JP5374051B2 - Modified graft copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified graft copolymer having a sufficiently long polyolefin chain length, and a high modification rate. <P>SOLUTION: The modified graft copolymer is obtained by modifying a functional group of a graft polymer satisfying the following conditions (a) to (e), and has a functional side chain obtained by the reaction of the functional group: (a) having 1-150 mass% graft rate; (b) having 500-400,000 weight average molecular weight measured by a GPC; (c) having 1.5-4 molecular weight distribution (Mw/Mn); (d) having a main chain of a polymer chain containing a monomer unit having a functional group; and (e) having a side chain of a polymer chain which is either one of a homopolymer chain of one kind selected from 3-28C &alpha;-olefins or a copolymer chain of two or more kinds selected therefrom, and a copolymer chain comprising a 3-28C &alpha;-olefin unit and an ethylene unit wherein the content of the ethylene unit is &le;50 mass%, and in which the mesopentad fraction [mmmm] is 30-80 mol%. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a modified graft copolymer, and more specifically, a specific structure obtained by modifying a graft copolymer having a main chain containing a specific monomer unit and a side chain which is a specific polyolefin chain. The present invention relates to a modified graft copolymer having

  Polyolefins such as polyethylene and polypropylene are excellent in moldability, mechanical properties, electrical characteristics, and have high chemical stability, and are therefore used in a wide range of fields such as automobiles, home appliances, sundries, and electronic and electrical equipment. However, since polyolefin has almost no polarity, it has poor affinity with different materials such as polar resins and polar compounds, and this often becomes a problem.

  Regarding this affinity problem, a method of modifying polyolefin with an organic acid has been studied. A secondary modification technique is also known in which a polyolefin modified with an acid anhydride or the like is further modified for the purpose of providing further functions or expanding applications.

  For example, Patent Document 1 discloses a secondary modified product obtained by modifying an ethylene random copolymer with an unsaturated dicarboxylic acid anhydride and then performing a modified treatment with a specific amino compound, and the secondary modified product. Disclosed are engine oil compositions and gear oil compositions. However, since the secondary modification amount of the secondary modified product obtained by this method depends on the amount of unsaturated dicarboxylic acid anhydride, there is a problem that it is difficult to obtain a high modified amount of the secondary modified product. In addition, reaction points for secondary modification in this secondary modified product are randomly arranged on the ethylene random copolymer as the main chain. Therefore, the secondary modified product is unlikely to have a structure in which the main chain is elongated and excellent performance is hardly obtained in applications such as compatibilization.

  Patent Document 2 discloses a release agent obtained by secondary modification of an ethylenically unsaturated dicarboxylic acid-modified polyolefin or the like with an organic polysiloxane having a functional group such as an epoxy group. However, the secondary modified product described in Patent Document 2 also has the above-described problems of the amount of secondary modification and structural problems.

In addition, a technique for defining the stereoregularity of the propylene chain as the main chain and improving the performance of the modified polyolefin is also known. For example, Patent Documents 3 and 4 disclose a secondary modified product obtained by further modifying an acid-modified propylene polymer having a specific stereoregularity, and a surface treatment agent and an adhesive containing the secondary modified product. And a method for producing a secondary modified product such as an agent and a paint (a method of performing secondary modification by a polymerization reaction starting from a reactive group introduced into a main chain propylene chain by a modification treatment) Disclosed is a method of performing secondary denaturation by reacting molecules). However, the amount of maleic anhydride modification is not high and it is difficult to control the modification position. Therefore, the above-mentioned problems are not solved even in the secondary modified products of Patent Documents 3 and 4.
Particularly in adhesives and paints, it is important for the propylene chain in the secondary modified product to have a sufficient chain length in order to obtain sufficient affinity with the polyolefin substrate in the polyolefin base material and composition. A modified product in which the modification position in the chain is random is not preferred. Therefore, the secondary modified products described in Patent Documents 3 and 4 are desired to be further improved in both the affinity for polar substances and the affinity for polypropylene substrates.

  As described above, in applications where compatibility and the like are required, the structure of the secondary modified body, the chain length of the polyolefin chain, and the amount of secondary modification are important. However, in the conventional secondary modified product, functional groups for modification are randomly arranged in the polyolefin chain, and it is difficult to increase the amount of functional groups. In addition, depending on the production method, the molecular weight tends to decrease due to side reactions during modification. Therefore, it has been desired to develop a secondary modified product having both a sufficiently long polyolefin chain and high modification.

JP-A-5-59119 JP-A-6-93026 JP 2004-269872 A JP 2007-39645 A

  The present invention has been made in such a situation. The polyolefin chain length is sufficiently long and the modified graft copolymer has a high modification amount, and the compatibilizing agent, the adhesive, and the water containing the modified graft copolymer. The object is to provide a dispersion or the like.

As a result of intensive studies, the present inventors have determined that a modified graft having a specific structure obtained by modifying a graft copolymer having a main chain containing a specific monomer unit and a side chain that is a specific polyolefin chain. It has been found that the above object can be achieved by the copolymer. The present invention has been completed based on such knowledge. That is, the present invention provides the following modified graft copolymers.
(1) A modified graft copolymer obtained by modifying a functional group of a graft copolymer, wherein the graft copolymer satisfies the following (a) to (e), and the functional group reacts: A modified graft copolymer having a functional side chain,
(A) Graft ratio is 1-150 mass%
(B) The weight average molecular weight measured by GPC is 500 to 400,000.
(C) Molecular weight distribution (Mw / Mn) is 1.5-4
(D) The main chain is a polymer chain containing a monomer unit having a functional group (e) The side chain is a kind of homopolymer chain selected from α-olefins having 3 to 28 carbon atoms or two or more kinds of co-polymer chains. It is either a polymer chain or a copolymer chain consisting of an ethylene unit having 50 to 50% by mass of an α-olefin unit having 3 to 28 carbon atoms and an ethylene unit, and a mesopentad fraction [mmmm] of 30 to 80 mol. % Of the polymer chain (2) The graft copolymer is formed by a copolymerization reaction between the reactive polyolefin satisfying the following (A) to (C) and the monomer forming the main chain of the graft copolymer. The modified graft copolymer according to (1) above,
(A) 0.5 to 1.0 terminal unsaturated group per molecule (B) Mesopentad fraction [mmmm] is 30 to 80 mol%
(C) One type of homopolymer or two or more types of copolymers selected from α-olefins having 3 to 28 carbon atoms, or α-olefins having 3 to 28 carbon atoms in which ethylene is 50% by mass or less. One or more monomers and a copolymer of ethylene (3) The functional group is a carboxylic acid anhydride residue, carboxyl group, hydroxyl group, epoxy group, amino group, isocyanate group, ester group The modified graft copolymer according to the above (1) or (2), which is a functional group selected from:
(4) The monomer forming the main chain of the graft copolymer is represented by the formula (III)

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms, and R ² represents a formula of (IV) to (VII)

Any one of the groups represented by R ³ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group having 1 to 12 carbon atoms including any one of an oxygen atom, a nitrogen atom and a silicon atom, and R ⁴ represents a hydrogen atom or A hydrocarbon group having 1 to 12 carbon atoms, R ⁵ having a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an epoxy group, an amino group, an isocyanate group, a hydroxyl group, or a carboxyl group; A group having 1 to 12 carbon atoms is shown. n is an integer of 0-5. ]
The modified graft copolymer according to any one of the above (1) to (3), which is one or more of the monomers represented by:
(5) Monomers forming the main chain of the graft copolymer are [I] acrylic acid and derivatives thereof, [II] methacrylic acids and derivatives thereof, [III] vinyl esters and derivatives thereof, and [IV] styrene. And a modified graft copolymer according to (4) above, which is one or two or more selected from derivatives thereof,
(6) Any of the above (1) to (3), wherein the monomer forming the main chain of the graft copolymer is one or more selected from the following group A and one or more selected from the following group B Modified graft copolymer according to
Group A; [V] maleic anhydride and its substituents, [VI] maleic acid and its esters, [VII] maleimide and its substituents Group B; compounds represented by the following formula (VIII)

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms, and R ⁶ represents a hydrocarbon group having 1 to 28 carbon atoms, or formulas (IV) to (VII)

Any one of these groups is shown. R ³ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group having 1 to 12 carbon atoms including any one of an oxygen atom, a nitrogen atom and a silicon atom, and R ⁴ represents a hydrogen atom or A hydrocarbon group having 1 to 12 carbon atoms, R ⁵ having a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an epoxy group, an amino group, an isocyanate group, a hydroxyl group, or a carboxyl group; A group having 1 to 12 carbon atoms is shown. n is an integer of 0-5. ]
(7) An aqueous dispersion or solution containing the modified graft copolymer according to any one of (1) to (6) above,
(8) A composition containing the modified graft copolymer according to any one of (1) to (6) above,
(9) A coating composition containing the modified graft copolymer according to any one of (1) to (6) above,
(10) An adhesive containing the modified graft copolymer according to any one of (1) to (6) above,
(11) A filler treating agent containing the modified graft copolymer according to any one of (1) to (6) above,
(12) A compatibilizing agent containing the modified graft copolymer according to any one of (1) to (6) above.

