical impact strength.

On the other hand, JP-A No. 47-6891 discloses a method of polymerizing styrene, acrylonitrile, and maleimide monomers in the presence of 1 to 20 wt% of a conjugated diolefin elastomer as a method of polymerizing a copolymer with high impact strength and high softening temperature. has been proposed, but although the copolymers produced by this method have high Izod impact strength and high softening temperature, they do not have sufficient practical impact strength.

However, in recent years, heat-resistant resins have been used for larger and more complex molded parts in the electrical equipment, electronic equipment, and automobile industry materials fields, and resins need to be improved not only in heat resistance but also in practical impact strength. There is a strong demand for improvement in moldability and moldability. Practical impact strength refers to the impact strength when a molded product is dropped or struck when it is put into practical use, especially in large molded products with high heat resistance, near areas where the wall thickness changes and areas with corner shapes. This area was the most vulnerable to impact, and improvements were needed.

This practical impact strength does not correspond to the Izot impact strength of the resin, and depends on the falling weight impact strength of the above-mentioned portion of the molded product rather than the Izot impact strength. In addition, in terms of molding processability, in general, in order to improve the heat resistance and practical impact resistance of the resin, copolymerization with a heat resistance imparting monomer is carried out, and as the amount and molecular weight of the rubbery component is increased, the molding process There is a tendency for the fluidity of the resin to decrease, and in such cases, increasing the molding temperature will slow down the molding cycle, and for large molded products, even if the molding pressure is NDO, there will be a problem in the mold. There was also the problem that the resin was not filled sufficiently, making it impossible to perform the molding process itself.

[Problem that the invention seeks to solve]

The object of the present invention is to provide a copolymer with a significantly improved balance of heat resistance, practical impact resistance, and moldability as a resin material for molded articles of large size and complicated shapes.

[Means for solving problems]

In view of the importance of this objective, the inventors conducted extensive studies and found that the dispersed phase is a special composite gel (hereinafter abbreviated as MG).
The inventors have discovered that the above objects can be achieved by using a novel copolymer consisting of the following, and have completed the present invention.

That is, the present invention.

A copolymer consisting of a continuous phase and a dispersed phase, comprising (a)
The dispersed phase is composed of a composite gel, and the composite gel is composed of (1) a rubbery polymer, (g) a copolymer of a styrene monomer and an acrylonitrile monomer, and (iii) a styrene monomer and an acrylonitrile monomer. and a copolymer of a maleimide monomer, and when the total amount of the composite gel is 100 parts by weight, (1) the rubbery polymer is 30 to 70 parts by weight,
The total amount of copolymers of the latter two (ii) and (iii) is 70
~30 parts by weight, and (b) the continuous phase is at least a dispersed composite gel-containing copolymer composed of a copolymer of a maleimide monomer, a styrene monomer, and an acrylonitrile monomer. be.

In the present invention, a copolymer consisting of a continuous phase and a dispersed phase is a copolymer in which one side is a continuous phase and the other is a dispersed phase, and each phase is composed of a polymer of two or more types of monomers. 4,
Here, when observing the dispersed phase using an electron microscope photograph,
It exists in the form of islands, and the continuous phase exists in the form of bubbles.

The continuous phase consists of methyl ethyl ketone and methanol.
The dispersed phase is also a portion that has the property of being dissolved in the mixed solvent of the third phase, while the dispersed phase is also a portion that has the property of not being dissolved in the solvent.

The dispersed phase of the present invention is composed of a composite gel (MG), and the NiG
is produced in a multi-stage process using bulk or solution polymerization methods. That is, the MG is produced by polymerizing a styrene monomer and an acrylonitrile monomer in the presence of a rubbery polymer by a bulk or solution polymerization method to form a dispersed gel phase (dispersed gel phase formation step). It is produced by polymerizing a maleimide monomer, a styrene monomer, and an acrylonitrile monomer in the presence of the dispersed gel phase by a solution polymerization method, and 2
It is formed to contain different types of copolymer components.

