JP5184776B2 - Masterbatch composition, composite material composition, composite material molded body, and production method thereof - Google Patents

Description

  The present invention relates to a resin-modifying master batch composition and the like.

  Conventionally, in order to improve various properties of a thermoplastic resin, in particular, rigidity, it has been practiced to mix inorganic fillers such as talc and improve the various properties due to its reinforcing effect. For example, talc is known to improve the rigidity of crystalline thermoplastic resins. However, in order to obtain sufficient rigidity, a large amount of talc has to be added, and it has not been able to sufficiently meet the demand for weight reduction of the molded body. Therefore, an inorganic filler that exhibits a large effect with a small amount of addition has been desired.

  Therefore, in recent years, a clay mineral, which is a kind of layered compound, is used as an inorganic filler, a composition containing a thermoplastic resin and an inorganic layered compound is melt-mixed using a twin screw extruder or the like, and the thermoplastic resin is Attempts have been made to delaminate layered clay minerals and disperse them in nano-order.

  In such a composite material composition, since it is difficult to finely disperse the layered compound, the composition containing the layered compound and the thermoplastic resin is mixed in advance, and after preparing the master batch composition, the other components are added. A method for producing a composite material composition by mixing is proposed.

  Patent Document 1 proposes, as a masterbatch composition, a composition containing layered silicate and modified polyolefin as essential components and, if necessary, non-modified polyolefin.

  Claim 13 of Patent Document 2 proposes a composition containing clay having a layered structure, a modified polyolefin, and an unmodified polyolefin as a masterbatch composition.

In paragraph 0035 of Patent Document 3, a composition containing a layered silicate and unmodified polypropylene is proposed as a masterbatch composition.
JP 2000-281847 A JP 2005-307201 A JP 2004-51827 A

  An object of this invention is to provide the masterbatch composition which can raise further the dispersibility of the layered compound in a thermoplastic resin, and can raise mechanical strength.

  As a result of intensive studies to solve the above problems, the present inventor has improved the dispersibility of the layered compound in the thermoplastic resin by using the following novel masterbatch composition, thereby increasing the mechanical strength. The inventors have found that the present invention can be performed, and have reached the present invention.

That is, the present invention
[1] Hydrogenation mainly composed of vinyl aromatic monomer unit and conjugated diene monomer unit grafted by component (A) layered compound whose organic layer is treated and component (B) acid anhydride A master batch composition containing a copolymer, wherein the component (B) has a number average molecular weight (Mn) of 300,000 or less, and a graft amount (acid value) of an acid anhydride of 1 mg CH ₃ ONa / g or more. The conjugated diene-derived 1,2-bond unit content in the copolymer before hydrogenation is 15% or more, the content of the component (A) is 10 wt% to 70 wt%, and the content of the component (B) A masterbatch composition having an amount of 30 wt% to 90 wt%;
[2] The master batch composition according to [1], wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component (B) is 1.1 or more;
[3] The master batch composition according to the above [1] or [2], wherein the acid value of the component (B) is 4 mg CH ₃ ONa / g or more;
[4] The master batch composition according to any one of [1] to [3] above, wherein the number average molecular weight (Mn) of the component (B) is 80,000 or less;
[5] In the X-ray diffraction analysis, the double value (2θ) of the diffraction angle is in the range of 1.5 ° to 3.5 °, and the peak value derived from the layered compound is present at 2.6 ° or less, Alternatively, the master batch composition according to any one of [1] to [4], wherein no peak is present;
[6] Any one of the above [1] to [5], wherein the amount of ungrafted unreacted material contained in the component (B) is 0.1 mgCH ₃ ONa / g or more and 5 mgCH ₃ ONa / g or less. The masterbatch composition according to item;
[7] A composite material composition comprising the masterbatch composition described in any one of [1] to [6] above and a polyolefin resin;
[8] A composite material molded body comprising the masterbatch composition according to any one of [1] to [6] above and a polyolefin resin;
[9] At least a layered compound in which component (A) is organically treated between layers, and component (B) vinyl aromatic monomer unit and conjugated diene monomer unit grafted with acid anhydride The present invention relates to a method for producing a masterbatch composition comprising a step of mixing a composition containing a hydrogenated copolymer using a screw extruder.