  In the graft copolymer used in the present invention, a polymer chain containing a monomer unit having a functional group is a main chain, and the amount of the functional group can be easily adjusted. Moreover, since the modified graft copolymer of the present invention has no modification point in the polyolefin chain, the polyolefin chain is not relatively shortened. Therefore, according to the present invention, a modified graft copolymer having a sufficiently long polyolefin chain length and a high modification amount can be obtained. Since the modified graft copolymer of the present invention has the above structure, it has excellent performance as an adhesive component, a coating component, and the like.

The modified graft copolymer of the present invention has a specific structure obtained by modifying a graft copolymer having a main chain containing a monomer unit having a functional group and a side chain that is a specific polyolefin chain. It is a modified graft copolymer. Moreover, the said graft copolymer is obtained by performing a graft copolymerization reaction using specific reactive polyolefin.
In the present specification, “reactive polyolefin” refers to a polyolefin that efficiently forms a graft copolymer with a radical initiator, specifically, 0.5 terminal unsaturated groups per molecule. It refers to the polyolefin having the above.
Moreover, as can be seen from the definition, not all molecules contained in the reactive polyolefin have terminal unsaturated groups and are not necessarily reactive. For this reason, unreacted polyolefin may be present at the end of the graft copolymerization reaction, but the amount of unreacted polyolefin can be reduced by controlling the amount of terminal unsaturated groups and purifying processes. Therefore, in this specification, the product of the graft copolymerization reaction is not expressed as a “composition” but is described as a “graft copolymer”.
Moreover, in this specification, the manufacturing stage of a graft copolymer is positioned as the first modification treatment, and the step of forming a functional side chain starting from a functional group is referred to as a secondary modification treatment.

[Graft copolymer]
The main chain of the graft copolymer contains a monomer unit having a functional group that forms a functional side chain by secondary modification treatment. The functional group that forms a functional side chain by secondary modification treatment is a functional group that forms the starting point of a polymerization reaction when forming a functional side chain, or reacts with a functional polymer, as will be described later. Means a functional group that can be In the present specification, the above-mentioned “functional group that forms a functional side chain by secondary modification treatment” may be abbreviated as “functional group I”.

  The functional group I can be used without particular limitation as long as it can form a functional side chain by secondary modification treatment. Preferred examples of the functional group I include a carboxylic anhydride residue, a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an isocyanate group, and an ester group.

  In the graft copolymer of the present invention, the amount of the monomer unit having the functional group I is preferably 0.05 to 20 mol% with respect to the amount of the monomer unit forming the main chain, 10 mol% is more preferable. By using the graft copolymer in the above range, a modified graft copolymer having sufficient affinity for both polar substances and polyolefins can be obtained. As will be described later, the type and amount of the monomer unit in the main chain of the graft copolymer can be controlled by changing the type and amount of the monomer used in the production of the graft copolymer.

The side chain of the graft copolymer is a single polymer chain selected from α-olefins having 3 to 28 carbon atoms or two or more copolymer chains, or an ethylene unit of 50% by mass or less, and 3 to 3 carbon atoms. It is a polymer chain of any of the copolymer chains composed of 28 α-olefin units and ethylene units.
Examples of the α-olefin having 3 to 28 carbon atoms include propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, -Tridedecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icocene and the like can be mentioned.

The side chain of the graft copolymer is a polymer chain having a mesopentad fraction [mmmm] of 30 to 80 mol%. The mesopentad fraction [mmmm] is preferably 30 to 75 mol%, more preferably 32 to 70 mol%.
When the mesopentad fraction is less than 30 mol%, the heat resistance and mechanical properties are lowered, and when it exceeds 80 mol%, the moldability and impact strength are lowered. The mesopentad fraction of the side chain of the graft copolymer can be known from the stereoregularity of the reactive polyolefin used in the production. Further, the stereoregularity of the methyl group, methine group, and methylene group derived from the reactive polyolefin of the graft copolymer can be determined by NMR analysis described later. Further, after the graft copolymer is thermally decomposed in a nitrogen atmosphere, the fragments forming the side chains are collected and measured by NMR.

The graft ratio of the graft copolymer is 1 to 150% by mass, preferably 2 to 130% by mass, and more preferably 5 to 100% by mass. When the graft ratio is less than 1% by mass, the affinity with a polar substance is lowered and the compatibilizing ability tends to be inferior, and when it exceeds 150% by mass, the affinity with a polyolefin is lowered and the compatibilizing ability tends to be inferior. .
The graft ratio of the graft copolymer is measured as follows.
Used as a raw material with the mass (W2) of the polymer of the monomer forming the main chain that did not participate in the graft copolymerization reaction with the solvent, and the insoluble graft copolymer component obtained by dissolving and removing the soluble polymer component It calculates as follows from the mass (W1) of reactive polyolefin.
Graft ratio (mass%) = (W2−W1) / W1 × 100
Further, the solvent to be used needs to dissolve a homopolymer or copolymer composed of a monomer that forms a main chain under dissolution conditions. Furthermore, it is necessary that the solvent used does not exhibit solubility for reactive polyolefins under the same dissolution conditions as described above. Not showing solubility means showing a dissolution amount of 1% by mass or less, and dissolving means that no insoluble matter is observed by visual observation of the solution.

The graft copolymer has a weight average molecular weight of 500 to 400,000, preferably 700 to 350,000, more preferably 1000 to 300000, and most preferably 1500 to 250,000. When the weight average molecular weight is less than 500, the mechanical strength decreases, and when it exceeds 400,000, the melt-kneading property decreases.
The molecular weight distribution (Mw / Mn) of the graft copolymer is 1.5 to 4, preferably 1.55 to 3, more preferably 1.6 to 2.5. When the molecular weight distribution is less than 1.5, the melt fluidity is lowered, and when it exceeds 4, a sticky component may be generated.
In addition, when calculating | requiring the weight average molecular weight and molecular weight distribution of a graft copolymer, a gel permeation chromatography (GPC) method can be used as follows.

The molecular weight distribution (Mw / Mn) can be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by the GPC method with the following apparatus and conditions.
GPC measuring device Detector: RI detector for liquid chromatography Waters 150C
Column: TOSO GMHHR-H (S) HT
Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 0.3% by mass
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by the Universal Calibration method using the constants K and α of the Mark-Houwink-Sakurada formula in order to convert the polystyrene-equivalent molecular weight into the molecular weight of the corresponding polymer.
Specifically, it was determined by the method described in “Size Exclusion Chromatography, Sadao Mori, P67-69, 1992, Kyoritsu Shuppan”.
K and α are described in “Polymer Handbook, John Wiley & Sons, Inc.”.
Further, it can be determined by a conventional method from the relationship between the intrinsic viscosity and the newly calculated absolute molecular weight.

The intrinsic viscosity [η] measured at 135 ° C. in decalin is preferably 0.01 to 2.5 dl / g, more preferably 0.02 to 2.2, and still more preferably 0.05 to 2.2. 2.0.
When the intrinsic viscosity [η] is 0.01 dl / g or more, functions such as resin compatibilization are improved, and when it is 2.5 dl / g or less, dispersibility in the resin is improved.

Furthermore, it is preferable that the graft copolymer does not contain a gel component. Reducing the gel component is a reactive polyolefin with a high amount of terminal unsaturated groups, which uses a reactive polyolefin that does not substantially contain molecules having unsaturated groups at both ends, and performs the graft polymerization reaction efficiently. Achieved.
(Method for measuring gel component)
Using a solvent that dissolves both the main chain component and side chain component of the graft copolymer, a glass separable flask equipped with a stirrer is made of a stainless steel 400 mesh (opening 0.034 mm) mesh, Add 50 mg of copolymer and fix to a stirring blade.
A solvent containing 0.1% by mass of an antioxidant (BHT) is added and dissolved with stirring at the boiling point for 4 hours.
After dissolution, the collected soot is sufficiently dried in vacuum, and the insoluble part is determined by weighing.
The gel component defined as the insoluble part is calculated by the following formula.
[Remaining amount in mesh (g) / Amount of charged sample (g)] × 100 (unit:%)
Examples of the solvent include paraxylene and toluene.
Usually, in the above formula, it is defined that the gel component is not included with a range of 0 to 1.5 mass%.

[Method for producing graft copolymer]
The graft copolymer can be produced by polymerization using a monomer that forms a main chain with a specific reactive polyolefin.

(Reactive polyolefin for side chain)
The reactive polyolefin used in the present invention is a kind of homopolymer selected from α-olefins having 3 to 28 carbon atoms or two or more kinds of copolymers, or ethylene having 50 mass% or less, and 3 to 3 carbon atoms. One of at least one monomer selected from 28 α-olefins and a copolymer of ethylene, having a mesopentad fraction [mmmm] of 30 to 80 mol%, and having terminals per molecule. A reactive polyolefin having an unsaturated group content of 0.5 to 1.0 is preferred. By satisfying the above conditions, the graft copolymer used in the present invention can be produced.

  The mesopentad fraction [mmmm] is preferably 30 to 75 mol%, more preferably 32 to 70 mol%.