In addition, if an emulsion polymerization method is used or if a maleimide monomer is copolymerized before the formation of a dispersed gel phase, it is difficult to form a dispersed phase having a composite gel according to the present invention, and therefore the object of the present invention is not achieved. It is not possible to improve the practical impact strength.

The composition of such MG is, when the total amount is 100 parts by weight, 30 to 70 parts by weight of rubbery polymer, preferably 30 to 5 parts by weight.
5 parts by weight, and the total amount of the copolymer is 70 to 30 parts by weight, preferably 70 to 45 parts by weight.

If it exceeds 70 parts by weight, the notched isot impact strength will drop, making it unsuitable as a high impact molding material. The copolymer in MG is (ii) styrenic monomer and acryloni)
and (iii) a copolymer of a styrene monomer, an acrylonitrile monomer, and a maleimide monomer, and (ii) is mainly a composite gel forming step. It is formed in the dispersed gel phase formation step. In the dispersed gel phase forming step, a maleimide monomer is not used. In the dispersed gel phase forming step, the total amount of the dispersed gel phase is 100 parts by weight, and the rubbery polymer is 71 to 31 parts by weight, the styrene is It is preferable that a dispersed gel phase of 29 to 69 parts by weight of the copolymer of the monomer and the acrylonitrile monomer is formed.The structure of the dispersed gel phase was analyzed by the method described in Section B of Example 1. be done.

As described above, the MG according to the present invention contains not only a rubbery polymer but also two
It must contain a species of polymer.

This is because if the amount of such polymer is 1, the practical impact strength is low.

Although the reason why the NiG of the present invention exhibits the effect of improving practical impact strength is not clear, considering that the practical impact strength depends on the amount and type of copolymer in the MG, it is clear that the MG of the present invention is continuous with the dispersed phase. It is presumed that this serves to improve the bondability with the phase and the reinforcing effect of the rubbery polymer. The composition of copolymers other than the rubbery polymer in MG can be adjusted by bulk polymerization or solution polymerization. Generally a polymerization initiator (
The larger the amount of organic peroxide (organic peroxide), the higher the conversion rate in the polymerization process, and the higher the treatment temperature in the first step of de-septanomerization, the more 1.2 vinyl The content of copolymers other than the rubbery polymer in MG tends to increase as polybutadiene with more bonds is used or as the rubbery polymer has a higher solution viscosity in a 5% styrene solution. The appropriate amount of adjustment can be achieved by a trial and error method.

The MG of the present invention contains one or more cells with a diameter of 005μ or more, preferably 0.07μ or more inside the MG, and such MG
It is preferable that the proportion of the total amount of MG having cells with a diameter of 0.05μ or more, preferably 0.07μ or more inside is 50% by weight or more, preferably 70% by weight or more based on the total amount of MG. Such cells are those found as islets in the MG phase in electron micrographs. If the diameter of this cell and the proportion of MG having cells with this diameter are outside the above range, the impact resistance will be low (・
In order to form MG having a zero-cell structure, it is effective to carry out the step of forming a dispersed gel phase by bulk or bath liquid polymerization. Furthermore, by selecting the composition of the rubbery polymer used (which can be adjusted by those skilled in the art), for example, the higher the amount of 1,2-vinyl in the butadiene component, the higher the 5% styrene @ solution of the rubbery polymer. There is a tendency that the higher the viscosity, the higher the cell diameter and the content in MG.

The cell diameter is measured as follows based on an electron micrograph at a magnification of 10,000 times. The diameters of 100 to 200 dispersed MGs in an electron micrograph at 10,000 times magnification are measured. Measure the long axis and short axis of the MG, and the diameter of the MG (Di) = (long axis - short axis)
/2. For all gels S, = +γπrLl
) i is calculated (rL is the number).

■ On the other hand, the long and short axes of the cells were also measured, and the cell diameter = (
For MG having a cell diameter of 0.05 μ or more, the MG diameter (di) = (longer axis + shorter axis)/2 is measured again.