  If the masterbatch composition of this invention is used, the dispersibility of the layered compound in a thermoplastic resin can be improved, and the mechanical strength of the said resin can be improved.

  The layered compound which is the component (A) of the present invention refers to a compound having a layered structure such as graphite, metal chalcogen compound, metal oxide, metal phosphate, clay mineral and the like. Among these, a layered clay mineral is preferable in terms of high delamination property.

  Examples of layered clay minerals include smectites such as montmorillonite, sapotite, hydelite, nontrite, hectorite, and stevensite, vermiculite, halloysite, and swellable mica. Any of the layered clay minerals, natural or synthetic, can be used. Furthermore, compounds obtained by subjecting talc to fluorine treatment by synthesis into swellable mica, or those obtained by hydrothermal synthesis as described above are exemplified. In addition, various compounds in which cations supported between layers are substituted with ions such as sodium, potassium, and lithium can be applied.

  Among the layered viscosity minerals, an organically treated layered clay mineral is particularly preferable in terms of delamination and fine dispersibility. The organic formation of the layered viscosity mineral can be generally performed by a wet method. After sufficiently solvating the layered silicate with water or alcohol, an organic cation is added and stirred to replace the metal ions between the layers of the layered silicate with the organic cation. Thereafter, the unsubstituted organic cation is sufficiently washed, filtered and dried. In addition, it is also possible to directly react the layered silicate and the organic cation in an organic solvent, or to heat and knead the layered silicate and the organic cation in an extruder in the presence of a resin.

  The cation exchange capacity of the layered clay mineral is preferably 50 meq / 100 g or more in terms of high ion exchanging ability of the organic cation during the organic treatment, and 200 meq / 100 g or less in terms of increasing delamination. Is preferred.

  Examples of organic cations used for organizing layered clay minerals include stearyl ammonium ion, hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, dodecyl ammonium ion, octadecyl ammonium ion, dioctyl dimethyl ammonium ion, trioctyl ammonium ion. , Distearyl ammonium ion, 1-hexenyl ammonium ion, 1-dodecenyl ammonium ion, 9-octadecel ammonium ion, 9,12-octadecel ammonium ion, ammonium salt consisting of 12-aminododecanoic acid and hydrochloric acid, alkyl Ammonium ion such as ammonium salt consisting of propylenediamine and hydrochloric acid, tetraethylphosphonium ion, triethylbenzine Foss phosphonium ion, tetra -n- butyl phosphonium ion, and phosphonium ions such as tri -n- butyl hexadecyl phosphonium ion. In the present invention, one or more layered clay minerals may be used.

  The content of the component (A) in the master batch composition is preferably 10 wt% or more, more preferably 15 wt% or more from the viewpoint of economy. Moreover, from the point of the melt mixing property of a masterbatch composition, 70 wt% or less is preferable, More preferably, it is 60 wt% or less, More preferably, it is 50 wt% or less.

  Component (B) of the present invention is obtained by hydrogenating a polymer mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit and grafting an acid anhydride.

  Examples of the vinyl aromatic monomer include monomers such as styrene, P-methylstyrene, tertiary butylstyrene, α-methylstyrene, 1,1-diphenylethylene, and among them, styrene is preferable.

  Examples of the conjugated diene monomer unit include butadiene and isoprene, and butadiene is preferable from the viewpoint of compatibility of the resin composition.

  The copolymer before grafting of hydrogenated and acid anhydrides has the following block structure in terms of processability during the production of the masterbatch, dispersibility of the layered compound, or mechanical strength of the polyolefin resin. What has is preferable.