In the case of a polymer mainly composed of polypropylene, stereoregularity is determined as follows.
The mesopentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic mesoracemi meso fraction [rmrm] described below are described in “Macromolecules, 6, 925 (1973)” by A. Zambelli and others. The meso fraction, the racemic fraction and the racemic meso-racemic meso fraction in the pentad unit in the polypropylene molecular chain measured by the methyl group signal of the ¹³ C-NMR spectrum in accordance with the method proposed in (1).
As the mesopentad fraction [mmmm] increases, the stereoregularity increases.
The ¹³ C-NMR spectrum can be measured according to the following apparatus and conditions in accordance with the attribution of peaks proposed by “Macromolecules, 8, 687 (1975)” by A. Zambelli and the like. it can.
Further, the mesotriad fraction [mm], the racemic triad fraction [rr] and the mesoracemi fraction [mr] described later were also calculated by the above method.

Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

<Calculation formula>
M = (m / S) × 100
R = (γ / S) × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

In the case of a polymer containing polybutene as a main component, stereoregularity is determined as follows.
Mesopentad fraction (mmmm) and abnormal insertion content (1,4 insertion fraction) were reported in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It was determined according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al.
That is, the signals of methylene group and methine group were measured using ¹³ C nuclear magnetic resonance spectrum, and the mesopentad fraction and abnormal insertion content in the poly (1-butene) molecule were determined.
^{The 13} C nuclear magnetic resonance spectrum was measured using the apparatus and conditions described above.
The stereoregularity index {(mmmm) / (mmrr + rmmr)} was calculated from the values obtained by measuring (mmmm), (mmrr) and (rmmr) by the above method.
The racemic triad fraction (rr) can also be calculated by the above method.
The 1-butene homopolymer and copolymer have a stereoregularity index {(mmmm) / (mmrr + rmmr)} of 20 or less, preferably 18 or less, more preferably 15 or less.
When the stereoregularity index exceeds 20, the flexibility is lowered.

In the case of a polymer mainly composed of an α-olefin having 5 or more carbon atoms, stereoregularity is determined as follows.
This stereoregularity index value M ₂ is T.P. Asakura, M .; Demura, Y .; It was determined in accordance with the method proposed in “Macromolecules, 24, 2334 (1991)” reported by Nishiyama.
That is, it is possible to obtain M ₂ by utilizing the fact that the CH ₂ carbon at the side chain α-position derived from a higher α-olefin is split and observed in the ¹³ C NMR spectrum, reflecting the difference in stereoregularity. it can.
This M ₂ can be replaced with the mesopentad fraction [mmmm] in the present invention.
The larger this value, the higher the isotacticity.
The ¹³ C nuclear magnetic resonance spectrum measuring apparatus and conditions are the same as described above, and the stereoregularity index value M ₂ is obtained as follows.
Six large absorption peaks based on the mixed solvent are observed at 127 to 135 ppm. Among these peaks, the fourth peak value from the low magnetic field side is set to 131.1 ppm, which is used as a reference for chemical shift.
At this time, an absorption peak based on CH ₂ carbon at the α-position of the side chain is observed in the vicinity of 34 to 37 ppm.
At this time, we obtain the M ₂ (mol%) using the following equation.
M ₂ = [(integral intensity of 36.2 to 35.3 ppm) / (integral intensity of 36.2 to 34.5 ppm)] × 100

The reactive polyolefin has 0.5 to 1.0, preferably 0.6 to 1.0, more preferably 0.7 to 1.0, and more preferably, terminal unsaturated groups per molecule. 0.8 to 1.0, more preferably 0.82 to 1.0, still more preferably 0.85 to 1.0, and most preferably 0.90 to 1.0.
If the number of terminal unsaturated groups is 0.5 or more, the concentration of unsaturated groups is high and the production efficiency of the graft copolymer is increased.
The terminal unsaturated group is preferably a vinylidene group, and the vinylidene group occupying the terminal unsaturated group is usually 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably. 80 to 100 mol%.
The reactive polyolefin used in the present invention contains substantially no component having two or more unsaturated groups per molecule, for example, a component containing unsaturated groups at both ends.
A component having two or more unsaturated groups per molecule acts as a so-called cross-linking agent, and therefore forms a cross-linked structure (H type) during graft polymerization, and a gel component is by-produced, which is not preferable.
Therefore, unsaturated polypropylene produced by thermal decomposition cannot be used.

In general, the terminal unsaturated group is measured by an infrared absorption spectrum method, a nuclear magnetic resonance spectrum method, a bromination method, or the like, and can be measured by any method.
The infrared absorption spectrum method can be performed in accordance with the method described in “New Edition Polymer Analysis Handbook, Japan Analytical Chemistry Society, Polymer Analysis Research Council”.
According to it, in the method for quantifying terminal unsaturated group by infrared absorption spectrum method, a vinyl group, a vinylidene group, unsaturated group, such as trans (vinylene) group, respectively, of the infrared absorption spectrum 910 cm ^-1, 888 cm ^-1 , From the absorption at 963 cm ⁻¹ .
The quantitative determination of vinylidene unsaturated groups by nuclear magnetic resonance spectroscopy is performed as follows.
The number when the terminal unsaturated group is a vinylidene group is determined by ¹ H-NMR measurement according to a conventional method.
Based on the vinylidene group appearing in δ 4.8 to 4.6 (2H) obtained from ¹ H-NMR measurement, the content (C) (mol%) of the vinylidene group is calculated by a conventional method.
Furthermore, the number of vinylidene groups per molecule is calculated from the number average molecular weight (Mn) and monomer molecular weight (M) determined by gel permeation chromatography (GPC) according to the following formula.
Terminal vinylidene groups per molecule (pieces) = (Mn / M) × (C / 100)
Moreover, as an example of the method by the nuclear magnetic resonance spectrum method, there is a method based on quantification of end groups. Specifically, the terminal groups produced and their abundance were measured by polymerization reaction with ¹ H-NMR and ¹³ C-NMR, and the number of terminal vinylidene groups per molecule was determined from the abundance of terminal vinylidene groups relative to the total amount of terminal groups. This is a calculation method.
The case of a propylene polymer is illustrated.
(Analysis of unsaturated terminal amount by ¹ H-NMR)
In the propylene polymer, [2] methylene group of vinylidene group (4.8 to 4.6 ppm) and [1] methylene group of vinyl group (5.10 to 4.90 ppm) are observed. The ratio to the total propylene polymer can be calculated by the following formula. [3] corresponds to the peak intensity corresponding to the methine, methylene and methyl groups of the propylene chain (0.6 to 2.3 ppm).
Terminal vinylidene group amount (A) = ([2] / 2) / [([3] + 4 × [1] / 2 + 3 × [2] / 2) / 6] × 100 Unit: mol%
Terminal vinyl group amount (B) = ([1] / 2) / [([3] + 4 × [1] / 2 + 3 × [2] / 2) / 6] × 100 Unit: mol%
(Analysis of terminal fraction by ¹³ C-NMR)
The propylene polymer of the present application is [5] terminal methyl group (near 14.5 ppm) of n-propyl terminal, [6] terminal methyl group (near 14.0 ppm) of n-butyl terminal, [4] methine of iso-butyl terminal. Groups (around 25.9 ppm), [7] methylene groups at the vinylidene terminal (around 111.7 ppm) are observed. The peak intensity of the terminal vinyl group amount in ¹³ C-NMR was calculated as follows using (A) and (B) obtained from ¹ H-NMR spectrum.
¹³ C-NMR terminal vinyl group content peak intensity = (B) / (A) × [7]
Here, the total concentration (T) of the end groups is expressed as follows.
T = (B) / (A) × [7] + [4] + [5] + [6] + [7]
Therefore, the ratio of each terminal is (C) terminal vinylidene group = [7] / T × 100 unit: mol%
(D) Terminal vinyl group = (B) / (A) × [7] × 100
(E) n-propyl terminal = [5] / T × 100
(F) n-butyl end = [6] / T × 100
(G) iso-butyl end = [4] / T × 100
It becomes.
The number of terminal vinylidene groups per molecule is 2 × (C) / 100 units: pieces / molecule.

The reactive polyolefin has a molecular weight distribution (Mw / Mn) of preferably 4 or less, more preferably 3.5 or less, more preferably 3 or less, and still more preferably 2.5 or less.
The molecular weight distribution is preferably as narrow as possible. This is because the reactive polyolefin forms a chain in the graft copolymer used in the present invention. This is because a polymer is formed. The molecular weight distribution can be measured by using the method described in the production of the graft copolymer.

The reactive polyolefin has an intrinsic viscosity [η] measured at 135 ° C. in decalin of 0.01 to 2.5 dl / g, preferably 0.05 to 2.5, more preferably 0.05 to 2.0. More preferably, it is 0.1-2.0, and most preferably 0.15-1.8 dl / g.
When the intrinsic viscosity [η] is within the above range, the polyolefin side chain length (chain length) of the graft copolymer is sufficient, and functions such as compatibilization are sufficiently exhibited. Moreover, since the concentration of terminal unsaturated groups is high during graft polymerization, radical polymerizability increases.