S2 = 4-: Calculate rr rn di2 (
m is the number). The weight percent of MG having cells of 0.05 tt or more is calculated by S2÷S, X100. Note that MGs with a diameter of 0.1μ or less are excluded from the calculation.

The dispersion composite gel-containing copolymer of the present invention has a continuous phase consisting of a maleimide monomer, a styrene monomer, and acrylonitrile (IJ).
It must contain a copolymer of base monomers as an essential component. Copolymers of maleimide monomers, styrene monomers, and acrylonitrile monomers are effective in providing an excellent balance of heat resistance and impact resistance. The composition of the total resin constituting the continuous phase is 1 to 30% by weight of maleimide monomer, more preferably 2 to 20% by weight, and 10 to 80% by weight of styrene monomer, more preferably 20 to 80% by weight.
70% by weight, more preferably 15-40% by weight of the acrylonitrile monomer.

The dispersed composite gel-containing copolymer of the present invention is produced by a continuous bulk or continuous solution polymerization method. That is, first, a styrene monomer and an acrylonitrile monomer are dissolved in a solvent to form a rubbery polymer solution.

The solution is then continuously fed into one or more stirred vessels to form a dispersed gel phase, and the polymerized compound with the formed dispersed gel phase is continuously fed into another reactor. Then, by continuing the polymerization reaction in the reactor, a composite gel skeleton is formed. After forming the skeleton and, if necessary, proceeding with final polymerization, unreacted monomers and solvent are removed from the reaction mixture at a temperature of usually 180 to 290°C to obtain a dispersed composite gel-containing copolymer. . In all such manufacturing steps, the conversion rate of monomers to polymer is usually 5 to 35% by weight in the dispersed gel phase formation step, based on the total monomers supplied to the reaction system, and 5 to 35% by weight in the composite gel skeleton formation step. In this case, the content is gradually increased to 20 to 80% by weight, and in the final polymerization method, it is increased to 30 to 80% by weight.

In the present invention, the styrenic monomers include styrene, α-methylstyrene, side chain alkyl-substituted styrene such as α-ethylstyrene, monochlorostyrene, dichlorostyrene, vinyltoluene, vinylxylene, 0-1-butyl Styrene, p-t-7" styrene such as tyrstyrene, p-methylstyrene; , 0-methoxystyrene, vinylnafretane, etc., but particularly preferred are styrene/and α-methylstyrene, and one or more of these styrenic monomers may be used.

The acrylonitrile monomer referred to in the present invention includes acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile, α-chloroacrylonitrile, and the like, with acrylonitrile being particularly preferred. One or more such monomers may be used.

Acrylonitrile is preferably used.

The maleimide monomer as used in the present invention is a straight monomer (in the formula, R represents hydrogen, or an alkyl, cycloalkyl, or aromatic residue having 1 to 15 carbon atoms), and includes, for example, Maleimide, N-methylmaleimide N-ethylmaleimide, N-propylmaleimide, N-t-butylmaleimide, N-inopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-naphthylmaleimide, N-o-chlorphene Examples include elmaleimide, and particularly preferred are maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

One or more types of such maleimide monomers are used.

In the present invention, the styrene monomer constituting the dispersed composite gel-containing copolymer is preferably styrene alone or a combination of styrene and α-methylstyrene. The composition ratio of methylstyrene is preferably 100/10 to 100/70.
, more preferably 100/15 to 100150.

Although the reason why such a composition ratio is preferable is not clear, by using styrene and α-methylstyrene together in a specific ratio, the proportion of the copolymer contained in the composite gel increases, so that such a component has a practical impact. It is presumed that this contributes to strength.

In the present invention, a part of the styrene monomer and acrylonitrile monomer of the copolymer constituent components is set at 2% relative to the total of the styrene monomer and acrylonitrile monomer.
At a proportion of 0% by weight or less, one or more of methacrylic ester monomers such as methyl methacrylate and acrylic ester monomers such as methyl acrylate may be substituted.