For example, the following general formula (AB) _n , A- (BA) _n , A- (BA) _n- B, B- (AB) _n
Or a linear block copolymer represented by the following general formula [(AB) _k ] _m -X, [(AB) _k -A] _m -X
[(BA) _k ] _m -X, [(BA) _k -B] _m -X
A linear block copolymer or a radial block copolymer represented by the formula (in the above formula, A represents a polymer block mainly composed of vinyl aromatic hydrocarbon units. B represents a diene unit or a vinyl aromatic unit. A polymer block mainly composed of one or more units selected from the group consisting of a vinyl aromatic unit in B is preferably 50 wt% or less in view of mechanical strength of the polyolefin resin. And more preferably 10 wt% or less, and n, k and m are integers of 1 or more, generally 1 to 6).

  X is, for example, silicon tetrachloride, tin tetrachloride, epoxidized soybean oil, polyhalogenated hydrocarbon compound, carboxylic acid ester compound, polyvinyl compound, bisphenol type epoxy compound, alkoxysilane compound, halogenated silane compound, ester compound, etc. A residue of a coupling agent or a residue of an initiator such as a polyfunctional organolithium compound is shown. From the viewpoint of high transparency of the thermoplastic copolymer and its composition, non-halogen coupling agents are preferred, and alkoxysilanes are more preferred.

  Moreover, the structures represented by the above general formula may be arbitrarily combined. The coupling agent compound may be used alone or in a mixture of two or more. For example, in the case of a copolymer of vinyl aromatic hydrocarbon and butadiene, the vinyl aromatic hydrocarbon units in the polymer block may be distributed uniformly or non-uniformly (for example, tapered). A plurality of uniformly distributed portions and / or non-uniformly distributed portions may coexist in each block.

  The copolymer before hydrogenation and acid anhydride grafting is a polymer block mainly composed of a vinyl aromatic monomer unit in terms of enhancing the peelability of the layered compound and the breaking strength of the composite material composition. It is preferable to contain one or more. The content of the polymer block mainly composed of vinyl aromatic monomer units is more preferably in the range of 5 wt% to 40 wt%, and still more preferably in the range of 10 wt% to 30 wt%.

  In the present invention, the “polymer block mainly composed of A units” means that 60 wt% or more of A (monomer) units are contained in the block.

  Examples of the method for producing the block copolymer include Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17879, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423. And the methods described in JP-B-48-4106, JP-B-56-28925, JP-B-51-49567, JP-A-59-166518, JP-A-60-186777, and the like. It is done.

  The vinyl content derived from the conjugated diene in the copolymer before hydrogenation is preferably at least 15 mol%, more preferably at least 25 mol%, from the viewpoint of the high breaking strength of the composite material composition. 30 mol% or more is more preferable, and 35 mol% or more is more preferable.

  The method for hydrogenating a polymer mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit is not particularly limited, and is performed using a known technique.

  The hydrogenation rate is preferably 50 mol% or more in the double bond in the conjugated diene from the viewpoint of heat resistance in the production of the master batch composition. 70 mol% or more is more preferable, and 85 mol% or more is more preferable.

  The acid anhydride to be grafted to the copolymer is maleic anhydride, hymic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] oct-5. -Ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-octa-1,3-diketospiro [4.4] Non-7-ene, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride, x-methyl-bicyclo [2.2. 1] Hept-5-ene-2,3-dicarboxylic acid anhydride, x-methyl-norbornene-5-ene-2,3-dicarboxylic acid anhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride Unsaturated dicarboxylic acid anhydride It can gel. Among the acid anhydrides, maleic anhydride or hymic anhydride is preferable in terms of availability and graft reactivity.

  Two or more of the above unsaturated carboxylic acid anhydrides can be used in combination, or a ring-opened product of unsaturated dicarboxylic acid anhydride and unsaturated dicarboxylic acid anhydride can be used in combination. If necessary, a ring-opened product of these unsaturated dicarboxylic acid anhydrides can also be used.