The intrinsic viscosity [η] is calculated by measuring the reduced viscosity (η _SP / c) in decalin at 135 ° C. with an Ubbelohde viscometer and using the following general formula (Huggins formula).
η _SP / c = [η] + K [η] ² c
η _SP / c (dl / g): Reduced viscosity [η] (dl / g): Intrinsic viscosity c (g / dl): Polymer concentration K = 0.35 (Haggins constant)

The reactive polyolefin preferably satisfies the following formula.
Racemic meso racemic meso fraction [rmrm]> 2.5 mol%
When the racemic meso racemic meso fraction [rmrm] of the reactive polyolefin exceeds 2.5 mol%, the randomness increases and the transparency is further improved.

In the reactive polyolefin, it is preferable that the melting point (Tm, unit: ° C.) and [mmmm] observed by a differential scanning calorimeter (DSC) satisfy the following relationship.
1.76 [mmmm] -25.0 ≦ Tm ≦ 1.76 [mmmm] +5.0
The above relational expression of the melting point (Tm, unit: ° C.) and [mmmm] observed with a differential scanning calorimeter (DSC) represents the uniformity of the mesopentad fraction of the reactive polyolefin.
When the stereoregularity of the reactive polyolefin is high, that is, when the stereoregularity distribution is narrow, it indicates that the graft copolymer has high uniformity of the side chain and is compatible with polypropylene resins and the like. To rise. When a high mesopentad fraction and a low mesopentad fraction are mixed or block-bonded, that is, when the stereoregularity distribution is wide, compatibility with a polypropylene resin or the like is lowered, which is not preferable. The above [mmmm] is measured as an average value, and it is not possible to clearly distinguish between a case where the stereoregularity distribution is wide and a case where the stereoregularity distribution is narrow, but as described above, the relationship with the melting point (Tm) is specified. By limiting to the range, a preferable highly uniform reactive propylene-based copolymer can be defined.
When the melting point (Tm) exceeds (1.76 [mmmm] +5.0), it indicates that there are partially highly stereoregular sites and sites that do not have stereoregularity.
Moreover, when melting | fusing point (Tm) does not reach (1.76 [mmmm] -25.0), there exists a possibility that heat resistance may not be enough.
From the above viewpoint, preferably 1.76 [mmmm] -20.0 ≦ Tm ≦ 1.76 [mmmm] +3.0
More preferably 1.76 [mmmm] -15.0 ≦ Tm ≦ 1.76 [mmmm] +2.0
It is.
The melting point (Tm) is determined by DSC measurement.
10 mg of a sample was heated from 25 ° C. to 220 ° C. at 320 ° C./min in a nitrogen atmosphere, held at 220 ° C. for 5 minutes, then cooled to 25 ° C. at 320 ° C./min, and held at 25 ° C. for 50 minutes. And it heated up from 25 degreeC to 220 degreeC at 10 degree-C / min. The peak top of the endothermic peak observed on the highest temperature side of the melting heat absorption curve detected during this temperature rising process was defined as the melting point (Tm).

It is preferable that the reactive polyolefin further satisfies the following regulations.
[Rrrr] / (1- [mmmm]) ≦ 0.1
When the above relationship is satisfied, stickiness is suppressed.
[Mm] × [rr] / [mr] ² ≦ 2.0
When the value of [mm] × [rr] / [mr] ² is 2.0 or less, a decrease in transparency is suppressed, and the balance between flexibility and elastic recovery is improved. [Mm] × [rr] / [mr] ² is preferably in the range of 1.8 to 0.5, more preferably 1.5 to 0.5.
20 ≦ component amount eluting at 25 ° C. or lower in temperature rising chromatography (W25) ≦ 100 (mass%)
The component amount (W25) of the reactive polyolefin eluted at 25 ° C. or less in the temperature rising chromatography is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.
W25 is an index indicating whether or not the reactive polyolefin is soft, and when this value is small, a component having a high elastic modulus increases or the mesopentad fraction [mmmm] is uneven.
In the said reactive polyolefin, a softness | flexibility is maintained as W25 is 20 mass% or more.
Note that W25 is not adsorbed by the packing material at a column temperature of 25 ° C. of TREF (temperature rising elution fractionation) in an elution curve obtained by measurement by temperature rising chromatography with the following operation method, apparatus configuration and measurement conditions. Is the amount (% by mass) of the component eluted at

(1) Operation method The sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C, then gradually cooled to 0 ° C at a temperature decrease rate of 5 ° C / hour, held for 30 minutes, and the sample is crystallized on the surface of the filler. Let
Thereafter, the column is heated to 135 ° C. at a heating rate of 40 ° C./hour to obtain an elution curve.
(2) Apparatus configuration TREF column: Silica gel column (4.6φ × 150 mm) manufactured by GL Science
Flow cell: GL Science Co., Ltd. optical path length 1 mm KBr cell Liquid feed pump: Senshu Kagaku Co., Ltd. SSC-3100 pump Valve oven: GL Science Co., Ltd. MODEL 554 oven (high temperature type)
TREF oven: GL Sciences 2 series temperature controller: Rigaku Kogyo REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO MIRAN 1A CVF
10-way valve: Barco Electric valve Loop: Barco 500 μl loop (3) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / L
Injection volume: 500 μl
Pump flow rate: 2.0 ml / min Detection wave number: 3.41 μm
Column packing: Chromosolv P (30-60 mesh)
Column temperature distribution: Within ± 0.2 ° C

The reactive polyolefin of the present invention is preferably produced by a metallocene catalyst.
Examples of the metallocene catalyst include (A) a transition metal compound composed of a metal element of 3 to 10 in the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and the like, and (B) a transition. Examples of the catalyst include a compound that can react with a metal compound to form an ionic complex, and can generate a terminal unsaturated group.
Examples of the transition metal compound include compounds composed of biscyclopentadienyl ligands such as zirconocene chloride and pentamethylcyclopentadienylzirconium dichloride, ethylenebisindenylzirconium dichloride, dimethylsilylene-bis- [2-methyl-4- [Phenylindenyl] zirconium dichloride, dimethylsilylene-bis- [2-methyl-4,5-benzoindenyl] zirconium dichloride, and other compounds comprising a bridged indenyl ligand, pentamethylcyclopentadienyltrimethoxytitanium, pentamethyl A compound comprising a monocyclopentadienyl ligand such as cyclopentadienyltrichlorotitanium, dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] Funium, dichloro [dimethylgermylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium, dichloro [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H -1-Azulenyl)] A compound composed of an azurenium ligand such as hafnium.

  Furthermore, the double bridge | crosslinking transition metal compound represented by the following general formula (I) is mentioned.

In the above general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table. Specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid series. A metal etc. are mentioned.
Among these, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity and the like, and zirconium is most preferable from the viewpoint of yield of terminal vinylidene group and catalytic activity.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from among (A), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same or different from each other.
As E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable, and at least one of E ¹ and E ² is a cyclopentadienyl group, A substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group;
X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y.
Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group; a vinyl group, a propenyl group, and a cyclohexenyl group. An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthonyl group, and the like.
Of these, alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable.

Examples of the alkoxy group having 1 to 20 carbon atoms include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a phenylmethoxy group, and a phenylethoxy group.
Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group.
Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and a methylethylamide group, a divinylamide group, and a dipropenylamide group. Alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.
Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group A substituted silyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group;
Of these, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group, and the like are preferable.

  Examples of the phosphide group having 1 to 20 carbon atoms include dialkyl phosphide groups, diethyl phosphide groups, dipropyl phosphide groups, dibutyl phosphide groups, dihexyl phosphide groups, dicyclohexyl phosphide groups, and dioctyl phosphide groups. A diaryl phosphide group such as a dibenzyl phosphide group, a diphenyl phosphide group, and a dinaphthyl phosphide group.

Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide , Anthracenyl Nils sulfide group, an aryl sulfide groups such as phenanthridine Nils sulfide groups.
Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, thearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.

On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X.
Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.
Examples of the amines include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexyl. Alkylamines such as amine and methylethylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, and phenylpropylamine; diphenylamine; Aryl amines such as dinaphthylamine are mentioned.

  Examples of ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether; , Aromatic ether compounds such as phenetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, cyclic compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, dioxane An ether compound is mentioned.

Examples of phosphines include phosphines having 1 to 20 carbon atoms.
Specifically, monohydrocarbon substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkylphosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine; vinyl Phosphine, propenylphosphine, cyclohexenylphosphine, etc. Noalkenylphosphine or dialkenylphosphine in which two alkenyl hydrogen atoms are substituted; Trialkenylphosphine in which three alkenyl hydrogen atoms are substituted; Phosphoryl arylphosphine such as benzylphosphine, phenylethylphosphine, phenylpropylphosphine; Diarylalkylphosphine or aryldialkylphosphine in which three hydrogen atoms of phosphine are substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methyl Naphthylphosphine, anthracenylphosphine, phenanthonylphosphine; And an aryl phosphine such as a hydrogen atom of phosphine alkylaryl three substituted with tri (alkylaryl) phosphines; alkyl aryl hydrogen atom fin two substituted di (alkylaryl) phosphines. Examples of the thioethers include the above sulfides.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, May be different. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among such crosslinking groups, at least one is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms.
As such a crosslinking group, for example, the general formula (a)

(D is a group 14 element of the periodic table, and examples thereof include carbon, silicon, germanium and tin. R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they are the same as each other. However, they may be different from each other, and may be bonded to each other to form a ring structure.

Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), a dimethylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisylylene group, and a diphenyldisilylene group. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

  Specific examples of the double-bridged transition metal compound represented by the general formula (I) include (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methylcyclopentadienyl) (3 '-Methylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride , (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2 , 1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1 '-Isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-methylene) (3-methylcyclopentadi Enyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) ) Zirconium dichloride, (1,2'-isopropylidene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopent Dienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride,

(1,2′-ethylene) (2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene ) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1 ′ -Methylene) (3,4-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene) (3 4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) (3 -Dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclohexane) Pentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-ethylcyclopenta) Dienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-isopropylcyclopentadiene) Enyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ( , 1′-dimethylsilylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ) (2,1′-dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride , (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5 ' -Phenylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclo Pentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadiene) Enyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'-n-butylcyclo) Pentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-phenylcyclopentadiene) ) (3'-methyl-5'-phenylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1 , 2′-ethylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) ) Zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) Zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride and the like In which zirconium in the compound is substituted with titanium or hafnium, and represented by the general formula (II) described later Mention may be made of the compound.
Moreover, the analogous compound of the metal element of another group may be sufficient.
A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.
Among the transition metal compounds represented by the general formula (I), the compound represented by the general formula (II) is preferable.

In the above general formula (II), M represents a metal element belonging to Groups 3 to 10 of the periodic table, and A ^1a and A ^2a each represent a bridging group represented by the general formula (a) in the above general formula (I). CH ₂ , CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C (CH ₃ ) ₂ C, (CH ₃ ) ₂ Si and (C ₆ H ₅ ) ₂ Si are preferred.
A ^1a and A ^2a may be the same as or different from each other.
R ^{4 to} R ¹³ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group.
Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the silicon-containing group are the same as those described in the general formula (I).
Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include p-fluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis ( (Trifluoro) phenyl group, fluorobutyl group and the like.
Examples of the heteroatom-containing group include C1-C20 heteroatom-containing groups. Specifically, nitrogen-containing groups such as a dimethylamino group, a diethylamino group, and a diphenylamino group; a phenylsulfide group, a methylsulfide group, and the like Sulfur-containing groups of: phosphorus-containing groups such as dimethylphosphino groups and diphenylphosphino groups; oxygen-containing groups such as methoxy groups, ethoxy groups, and phenoxy groups.
Among these, as R ⁴ and R ⁵ , a group containing a hetero atom such as halogen, oxygen, or silicon is preferable because of high polymerization activity.
R ^{6 to} R ¹³ are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
X and Y are the same as in general formula (I). q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

  Among the double-bridged transition metal compounds represented by the general formula (II), when both indenyl groups are the same, the transition metal compounds belonging to Group 4 of the periodic table include (1,2'-dimethylsilylene). ) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2 '-Dimethylsilylene) (2,1'-dimethylsilylene) bis (3-ethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-isopropylindenyl) ) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethyl) Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethyl Silylene) bis (4-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,7-dimethylindenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-ethoxymethylindene Nyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethyl) Silylene) bis (3-ethoxyethylindenyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methoxymethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis ( 3-methoxyethylindenyl) zirconium dichloride, (1,2′-phenylmethylsilylene) (2,1′-phenylmethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-phenylmethylsilylene) (2, 1'-phenylmethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (indenyl) zirconium dichloride, (1,2'-dimethyl Silylene) (2,1′-isopropylidene) bis (3-methylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) Bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethyl Silylene) (2,1′-isopropylidene) bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) bis (3-phenylindenyl) zirconium dichloride , (1,2'-dimethylsilylene) (2,1'- Styrene) (indenyl) zirconium dichloride,

(1,2'-dimethylsilylene) (2,1'-methylene) bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) bis (3-isopropyl Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1 ' -Methylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diphenyl) Silylene) (2,1′-methylene) bis (indenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) bis (3-methylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) bis (3-n-butylindenyl) zirconium dichloride, ( 1,2′-diphenylsilylene) (2,1′-methylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) bis (3-trimethylsilyl) Indenyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium, are not limited thereto.
Further, it may be a compound similar to a metal element other than Group 4.
A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

On the other hand, among the double bridged transition metal compounds represented by the general formula (II), when R ⁵ is a hydrogen atom and R ⁴ is not a hydrogen atom, the transition metal compound of Group 4 of the periodic table is ( 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ( Indenyl) (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (indenyl) (3-trimethylsilylindenyl) zirconium dichloride (1,2'-dimethylsilylene) ) (2,1′-dimethylsilylene) (indenyl) (3-phenylindenyl) zirconium dichloride, (1,2′-dimethyl) Rylene) (2,1′-dimethylsilylene) (indenyl) (3-benzylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-neopentyl) Indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-phenethylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′ -Ethylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) (indenyl) (3-methylindenyl) zirconium dichloride, (1,2 '-Ethylene) (2,1'-ethylene) (indenyl) (3-trimethylsilylindenyl) zyl Conium dichloride, (1,2′-ethylene) (2,1′-ethylene) (indenyl) (3-phenylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) ( Indenyl) (3-benzylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) (indenyl) (3-neopentylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) (indenyl) (3-phenethylindenyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium, are not limited thereto. .
Further, it may be a compound similar to a metal element other than Group 4.
A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

As a compound capable of reacting with the transition metal compound (B) constituting the catalyst used in the present invention to form an ionic complex, a high purity terminal unsaturated olefin polymer having a relatively low molecular weight can be obtained, and A borate compound is preferable in terms of high catalyst activity.
Examples of borate compounds include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and methyl (tri-n-butyl) ammonium tetraphenylborate. , Benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetra Benzylpyridinium phenylborate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) borate trie Ruammonium, tetrakis (pentafluorophenyl) borate tri-n-butylammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (pentafluorophenyl) ) Tetraethylammonium borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate , Tetrakis (pentafluorophenyl) methylanilinium borate, tetrakis (pentafluorophenyl) dimethylanilinium borate, tetra Scan (pentafluorophenyl) borate trimethyl anilinium,

  Methyl pyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2- Cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylaniline borate Nitrogen, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis Ntafluorophenyl) triphenylcarbenium borate, methylanilinium tetrakis (perfluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid (1,1′-dimethylferrocete) Nium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (penta Fluorophenyl) sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate and the like. These can be used individually by 1 type or in combination of 2 or more types. When the molar ratio of hydrogen and transition metal compound (hydrogen / transition metal compound) described later is 0, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and tetrakis (Perfluorophenyl) methylanilinium borate and the like are preferable.

The catalyst used in the production method of the present invention may be a combination of the component (A) and the component (B). In addition to the component (A) and the component (B), an organoaluminum compound is used as the component (C). Also good.
As the organoaluminum compound (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride. Dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride and ethylaluminum sesquichloride.
These organoaluminum compounds may be used alone or in combination of two or more.
Among these, in the present invention, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum and trinormaloctylaluminum is preferable, and triisobutylaluminum, trinormalhexylaluminum and trimethylaluminum Normal octyl aluminum is more preferred.

The amount of component (A) used is usually 0.1 × 10 ^{−6 to} 1.5 × 10 ⁻⁵ mol / L, preferably 0.15 × 10 ^{−6 to} 1.3 × 10 ⁻⁵ mol / L, More preferably, it is 0.2 × 10 ^{−6 to} 1.2 × 10 ⁻⁵ mol / L, and particularly preferably 0.3 × 10 ^{−6 to} 1.0 × 10 ⁻⁵ mol / L.
When the amount of component (A) used is 0.1 × 10 ⁻⁶ mol / L or more, the catalytic activity is sufficiently expressed, and when it is 1.5 × 10 ⁻⁵ mol / L or less, the heat of polymerization is easy. Can be removed.
The use ratio (A) / (B) of the component (A) and the component (B) is preferably 10/1 to 1/100, more preferably 2/1 to 1/10 in terms of molar ratio.
When (A) / (B) is in the range of 10/1 to 1/100, an effect as a catalyst can be obtained and the catalyst cost per unit mass polymer can be suppressed.
Further, there is no fear that a large amount of boron exists in the target reactive polyolefin.
The use ratio (A) / (C) of the component (A) and the component (C) is preferably 1/1 to 1/10000, more preferably 1/5 to 1/2000, and further preferably 1 in terms of molar ratio. / 10 to 1/1000.
By using the component (C), the polymerization activity per transition metal can be improved. When (A) / (C) is in the range of 1/1 to 1/10000, the balance between the effect of addition of component (C) and economy is good, and aluminum is contained in the target reactive polyolefin. There is no fear of being present in large quantities.
In the production method of the present invention, the preliminary contact may be performed using the above-described component (A) and component (B), or component (A), component (B) and component (C).
The preliminary contact can be performed by bringing the component (A) into contact with, for example, the component (B). However, the method is not particularly limited, and a known method can be used.
Such preliminary contact is effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the component (B) used as the cocatalyst.