The rubbery polymer referred to in the present invention includes polybutadiene rubber, acrylonitrile-butazinine copolymer rubber (NB
R), diene rubbers such as styrene-ptazinine copolymer rubber (SBR), acrylic rubbers such as polybutyl acrylate, polypropyl acrylate, and ethylene-
Propylene-diene rubber (EPDM) or the like can be used. Particularly preferably, polybutadiene rubber and SBR are used.

In the copolymer of the present invention, the ratio of the dispersed composite gel is 4 to 4.
100/70 is preferable, more preferably 6-100/
70, particularly preferably 6 to 10 times.

The ratio of such a dispersed composite gel is measured by the following method. Partially dissolve 0.41 of the copolymer in 30CH of a 7/3 mixture of toluene/methyl ethyl ketone.

After centrifugation, the weight of the insoluble matter swollen with the solvent is weighed (W
l) Do. After weighing, the insoluble matter is vacuum dried and weighed again (W
2) Do. The ratio is given by w, ÷W;

This ratio depends on the amount of one type of polymerization initiator, the temperature and residence time during the devolatilization treatment, and further depends on the amount of maleimide monomer. Those skilled in the art can set appropriate ratios by selecting manufacturing process conditions by trial and error. When the ratio is less than 4, the impact strength is extremely low and the fluidity is also low. Moreover, even if it exceeds 11, the practical impact strength becomes small.

In the copolymer of the present invention, 30°C of the copolymer in the continuous phase
, 0.5 wt% dimethylformamide (DMF)
The reduced viscosity of the solution is preferably 0.5 to hot7! st
, more preferably 0.6 to 0.9 dll? , particularly preferably 0.6 to 0.85 de/y. When this value exceeds 1.0, fluidity deteriorates extremely, and when it is less than 0.5, impact strength decreases. Reduced viscosity is measured as follows. That is, the copolymer resin is dispersed in a mixed solvent of methyl, ethyl ketone/methanol 773, the insoluble components are removed by centrifugation, and the solvent containing the soluble components is separated by approximately 2.
Pour into 0 times the volume of methanol and reprecipitate. After filtering and drying this precipitate, the reduced viscosity is measured using dimethylformamide.

To the dispersion composite gel-containing copolymer of the present invention, 9 antioxidants such as ordinary hindered phenol antioxidants, phosphorus antioxidants, and sulfur antioxidants are added to improve thermal stability. A lubricant can also be added to further improve fluidity. Depending on the purpose, fiber reinforcing agents such as glass fibers, inorganic fillers, colorants, and pigments can also be blended.

Furthermore, the resin composition of the present invention may include tetrapromo bisphene/-/.
Flame retardation can be achieved by mixing general rhodanized organic compound flame retardants such as L'A, 7'' cabromobiphenyl ether, and brominated polycarbonate with antimony oxide.

The dispersed composite gel-containing copolymer of the present invention is polyvinyl chloride, styrene-acrylonitrile resin, polycarbonate, polybutylene terephthalate.

Polyethylene terephthalate, nylon 6, nylon 6
6, nylon 12, polyphenylene oxide, polyphenylene sulfide, and other resins for molding.

The present invention will be specifically explained below with reference to Examples, but these are not intended to limit the scope of the present invention.

Example 1. Reference Example 1゜Production of a 0-minute dispersion gel-containing polymer A dispersion composite gel-containing polymer was produced using a continuous bulk polymerization device in which a preheater and a vacuum tank were connected to the outlet of five reactors equipped with agitators in series. did. In the first reactor, 6 parts by weight of a rubbery polymer (Block 5BR containing 25 parts by weight of styrene component and 75 parts by weight of polybutadiene) and 20 parts by weight of ethylbenzene.
Parts by weight, 40 parts by weight of styrene, 10i of α-methylstyrene
A raw material solution consisting of i part of acrylonitrile and 24 parts by weight of acrylonitrile was continuously fed. The stirring speed of the first reactor was 350 revolutions. Further, 3 parts by weight and 22 parts by weight of N-phenylmaleimide were continuously supplied to the second and third reactors, respectively. An organic peroxide was used as a polymerization initiator, and dodecyl mercaptan was used as a molecular weight regulator. The temperature of the preheater was maintained at 260 to 280°C, and the degree of vacuum of the vacuum chamber was 7Q torr. The reaction temperature was adjusted so that the amount of rubbery polymer in the final dispersed gel-containing copolymer was 14 parts by weight.