The graft amount (acid value) of the acid anhydride of component (B) is indispensably 1 mg CH ₃ ONa / g or more from the viewpoint of dispersibility of the layered compound (A). 4 mgCH ₃ ONa / g or more is more preferable, 6 mgCH ₃ ONa / g or more is more preferable, and 7 mgCH ₃ ONa / g or more is most preferable.

Moreover, the graft amount (acid value) of the acid anhydride of the master batch composition can be determined from the product of the ratio of the component (B) and the graft amount (acid value). From the viewpoint of dispersibility of the layered compound, 1 0.5 mg CH ₃ ONa / g or more is preferable. 2.5 mgCH ₃ ONa / g or more is more preferable, and 5.5 mg CH ₃ ONa / g or more is more preferable.

  The acid value can be determined by titration of sodium methylate. The graft amount (acid value) of the acid anhydride in the component (B) can be determined, for example, by titrating the copolymer after washing with acetone.

On the other hand, ungrafted unreacted substance content (content of unreacted acid anhydride and unreacted ring opening product) contained in component (B) is determined by titrating the acetone extract. Can do. The amount of unreacted unreacted material (content of unreacted acid anhydride and unreacted product of the ring-opened product) contained in component (B) is 0 in terms of dispersibility of the layered compound (A). .1 mgCH ₃ ONa / g or more is preferable, and 0.5 mgCH ₃ ONa / g or more is more preferable. Further, preferably less 5mgCH ₃ ONa / g in terms of storage stability of the masterbatch, more preferably 4mgCH ₃ ONa / g, more preferably from 3mgCH ₃ ONa / g. In order to satisfy the above unreacted material amount, it is preferable to suppress the amount of reduced pressure.

  The ring opening rate of the grafted acid anhydride is preferably 90% or less from the viewpoint of stable releasability at the time of producing the master batch. 50% or less is more preferable, and 10% or less is still more preferable.

  In order to graft an acid anhydride onto a hydrogenated polymer mainly composed of a vinyl aromatic monomer unit and a conjugated diene monomer unit, various conventionally known methods can be employed. For example, a method of dissolving a vinyl aromatic compound-conjugated diene compound copolymer hydrogenated product in a solvent such as toluene or xylene and adding an unsaturated dicarboxylic acid anhydride thereto to carry out a graft reaction, or an extruder Examples thereof include a method in which a vinyl aromatic compound-conjugated diene compound hydrogenated product is melted and an unsaturated dicarboxylic acid anhydride is added thereto to cause a graft reaction. In any case, in order to efficiently graft copolymerize the unsaturated carboxylic acid anhydride, it is preferable to carry out the grafting reaction in the presence of a radical initiator. The grafting reaction is usually performed under conditions of 60 to 350 ° C. The ratio of the radical initiator used is usually in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin before modification.

  The radical initiator is preferably an organic peroxide such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne-3, 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl- 2.5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octoate, tert-butyl Ruperupibareto and cumyl perpivalate and tert- butyl hydroperoxide diethyl acetate. Other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate can also be used.

  The number average molecular weight (Mn) of the component (B) is preferably 40,000 or more in terms of peelability of the layered compound, and is preferably 300,000 or less in terms of extrudability. The range of 40,000 to 160,000 is more preferable, and the range of 50,000 to 80,000 is more preferable.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component (B) is preferably 1.1 or more in terms of workability. 1.2 or more is more preferable, and 1.3 or more is more preferable.

  The number average molecular weight and weight average molecular weight are measured, for example, by gel permeation chromatography (apparatus: LC-10 (manufactured by Shimadzu Corporation, trade name), column: TSKgelGMHXL (4.6 mmID × 30 cm), solvent: tetrahydrofuran). It can obtain | require from the polystyrene conversion molecular weight by.