The reactive polyolefin of the present invention preferably has a small amount of the catalyst residue.
In particular, the transition metal content is 5 mass ppm or less, the aluminum content is 300 mass ppm or less, and the boron content is 5 mass ppm or less.
Examples of the transition metal include titanium, zirconium and hafnium, and the total amount thereof is 5 ppm by mass or less.
The content of aluminum is preferably 280 mass ppm or less.
These metal components can be measured by an ICP (High Frequency Inductively Coupled Plasma Spectroscopy) measuring device.
When a reactive polyolefin with little catalyst residue is used, the resulting graft copolymer is preferable because of its high purity.

(Main chain monomer)
As described above, the main chain of the graft copolymer used in the present invention contains a monomer unit having a functional group (functional group I) that forms a functional side chain by secondary modification treatment. The main chain can be formed by performing a polymerization reaction using a monomer containing the functional group I.
In general, a monomer having a functional group varies greatly in reactivity depending on the type of the functional group. Therefore, in order to produce a main chain graft copolymer having desired properties and lengths in the present invention, it is preferable to use an appropriate combination of monomers. Hereinafter, the case where a dibasic acid compound such as maleic acid is used as a monomer and the case where it is not used will be described separately.

  When a dibasic acid compound is not used, a monomer represented by the formula (III) is preferable.

In the formula (III), R ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, an aryl group, an aralkyl group, and an arylalkyl group. R ² represents formula (IV) to formula (VII)

Any one of the groups represented by R ³ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group having 1 to 12 carbon atoms including any one of an oxygen atom, a nitrogen atom and a silicon atom, and R ⁴ represents a hydrogen atom or A hydrocarbon group having 1 to 12 carbon atoms, R ⁵ having a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an epoxy group, an amino group, an isocyanate group, a hydroxyl group, or a carboxyl group; A group having 1 to 12 carbon atoms is shown. n is an integer of 0-5.

  When a graft copolymer is produced using the above monomer, one or more monomers having a functional group I and one or more monomers having no functional group I may be used in combination. Preferable examples of the functional group I include a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an isocyanate group, and an ester group.

  Specific examples of the monomer represented by the formula (III) include the following compounds [I] to [IV].

[I] Acrylic acid and its derivatives (1) Acrylic acid (2) Acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, normal octyl acrylate, 2-ethylhexyl acrylate; polyethylene glycol monoacrylate, Polyethylene glycol polypropylene glycol acrylate, poly (ethylene glycol-n-tetramethylene glycol) monoacrylate, propylene glycol polybutylene glycol monoacrylate, long-chain polyalkylene glycols having a molecular weight of 30000 or less (3) acrylic acid Gold acrylate composed of acrylic and typical metal elements such as sodium, potassium acrylate, magnesium acrylate, calcium acrylate Salt (4) Acrylic esters containing an oxygen, nitrogen, sulfur or silicon atom in the ester residue, such as glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxy Acrylic esters having a functional group such as propyl acrylate, 4-hydroxybutyl acrylate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane; polyethylene Glycol monoacrylate, polyethylene glycol polypropylene glycol acrylate, poly (ethylene glycol-n-tetramethylene glycol) monoacrylate, propylene glycol polymer Long-chain polyalkylene glycols having a hydroxyl group such as butylene glycol monoacrylate and polypropylene glycol monoacrylate (5) Acrylamide (6) N-substituted acrylamide containing oxygen, nitrogen, sulfur and silicon atoms in the substituent, for example N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-cyclohexylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dibutylacrylamide, N, N-dicyclo Xylacrylamide, N- (2-hydroxyethyl) -acrylamide, N- (2-hydroxypropyl) -acrylamide, N, N-dimethylaminoethylacrylamide, N-methylolacrylamide, etc. N- substituted acrylamides (7) acrylonitrile

[II] α-Alkyl substituted methacrylic acid and acrylic acid (hereinafter, these may be collectively abbreviated as “methacrylic acid”) and their derivatives α of the monomer of [I] above Monomer having an alkyl group such as a methyl group at the position (preferably an alkyl group having 6 or less carbon atoms)

[III] Vinyl esters and derivatives thereof, for example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl isolamate, vinyl pivalate, vinyl undecanoate, vinyl palmitate and derivatives thereof

[IV] Styrene, further α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, mesitylstyrene, 2,4-dimethylstyrene Alkyl styrenes such as 2,5-dimethylstyrene and 3,5-dimethylstyrene; alkoxystyrenes such as p-methoxystyrene, o-methoxystyrene and m-methoxystyrene; p-chlorostyrene, m-chlorostyrene, o-bromostyrene, p-fluoros Ren, m- fluorostyrene, o- fluorostyrene, halogenated styrenes such as o- methyl -p- fluorostyrene; trimethylsilyl styrene, styrene and its derivatives such as vinyl benzoate

Preferred monomers and preferred monomer combinations include the following.
[I] As acrylic acid and derivatives thereof, all of the above compounds are preferable, and in particular, all compounds except metal acrylate are preferable.
[II] Graft polymerization is possible only with methacrylic acids and their derivatives, but [II] methacrylic acids and their derivatives by combining [I] acrylic acid and its derivatives / [II] methacrylic acids and their derivatives The amount of graft polymerization of the derivative is preferable.
In particular, combinations of acrylic acid and acrylic acid esters with methacrylic acid and methacrylic acid esters are preferable.
[I] A preferable molar ratio of acrylic acid and its derivative / [II] methacrylic acid and its derivative is [I] / [II] (molar ratio) of 0.1 to 2, preferably 0.2 to 1. 5, More preferably, it is 0.3-1.2, More preferably, it is the range of the range of 0.5-1.0.
When [I] / [II] (molar ratio) is 0.1 or more, the amount of graft polymerization of [II] methacrylic acid and its derivatives increases, and when it is 2 or less, it does not participate in graft polymerization [I]. Acrylic acid and its derivatives / [II] methacrylic acids and their copolymers are preferred because they do not by-produce.
Graft polymerization is possible only with styrene and its derivatives, but the combination of [I] acrylic acid and its derivatives / [VI] styrene and its derivatives increases the amount of graft polymerization of styrene and its derivatives. .
In particular, combinations of acrylic acid, acrylic acid esters, styrene, and derivatives thereof are preferable.
[I] A preferred molar ratio of acrylic acid and its derivative / [VI] styrene and its derivative is [I] / [VI] (molar ratio) of 0.1 to 2, preferably 0.2 to 1.5, More preferably, it is 0.3-1.2, More preferably, it is the range of the range of 0.5-1.0.
When [I] / [VI] (molar ratio) is 0.1 or more, the amount of graft polymerization of [VI] styrene and its derivatives increases. And a copolymer of / [VI] styrene and derivatives thereof is preferable because it does not by-produce.

  When using a dibasic acid compound, it is preferable to use together one or more monomers selected from the following group A and one or more monomers selected from the following group B.

Group A [V] Maleic anhydride and its substituent [VI] Maleic acid and its ester [VII] Maleimide and its substituent Group B Compounds represented by the following formula (VIII)

In formula (VIII), R ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms, and R ⁶ represents a hydrocarbon group having 1 to 28 carbon atoms or (IV) formula to (VII) )formula

Any one of these groups is shown. R ³ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group having 1 to 12 carbon atoms including any one of an oxygen atom, a nitrogen atom and a silicon atom, and R ⁴ represents a hydrogen atom or A hydrocarbon group having 1 to 12 carbon atoms, R ⁵ having a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an epoxy group, an amino group, an isocyanate group, a hydroxyl group, or a carboxyl group; A group having 1 to 12 carbon atoms is shown. n is an integer of 0-5.

Specific examples of the monomer of group A include
[V] Maleic anhydride, such as maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, phenyl maleic anhydride, diphenyl maleic anhydride and its substitutes [VI] Maleic acid, methyl maleic acid, dimethyl maleate, maleate Maleic acid such as diethyl acid, dibutyl maleate, monomethyl maleate and the like [VII] maleimide, N-alkyl substituted maleimide, N-methyl maleimide, N-ethyl maleimide, N-phenyl maleimide, and other maleimides and substituted products thereof Can be mentioned.
Specific examples of monomers of group B include
[I] Acrylic acid and its derivative [II] Methacrylic acid and its derivative [III] Vinyl ester and its derivative [IV] Styrene and its derivative [VIII] α-olefin.
Examples of the compounds [I] to [IV] include the compounds described above. Examples of α-olefin compounds include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1- Examples thereof include α-olefins having 2 to 28 carbon atoms such as tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicocene.

  The monomer of group A is a monomer in which the same kind of monomers are difficult to polymerize because of the low electron density of double bonds. Therefore, in the present invention, the content of the monomer of the A group is improved by polymerization in combination with the monomer of the B group. Moreover, in this invention, since the reactivity of reactive polyolefin can be improved by using the monomer of A group, the effect that a graft copolymer can be manufactured efficiently is also acquired.