Reference Example 1 uses a commercially available super heat-resistant brand of ABS as a reference sample for physical property evaluation.

Analysis of B0 polymer (1) Structural analysis of the dispersed gel phase and confirmation of the formation of the dispersed gel phase The reaction mixture was sampled from the outlet of the first reactor, and the structure of the dispersed gel phase was analyzed. Add 200 ppm of paratasia butylcatechol and incubate at 60°C and 10 torr for 3 hours at 100°C and 10 torr.
torr for 3 hours, 200℃ 10 torr for 2 hours,
It was treated at 250° C. and 70 torr for 2 hours to remove unreacted monomers and solvent. It was confirmed that polymerization did not substantially occur during this operation.

This treated product 1f was allowed to stand overnight in 30 cc of a mixed solvent of methyl ethyl ketone and methanol at a ratio of 7:3, and then the insoluble matter was separated by centrifugation. Insoluble matter was analyzed by elemental analysis and IR method after drying, and the composition was determined using the mass balance value. The results are shown in Table 1.

An electron micrograph (transmission type, magnification: 10,000 times) of the above-mentioned treated product was taken, and the presence or absence of the formation of a dispersed gel phase was observed. The results are shown in Table 1.

(2) Structural analysis of dispersed multistage gel The finally obtained copolymer 11 was left overnight in a mixed solvent of 30Ce of methyl ethyl ketone and methanol at a ratio of 7:3, and separated into insoluble and soluble components by centrifugation. did. Insoluble matter was analyzed by elemental analysis and IR method after drying, and the composition was determined using the mass balance values in the manufacturing process. In addition, the soluble content was reprecipitated using 400 CC of methanol, the continuous phase copolymer was recovered, and after drying, the composition was analyzed, and further 025
The copolymer of No. 2 was dissolved in 50 CC of dimethylformamide, and the reduced viscosity was determined using an Uberote viscometer. We also calculated the ratio.

Electron micrograph of the finally obtained copolymer (transmission type 1
The cells within the gel were observed. Table 1 shows the results.
Shown below.

C0 Physical Property Evaluation C-1, Molding After drying the obtained copolymer at 80°C for 3 hours, it was molded with an injection molding machine at a molding temperature of 240°C and a mold temperature of 60°C.

Evaluation of C2 physical properties (1) Izod impact strength: JIS K
687].

(2) Evaluation of flame resistance: ASTM D 1525
Measure the Vicat softening point according to.

(3) Evaluation of molding processability: Evaluation was performed based on the oil pressure of the molding machine (short shot oil pressure) required for the lowest injection pressure that does not cause short shots in injection molding. Commercially available A
Based on BS (R heat resistant brand, reference example), evaluation was made based on the difference in short shot oil pressure. (If the difference value is negative, the oil pressure is lower than that of commercially available ABS (super heat resistant brand) (it is evaluated as a material with good fluidity during molding processing) (4) Evaluation of practical impact strength: Figure 1 (a) is made by injection molding.
), a falling weight impact strength test was conducted on three parts of the molded product having the shape shown in FIG. 1(b), part (1), part (2), and part (3). Tip of falling weight R = 6.4 m
1 m, and the inner diameter of the loading platform was 25 m/rn. Part (1) is a part whose thickness changes, part (2) is a part near the corner, and part (3) is a standard part.

C-3, the evaluation results are shown in Table 1.

Example 2゜Example 1 except that the type of rubbery polymer used was polybutadiene. Manufacturing evaluation was performed in the same manner as above. Table 1 shows the results.
Shown below.