  The masterbatch composition of the present invention comprises a polymer mainly composed of an unmodified vinyl aromatic monomer unit and a conjugated diene monomer unit in addition to the component (A) and the component (B), if necessary. A hydrogenated product may be contained. The content of such a hydrogenated polymer in the master batch composition is preferably 40 wt% or less, more preferably 25 w% or less, and even more preferably 10% or less, from the viewpoint of dispersibility of the layered compound.

  Moreover, the masterbatch composition of the present invention may contain a modified or non-modified thermoplastic resin in addition to the component (A) and the component (B) as necessary. The content of the thermoplastic resin is preferably 30% by weight or less, more preferably 20% by weight or less, and further preferably 10% by weight or less from the viewpoint of dispersibility of the layered compound.

  Here, the modified thermoplastic resin refers to a thermoplastic resin having at least one functional group selected from a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, an imino group, a silanol group, and an alkoxysilane group. . Among these, a modified polyolefin having at least one functional group is preferable.

  Examples of the polyolefin used in the modified polyolefin include, for example, homopolymers of α-olefins such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene, or random or block copolymer consisting of two or more types. It is a coalescence. Specifically, polyethylene, polypropylene, polybutene-1, polyisobutene, poly-3-methylpentene-1, poly-4-methylpentene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, propylene-4 -Methylpentene-1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, decene-1-4-methylpentene-1 copolymer and the like.

  Examples of the production of modified polyolefin include a method of graft copolymerization or block copolymerization of an unsaturated monomer with polyolefin. Examples of the unsaturated monomer include mono- or dicarboxylic acid such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, and unsaturated carboxylic acid derivatives that are anhydrides thereof; hydroxyethyl (meth) acrylate, ( (Meth) acrylic acid esters such as glycidyl acrylate and aminoethyl (meth) acrylate; alkoxysilanes having vinyl groups such as vinyltrimethoxysilane and γ-propyltrimethoxysilane γ are included. Among these, maleic anhydride and glycidyl methacrylate are particularly preferable because of excellent dispersibility of the layered silicate.

  The weight average molecular weight of the modified polyolefin used in the present invention is not particularly limited as long as the object of the present invention is not impaired, but the weight average molecular weight is preferably 10,000 or more, more preferably 30,000 or more.

  Moreover, you may add a small amount of organic acids, such as a stearic acid, an oleic acid, or a linoleic acid, to the masterbatch composition of this invention from the viewpoint of the dispersibility of a layered compound as needed.

  The manufacturing method of the masterbatch composition of the present invention is not particularly limited, and a known method can be used. For example, a melt kneading method using a general mixer such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, etc., each component is dissolved or dispersed and mixed, and then the solvent is heated. The removal method is used, and the melt kneading method using an extruder is particularly preferred from the viewpoint of productivity and good kneading properties.

  From the viewpoint of dispersibility of the layered compound, a melt mixing method using a twin screw extruder is better. From the viewpoint of dispersibility of the layered compound, it is better that the screw rotation speed and the melting temperature are higher. 300 degreeC or less is preferable and 260 degrees C or less is more preferable at the point which suppresses the thermal deterioration of a layered compound or resin.

  After mixing all the raw materials of the master batch, it is charged into the twin screw extruder, or after the component (B) or thermoplastic resin is charged into the twin screw extruder, the other components are introduced from the discharge side from the charging port. You may throw in once or several times.

  In the master batch composition of the present invention, the double value (2θ) of the diffraction angle is preferably in the range of 1.5 ° to 3.5 ° in the X-ray diffraction analysis in view of the dispersibility of the layered compound. In addition, it is preferable that the peak value derived from the layered compound is present at less than 2.7 ° or no peak is present. When the peak value exists, it is preferably 2.6 ° or less, more preferably 2.4 ° or less, but most preferably no peak.

  The peak value can be measured using a sample obtained by pressing the master batch composition at 230 ° C. to a thickness of 1 mm using an X-ray diffractometer RINT2000 (manufactured by Rigaku, trade name, target: Cu, 40 kV, 300 mA). When there are two peaks, it means the average value of the peak values.