The combination of the compound of group A and the compound of group B is such that the compound of group A / the compound of group B (molar ratio) is usually about 0.1 to 2, preferably 0.5 to 1.5, more preferably It is in the range of 0.8 to 1.2, more preferably 0.9 to 1.1.
When the molar ratio is 0.1 or more, the amount of graft polymerization of the group A compound increases, and when it is 2 or less, a copolymer of the group A compound / group B compound not involved in the graft polymerization is by-produced. Not preferred.
The combination of the compounds of Group A and Group B is preferably a combination of [V] maleic anhydride of Group A and its substituents and a compound of Group B. [V] Maleic anhydride of Group A and [I] of Group B A combination of acrylic acid and its derivatives, [III] vinyl ester and its derivatives, and [VIII] α-olefin is more preferred.

  When a graft copolymer is produced using the above monomer, one or more monomers having a functional group I and one or more monomers having no functional group I may be used in combination. Preferable examples of the functional group I include a carboxylic anhydride residue, an amino group, an isocyanate group, and an ester group.

The radical initiator used in the graft copolymerization of the present invention is not particularly limited and can be appropriately selected from conventionally known radical initiators such as various organic peroxides and azo compounds. Both compounds are suitable radical initiators.
Examples of organic peroxides include dibenzoyl peroxide, di-8,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, and di (2,4-dichlorobenzoyl) peroxide. Diacyl peroxides, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl Peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, Dialkyl such as α, α'bis (t-butylperoxy) diisopropylbenzene Peroxides, peroxyketals such as 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylperoxyoct , Alkyl peresters such as t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di Examples include peroxycarbonates such as -sec-butylperoxydicarbonate and t-butylperoxyisopropylcarbonate. Among these, dialkyl peroxides are preferable.
Examples of the azo compound include azobisisobutyronitrile and azobisisovaleronitrile.
A radical initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

There is no restriction | limiting in particular as the usage-amount of the radical initiator in a graft copolymerization reaction, According to the desired physical property of a graft copolymer, it selects suitably.
A radical initiator is used in 0.001-10 mass parts with respect to 100 mass parts of reactive polyolefin, Preferably it is used in 0.005-5 mass parts.

  The amount of the monomer used to form the main chain can be appropriately determined according to the purpose, but is selected in the range of 0.2 to 200 parts by mass with respect to 100 parts by mass of the reactive polyolefin. The The amount used is preferably 0.3 to 150 parts by mass, more preferably 0.4 to 130 parts by mass, and still more preferably 1 to 100 parts by mass. When the amount used is 0.2 parts by mass or more, the amount of monomers to be copolymerized in the graft polymer increases, and functions such as compatibilization are likely to be exhibited. The coalescence is preferable because no by-product is formed.

The graft polymerization method is not particularly limited, but, for example, by reacting reactive polyolefin, the above-described monomer and radical initiator by melt kneading using a roll mill, a Banbury mixer, an extruder, or the like, Graft copolymers can be produced. The reaction conditions include a temperature of 60 to 140 ° C. and 0.01 to 0.5 hours.
In addition, hydrocarbon solvents such as butane, pentane, hexane, cyclohexane and toluene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, and suitable organic solvents such as liquefied α-olefins or solvent-free Under certain conditions, a graft copolymer can also be produced. The reaction conditions include 40 to 140 ° C., preferably 50 to 140 ° C. and 0.1 to 10 hours.
When graft polymerization is carried out under normal high-temperature conditions, molecular weight and viscosity are reduced due to decomposition of the reactive polyolefin, and gel is easily generated due to a crosslinking reaction. However, the above conditions are relatively low temperatures, there is no decrease in molecular weight or viscosity, and side reactions such as crosslinking reactions are also suppressed.

The graft copolymerization of the present invention may be performed in the presence of a Lewis acid, and examples of the Lewis acid include the following compounds.
(1) Halides of group 2 to group 4 elements (chlorine, bromine, fluorine, iodine), alkylates (hydrocarbon groups having 1 to 20 carbon atoms), alkyl halides (2) aluminum, boron, Lewis acids consisting of zinc, tin, magnesium, calcium atoms Specific examples of Lewis acids include magnesium chloride, calcium chloride, zinc chloride, boron trichloride, aluminum trichloride, gallium trichloride, silicon tetrachloride, silicon tetrachloride, and Compound in which chlorine atom is converted to bromine atom or fluorine atom, butylethylmagnesium, diethylzinc, trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, trimethylboron, triethylboron, triethylgallium, trimethylgallium, diethylaluminum monochloro Re , Ethylaluminum dichloride, and ethylaluminum sesquichloride, among which zinc compounds, aluminum compounds, and boron compounds are preferred.

As the amount of Lewis acid used in the graft polymerization reaction, Lewis acid / monomer (mol / mol) is 0.01 to 1, preferably 0.05 to 1, and more preferably 0.1 to 0.5. . If the Lewis acid / monomer (mole / mole) is 0.01 or more, the graft ratio is high, and if it is 1 or less, the removal of the Lewis acid residue by deashing is unnecessary, so there is no coloring. Is preferable.
The Lewis acid is added before the radical initiator is added, and a graft polymerization reaction is performed, or a graft polymerization reaction is performed by using a monomer and a Lewis acid previously brought into contact with each other.

[Modified Graft Copolymer and Method for Producing the Same]
In the present invention, a modified graft copolymer having a functional side chain is produced by reacting the functional group I in the graft copolymer with a modifier and performing a secondary modification treatment. As a method for producing the modified graft copolymer, there are two methods as shown below.
In addition, a functional group in the modifying agent that reacts with the functional group I may be abbreviated as a functional group II. The functional side chain refers to a side chain having a property different from that of the reactive polyolefin, and specifically includes a carboxylic acid anhydride residue, a carboxyl group, an ester group, an amide group. And a side chain having a polar group such as an amino group or a hydroxyl group and an aromatic group such as a phenyl group. By having these functional side chains, the modified graft copolymer of the present invention has improved affinity for polar substances and the like.

  The first method for producing the modified graft copolymer is (1) a method of forming a functional side chain by utilizing the starting point of the polymerization reaction formed by the functional group I. The graft copolymer is modified with a modifying agent having a carbon-carbon double bond (modifying agent A), and then the modifying agent (modifying agent B) that reacts with the carbon-carbon double bond is reacted. This is a method of forming a side chain. The second method is (2) a method in which a functional polymer having functional group II or the like (modifier C) is used and reacted with functional group I to form a functional side chain.

The functional group II contained in the modifier A or C can be used without particular limitation as long as it reacts with the functional group I. For example, carboxylic anhydride residue, carboxyl group, amino group, hydroxyl group, epoxy Group, isocyanate group and the like. In the transesterification reaction, an ester group can also be used.
The reaction between the functional group I and the functional group II includes an esterification reaction between a carboxyl group and a hydroxyl group, a ring-opening reaction between a carboxyl group and an epoxy group, a ring-opening reaction between a primary or secondary amino group and an epoxy group, carboxyl Group and primary or secondary amino group amidation reaction, carboxyl group and tertiary amino group quaternary ammonium reaction, carboxyl group and isocyanate group urethanation reaction, primary or secondary amino group and isocyanate group Urethanization reaction, reaction of hydroxyl group containing phenol and isocyanate group, and the like.

(1) A method of forming a functional side chain using the starting point of the polymerization reaction formed by the functional group I In this method, a modifier having a functional group II and a polymerizable carbon-carbon double bond (modification Agent A) is used to react with the functional group I of the graft copolymer. Next, a polymerization reaction is performed using the polymerizable carbon-carbon double bond and the modifier B to form a functional side chain.
In the case of this method, the graft copolymer preferably has a monomer unit amount having a functional group I of 0.05 to 10 mol% with respect to the monomer unit amount forming the main chain. More preferably, 1 to 5 mol%. Within the above range, by-product of a cross-linked product can be avoided, and excellent adhesiveness can be obtained for polyolefins and different materials such as polar resins and polar compounds.

  Specific examples of the modifier A include, for example, (meth) acrylic acid, (meth) acrylic acid-2-hydroxyethyl, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, and 2-isocyanatoethyl (meth). Examples thereof include (meth) acrylic acid derivatives such as acrylate, and styrene derivatives such as parahydroxystyrene. In addition, (meth) acrylic acid represents acrylic acid or methacrylic acid, and (meth) acrylic acid derivatives have the same meaning.

  As a specific combination, when the functional group I is a maleic anhydride residue, the modifier A includes (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid dimethylaminoethyl, glycidyl (meth) acrylate. 2-isocyanatoethyl (meth) acrylate, and when the functional group I is a hydroxyl group, the modifier A includes 2-isocyanatoethyl (meth) acrylate, (meth) acrylic acid, and glycidyl (meth) acrylate. When the functional group I is a carboxyl group, examples of the modifier A include (meth) acrylic acid-2-hydroxyethyl, glycidyl (meth) acrylate, and (meth) acrylic acid dimethylaminoethyl. Is an epoxy group, the modifier A includes (meth) acrylic acid-2-hydroxyethyl, ( T) Dimethylaminoethyl acrylate, 2-isocyanatoethyl (meth) acrylate, and when functional group I is an amino group, as modifier A, glycidyl (meth) acrylate, 2-isocyanatoethyl (meth) In the case where the functional group I is an isocyanate group, the modifier A includes those having active hydrogen such as 2-hydroxyethyl (meth) acrylate and dimethylaminoethyl (meth) acrylate. .