Comparative example 1゜N-phenylmaleimide was added to the first reactor.
Production and evaluation were carried out in the same manner as in Example 2, except that the part by weight was changed to 2.2 parts by weight in the second reactor. A copolymer containing a maleimide monomer as a component is contained in the dispersed gel phase, and a copolymer containing a dispersed gel, which is not a composite gel and is outside the scope of the present invention, was obtained. As a result of physical property evaluation, the Izot impact strength, Vigat softening point, and moldability were the same as in Example 2, but the practical impact strength was inferior. The results are shown in Table 1.

Comparative Example 2° A rubber-like polymer was produced and evaluated in the same manner as in Example 1, except that the rubbery polymer used was changed to 3 parts by weight of polybutadiene, 40 parts by weight of the styrene component, and 3 parts by weight of Block 5BR, which was 60 parts by weight of polybutadiene. A copolymer containing a dispersed composite gel was obtained in which the cell diameter of the dispersed composite gel was small and was outside the scope of the present invention.

Compared to Example 1, the practical impact strength was inferior. demon.

Comparative Example 3 A product was produced and evaluated in the same manner as in Example 2, except that the stirring speed of the first reactor was set to 90 revolutions and the temperature of the preheater was changed to 290 to 310°C. A composition was obtained in which the copolymer content in the dispersed composite gel was high and was outside the scope of the present invention. Compared to Example 2, the practical impact strength was inferior.

Comparative Example 4゜In the presence of 14 parts by weight of polybutadiene rubber latex, 8 parts by weight of styrene, 2 parts by weight of α-methylstyrene, and 3 parts by weight of acrylonitrile were polymerized by a batch emulsion polymerization method, and then 10 parts by weight of N-phenylmaleimide was added. part, styrene 10
parts by weight, 2 parts by weight of α-methylstyrene, and 5 parts by weight of acrylonitrile were polymerized. A composition was obtained in which the content of the copolymer in the dispersed composite gel was small and the cell diameter was small, which was outside the scope of the present invention. In particular, the practical impact strength was low.

〔Effect of the invention〕

As detailed above, the dispersed composite gel-containing copolymer of the present invention has excellent practical impact strength, heat resistance, and moldability, and also has an excellent appearance, and is used as a component material for electrical equipment, electronic equipment, automobiles, etc. Its industrial value is extremely large in terms of industrial applications.

[Brief explanation of drawings]

FIG. 1 shows the shape of the molded product used in the falling weight impact test. (a) is a plan view, and (b) is a sectional view.

Claims (6)

[Claims] (1) A copolymer consisting of a continuous phase and a dispersed phase, comprising (a
) The dispersed phase is composed of a composite gel, and the composite gel comprises (i) a rubber polymer, (ii) a copolymer of a styrene monomer and an acrylonitrile monomer, and (iii) a styrenic monomer and acrylonitrile. and a copolymer of a maleimide monomer and a maleimide monomer, and when the total amount of the composite gel is 100 parts by weight, (i) the rubbery polymer is 30 to 70 parts by weight; , the total amount of the latter two copolymers (ii) and (iii) is 70 to 30 parts by weight, and (b) the continuous phase is at least a maleimide monomer, a styrene monomer, and an acrylonitrile monomer. A dispersed composite gel-containing copolymer composed of a copolymer with a monomer. (2) The ratio of the total amount of the composite gel containing cells with a diameter of 0.05 μ or more inside the composite gel is 50% by weight or more with respect to the total amount of the composite gel. Dispersed composite gel-containing copolymer. (3) The dispersed composite gel-containing copolymer according to claim 1 or 2, wherein the styrenic monomers are styrene and α-methylstyrene. (4) The ratio of styrene and α-methylstyrene is 100/
The dispersed composite gel-containing copolymer according to claim 3, which has a molecular weight of 10 to 100/70. (5) The dispersed composite gel-containing copolymer according to any one of claims 1 to 3, wherein the composite gel has a crosslinking degree index of 4 to 11 times. (6) 30°C, 0.5w of the copolymer constituting the continuous phase
Reduced viscosity in t% dimethylformamide solution is 0
．． The dispersed composite gel-containing copolymer according to any one of claims 1 to 4, wherein the dispersion composite gel content is 5 to 1.0 dl/g.