  The masterbatch composition of the present invention is suitable for a composite material composition mainly composed of polyolefin, particularly a composite material composition mainly composed of polypropylene.

  The composite material composition is, for example, a resin mainly composed of polypropylene and the masterbatch composition of the present invention, such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, etc. It can be produced by melt kneading using a general mixer.

  In the composite material composition, the content of the component (A) layered compound is preferably 0.1 wt% or more in view of the high rigidity and fracture strength of the composite material composition. 10 wt% or less is preferable in terms of breaking strength. 0.3 wt% to 7 w% is more preferable, and a range of 0.5 wt% to 5 wt% is more preferable.

  The present invention also provides a composite material molded body obtained by mixing the masterbatch composition according to the present invention and a polyolefin resin. Such a composite material molded body is obtained by molding the composite material composition according to the present invention into a desired shape, and is a high quality product excellent in rigidity and fracture strength.

  Hereinafter, the present invention will be described more specifically with reference examples, examples, and comparative examples, but the present invention is not limited to these examples.

(1) Preparation of Masterbatch Composition (1-1) Layered Compound of Component (A) As Component (A) Layered Compound, Dimethyldialkylammonium / Synthetic Mica (Organic Modified Fluorinated Mica, Somasif MAE, Corp Chemical Co., Ltd.) Manufactured, trade name, organic substance amount: 37 wt%).

(1-2) Preparation of hydrogenated copolymer (1-2-1) Preparation of hydrogenation catalyst For hydrogenation reaction of a copolymer mainly composed of vinyl aromatic monomer units and conjugated diene monomer units. The hydrogenation catalyst used was prepared by the following method.
Charge 1 liter of dry and purified cyclohexane to a nitrogen-substituted reaction vessel, add 100 mmol of biscyclopentadienyltitanium dichloride, add an n-hexane solution containing 200 mmol of trimethylaluminum with sufficient stirring, and For about 3 days.

(1-2-2) Preparation of Hydrogenated Copolymer A-M0 (No Acid Anhydride Grafting) Batch polymerization was carried out using a stirrer with an internal volume of 10 L and a jacketed tank reactor. First, 6.4 L of cyclohexane and 160 g of styrene are added, and TMEDA is added in advance so that the number of moles of Li of n-butyllithium is 0.50 times, and a predetermined amount of n-butyllithium initiator is added. Polymerization was performed at a temperature of 65 ° C., and after completion of the polymerization, a cyclohexane solution containing 680 g of butadiene (monomer concentration of 22 wt%) was continuously supplied to the reactor at a constant rate over 60 minutes, and after completion of the polymerization, 160 g of styrene was contained. A cyclohexane solution (monomer concentration of 22 wt%) was continuously supplied to the reactor at a constant rate over 10 minutes, and a copolymer was obtained after completion of the polymerization.
The styrene content was 32 wt%, and the 1,2-bond units in butadiene were 33%.
To the obtained copolymer, 100 ppm of the above hydrogenation catalyst was added as titanium per 100 parts by weight of the polymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 75 ° C. 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the hydrogenated copolymer. .
The number average molecular weight (Mn) of the obtained hydrogenated copolymer was 68,000, and the hydrogenation rate in the double bond of butadiene contained in the hydrogenated copolymer was 99%.

(1-2-3) Preparation of hydrogenated copolymer B-M0 (without acid anhydride grafting) In the same procedure as in (1-2-2), the n-butyllithium initiator was changed to contain styrene. The amount was 32 wt%, and the 1,2-bond unit in butadiene was 33% to obtain a copolymer before hydrogenation. Thereafter, hydrogenation was carried out in the same manner, the number average molecular weight (Mn) was 132,000, and the hydrogenation rate in the double bond of butadiene contained in the hydrogenated copolymer was 99%.

(1-2-4) Preparation of hydrogenated copolymers A-M5 and A-M10 (with acid anhydride graft) A-M0 obtained in (1-2-2) was placed in a twin-screw extruder. Perhexa 25B (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was used as a radical generator, and an anhydrous malee was reacted with the copolymer to produce a copolymer having a graft amount (acid value) of 5 mg CH ₃ ONa / g (A -M5) and give 10mgCH ₃ ONa / g of copolymer (a-M10).

(1-2-5) Preparation of hydrogenated copolymer B-M10 (with acid anhydride graft) B-M0 obtained in (1-2-2) was subjected to radical generator in a twin-screw extruder. Perhexa 25B (manufactured by Nippon Oil & Fats Co., Ltd., trade name) was used, and the maleic anhydride was reacted with the copolymer to obtain a copolymer having a graft amount (acid value) of 10 mg CH ₃ ONa / g.

(1-2-6) Preparation of hydrogenated copolymer C-M5 (with acid anhydride graft) In the same procedure as in (1-2-2), the n-butyllithium initiator was changed to contain styrene. The amount of the copolymer before hydrogenation was 32% by weight, and the 1,2-bond unit in butadiene was 45%. Thereafter, hydrogenation was carried out in the same manner, the number average molecular weight (Mn) was 90000, and the hydrogenation rate in the double bond of butadiene contained in the hydrogenated copolymer was 99%.
In the twin-screw extruder, Perhexa 25B (manufactured by Nippon Oil & Fats Co., Ltd., trade name) was used as a radical generator in the obtained polymer, and anhydrous maleic was reacted with the copolymer. Thereafter, acetone was washed.
The graft amount (acid value) contained in the obtained copolymer was 5 mg CH ₃ ONa / g, and the unreacted amount (acid value) not grafted was 0.2 mg CH ₃ ONa / g.
Table 1 shows the molecular weight, graft amount (acid value), and unreacted unreacted amount (acid anhydride that could not be added to the added molecular chain and its ring-opened product content) of each hydrogenated copolymer.

(1-3) Preparation of Masterbatch Composition A masterbatch composition having the composition shown in Table 2 was prepared at 250 ° C. and 250 rpm using a twin screw extruder.

(2) Preparation of composite material composition As a composite material composition of the present invention, a polypropylene composition was prepared. Using the masterbatch composition obtained in (1-3), add polypropylene BC03MSW (trade name, manufactured by Nippon Polypro Co., Ltd.) so that the amount of somasif MAE is 4 wt%, and mix with a twin screw extruder. did.

(3) Evaluation method (3-1) Styrene content, 1,4-bond / 1,2-bond unit, ethylene unit or butylene unit amount Vinyl aromatic monomer unit, 1,4-bond unit of butadiene and The amount of 1,2-bond units, ethylene units or butylene units was measured by nuclear magnetic resonance spectrum analysis (NMR). JNM-LA400 (manufactured by JEOL, trade name) is used as a measuring instrument, deuterated chloroform is used as a solvent, sample concentration is 50 mg / ml, observation frequency is 400 MHz, chemical shift standard is TMS (tetramethylsilane), pulse delay 2. 904 seconds, 64 scans, pulse width 45 °, and measurement temperature 26 ° C.

(3-2) Weight average molecular weight and molecular weight distribution LC-10 (manufactured by Shimadzu Corporation, trade name) is used for the apparatus, two TSKgelGMHXL (4.6 mmID × 30 cm) are used for the column, the oven temperature is 40 ° C., and the solvent is used. Was measured with tetrahydrofuran (1.0 ml / min). Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were calculated as molecular weight in terms of polystyrene.

(3-3) Dispersibility of filler in masterbatch A sample obtained by pressing the masterbatch composition of Table 2 to a thickness of 1 mm at 230 ° C was used as an X-ray diffractometer RINT2000 (manufactured by Rigaku, trade name, target: Cu, 40 kV, 300 mA). ) And analyze the range where the double value (2θ) of the diffraction angle is 1.5 ° to 3.5 °.
Less than 2.2 ° or absence of a peak is the finest dispersion, and ◎, more than 2.2 ° and 2.4 ° or less is the next best, and ○ is greater than 2.4 ° and less than 2.6 ° Is next better, ○ ', and 2.7 ° or more is x.

(3-4) Elastic Modulus of Polypropylene Composition A strip-shaped sample obtained by injection-molding the polypropylene composition obtained in (2) at 230 ° C. into a thickness of 3 mm, a width of 10 mm, and a length of 80 mm was obtained at 23 ° C., 50 It was measured at% RH at a three-point bending, a fulcrum distance of 50 mm and a test speed of 2 mm / min. Larger values are preferred.

[Examples 1 to 5, Comparative Example 1]
The evaluation test results of Examples 1 to 5 and Comparative Example 1 are shown in Table 2.
When the graft amount (acid value) of the acid anhydride is 1 mg CH ₃ ONa / g or more, for the first time, the dispersibility of the layered compound in the master batch is high, and the propylene composition prepared using the master batch has a high elastic modulus. You can see that
Among them, the graft amount of acid anhydride is 6 mg CH ₃ ONa / g or more, the number average molecular weight (Mn) is 80,000 or less, and the amount of unreacted unreacted material (unreacted acid anhydride and ring opening thereof) It can be seen that when the content of the unreacted product is 0.5 mg CH ₃ ONa / g or more, a very good dispersibility of the layered compound and a propylene composition having a high elastic modulus can be obtained.

[Examples 1, 6 and 7, Comparative Example 2]
The evaluation test results of Examples 1, 6, 7 and Comparative Example 2 are shown in Table 3.
Only when the content of the component (A) is 10 wt% to 70 wt% and the content of the component (B) is 30 wt% to 90 wt%, the dispersibility of the layered compound in the master batch is enhanced.

The masterbatch composition of the present invention can be suitably used in the field of composite material compositions such as polypropylene resin.

Claims (9)

Component (A) layered compound that has been subjected to organic treatment between layers, and
A masterbatch composition containing a hydrogenated copolymer mainly composed of vinyl aromatic monomer units and conjugated diene monomer units grafted with component (B) acid anhydride,
The component (B) has a number average molecular weight (Mn) of 300,000 or less, an acid anhydride graft amount (acid value) of 1 mg CH ₃ ONa / g or more, and 1, which is derived from a conjugated diene in a copolymer before hydrogenation. 2- Bond unit content is 15% or more,
The masterbatch composition whose content of the said component (A) is 10 wt%-70 wt%, and whose content of the said component (B) is 30 wt%-90 wt%.   The masterbatch composition of Claim 1 whose ratio (Mw / Mn) of the weight average molecular weight (Mw) of the said component (B) and number average molecular weight (Mn) is 1.1 or more. When the acid value of component (B) is 4mgCH ₃ ONa / g or more, the masterbatch composition according to claim 1 or 2.   The master batch composition according to any one of claims 1 to 3, wherein the number average molecular weight (Mn) of the component (B) is 80,000 or less. In X-ray diffraction analysis,
The double value (2θ) of the diffraction angle is in the range of 1.5 ° to 3.5 °,
The master batch composition according to any one of claims 1 to 4, wherein a peak value derived from the layered compound is present at 2.6 ° or less or no peak is present. The unreacted amount ungrafted contained in component (B) is 0.1mgCH ₃ ONa / g or more, 5MgCH is ₃ ONa / g or less, a master batch according to any one of claims 1 to 5 Composition.   The composite material composition containing the masterbatch composition of any one of Claims 1-6, and polyolefin resin.   A composite material molded body comprising the masterbatch composition according to any one of claims 1 to 6 and a polyolefin resin. at least,
Component (A) layered compound that has been subjected to organic treatment between layers, and
A composition containing a hydrogenated copolymer mainly composed of vinyl aromatic monomer units and conjugated diene monomer units grafted with component (B) acid anhydride is mixed using a screw extruder. The manufacturing method of a masterbatch composition including a process.