The modification with the modifier A can be performed by a solution reaction or a melt reaction.
In the case of a solution reaction, the solvent includes aromatic hydrocarbons such as toluene, xylene and mixed xylene; aliphatic hydrocarbons such as n-hexane, n-heptane, isooctane and decane; alicyclic rings such as cyclohexane and methylcyclohexane Formula aliphatic hydrocarbons; halogenated hydrocarbons such as perchlorethylene, chlorobenzene, and o-dichlorobenzene; carboxylic acid esters such as methyl acetate and ethyl acetate; alcohols such as ethanol, isopropanol, and butanol can be used. . The concentration of the graft copolymer is preferably in the range of 1 g / liter to 1500 g / liter and capable of being stirred in a dispersed or dissolved state.
In the case of a melt reaction, any apparatus that can carry out a batch-type melt reaction or a continuous-type melt reaction can be used without particular limitation. For example, it can be carried out using a Banbury mixer, a kneader, an extruder, or the like. The reaction is usually carried out at a temperature higher than the melting point of the polymer, and the reaction time is suitably 1 minute to 3 hours.

  The amount of the modifier A used is preferably in the range of 0.1 to 1.2 mol of the modifier A with respect to 1 mol of the functional group I. The reaction temperature is usually 30 to 200 ° C, preferably 40 to 150 ° C. The reaction time is usually 1 minute to 10 hours, preferably 5 minutes to 5 hours. Further, it is preferable to use a known polymerization inhibitor such as hydroquinone monomethyl ether / oxygen.

  Moreover, you may use a catalyst for the said reaction. Known catalysts such as alkali metal oxides, hydroxides, carbonates, carboxylic acids, inorganic acids, tertiary amines and organotin compounds can be used as the catalyst. Specifically, p-toluenesulfonic acid, pyridine, 4-dimethylaminopyridine, triethylamine, dimethylbenzylamine, tetramethylammonium bromide, sulfuric acid, 1,8-diazabicyclo [5,4.0] -7-undecenoic acid, dibutyl Tin dilaurate, tin dibutyldiacetate, N-methylmorpholine, N- (dimethylaminoethyl) morpholine, N, N, N ′, N′-tetramethylethylenediamine, 6-dimethylamino-1-hexanol, 5-dimethylamino-3 -Methyl-1-pentanol, N, N-dimethylethanolamine, 1-methylimidazole and the like.

  The reaction rate of the above reaction is preferably 30 to 100%, more preferably 50 to 100%. If it is less than 30%, the number of secondary modification reaction points decreases, and it is difficult to obtain the desired modified graft copolymer.

The modifier B is a compound that has a group that reacts with a carbon-carbon double bond and forms a functional side chain by a polymerization reaction. Examples of the modifier B include [I] acrylic acid and derivatives thereof, [II] methacrylic acids and derivatives thereof, [III] vinyl esters and derivatives thereof, [IV] styrene and derivatives thereof, and [V] maleic anhydride and derivatives thereof. Substituted substances, [VI] maleic acid and esters thereof, [VII] maleimide and substituted substances thereof, and [VIII] α-olefins can be mentioned. Specific examples of these are as described above.
The amount of the modifier B used is such that the mass ratio of the graft copolymer / modifier B to the graft copolymer after treatment with the modifier A is usually 1/20 to 20/1, preferably 1/10 to 10. 10/1, more preferably 1/5 to 5/1. Within this range, excellent affinity can be obtained for polyolefins and polar substances.

  The polymerization reaction with the modifier B is preferably performed using a catalyst, and any of a radical polymerization catalyst, an anionic polymerization catalyst, and a cationic polymerization catalyst can be used, and a radical polymerization catalyst is preferred. As the radical polymerization catalyst, the organic peroxides and azo compounds described in the production of the graft copolymer can be used. The amount of the radical polymerization catalyst used is such that the mass ratio with the modifier B is that the radical polymerization catalyst / modifier B is usually 1/1000 to 1/10, and preferably 1/500 to 1/20. As a method for adding the radical polymerization catalyst, any of batch addition, divided addition and continuous addition can be used.

  The polymerization reaction by the modifier B can be performed by a solution reaction or a melt reaction, and the details regarding the solvent and the apparatus are as described in the modification by the modifier A. Reaction temperature is 20-200 degreeC normally, Preferably it is 30-150 degreeC, More preferably, it is 40-110 degreeC. The reaction time is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours. Further, in order to bring the conversion rate of the modifier B close to almost 100%, it is preferable to add a radical polymerization catalyst at the end of the reaction, and further carry out the polymerization reaction while keeping the temperature at a high temperature (80 to 110 ° C.).

The secondary modification treatment using the modifiers A and B and the resulting modified graft copolymer are exemplified below.
An example in which the dibasic acid compound is not used as a monomer for the main chain and the reaction between the functional group I and the functional group II is not a transesterification reaction is as follows.

In the above formula, X represents a functional group I, and Y represents a functional group II. X and Y are specifically groups selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an isocyanate group, and X and Y are different groups. L is a site for linking a polymerizable moiety (—CR ¹ = CR ² R ³ ) and Y, and —CO—O— group or —C ₆ H ₄ — group (phenylene ring) directly bonded to the polymerizable moiety. Is a linking group composed of an atom selected from carbon, hydrogen, oxygen and nitrogen atoms, containing either of the above as an essential component. W represents —CO—O—, —CO—O—CR ⁴ ₂ —CR ⁵ (OH) —, —CO—NR ⁴ —, —CR ⁵ (OH) —CR ⁶ ₂ —O—, —NR ⁴ —. A group selected from CO—O—, —CR ⁴ (OH) —CR ⁵ ₂ —NR ⁶ —, —NR ⁴ —CO—NR ⁵ —, —CR ⁴ (OH) —CR ⁵ ₂ —O—CO—; is there. R ^{1 to} R ⁶ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different.

  An example of a part of the functional side chain of the modified graft copolymer obtained by the treatment with the modifier B after the treatment with the modifier A is as follows. In the following example, styrene is used as the modifier B.

  Moreover, the example in the case of using a dibasic acid compound as a monomer for main chains is as follows.

In the above formula, Z represents a functional group I, and N represents a functional group II. Specifically, Z is a carboxylic acid anhydride residue or a carboxyl group, and N is a group selected from a hydroxyl group, an epoxy group, an amino group, and an isocyanate group. L is a site linking a polymerizable moiety (—CR ¹ = CR ² R ³ ) and N, and is a —CO—O— group or a —C ₆ H ₄ — group (phenylene ring) directly bonded to the polymerizable moiety. Is a linking group composed of an atom selected from carbon, hydrogen, oxygen and nitrogen atoms, containing either of the above as an essential component. S is —CO—O—, —CO—O—CR ⁴ ₂ —CR ⁵ (OH) —, —CO—NR ⁴ —, and

Is a group selected from R ^{1 to} R ⁵ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different.

(2) Method of forming functional side chain using functional polymer having functional group II In this method, functional polymer having functional group II (modifier C) is used to form functional group I. To form functional side chains.
In the case of this method, the graft copolymer preferably has a monomer unit amount having a functional group I of 0.05 to 20 mol% with respect to the monomer unit amount forming the main chain. More preferably, it is 1 to 10 mol%. Within the above range, by-product of a cross-linked product can be avoided, and excellent adhesiveness can be obtained for polyolefins and different materials such as polar resins and polar compounds.

  The modifier C preferably has a specific molecular weight in order for the functional side chain to exhibit sufficient compatibility, hydrophilicity, and adhesiveness, and the weight average molecular weight Mw in terms of polystyrene measured by GPC is 100 to 100. 100000 or less are preferable, More preferably, it is 300-80000, More preferably, it is 500-60000. When Mw satisfies the lower limit, the compatibility and hydrophilicity of the modified graft copolymer are improved. As a result, for example, in an aqueous dispersion using polyacrylic acid, polyetheramine or the like as the modifier C, the effect of stabilizing the particle diameter is obtained. When Mw satisfies the upper limit, an appropriate viscosity can be obtained, and at the same time, a good balance between the polyolefin chain and the functional side chain can be obtained, and excellent compatibility and adhesiveness can be obtained.

  The amount of the functional group II in the modifier C may be one per molecule of the modifier from the viewpoint of the formation efficiency of the functional side chain. Moreover, from a viewpoint of reduction of gel production | generation, 1-10 are preferable per modifier | denaturant molecule, More preferably, it is 1-5, Most preferably, it is one. A large number of functional groups is not preferable because a three-dimensional network structure is easily formed and a gel is easily generated. The formation of this gel can also be controlled by adjusting the type of functional group II. That is, even if it has multiple functional groups II, generation | occurrence | production of a gel can be suppressed because the number of highly reactive functional groups is appropriate. Specific examples include hydrophilic polymers having a plurality of hydroxyl groups and one amino group having a higher reactivity.

  Specific examples of the modifying agent C include natural polymers, semi-synthetic polymers, and synthetic polymers.

  Natural polymers include potato starch, corn starch, wheat starch, potato starch, tapioca starch, rice starch, and other seaweed components (such as soda alginate), gum arabic, tragacanth gum, and konjac ingredients. Examples thereof include animal products such as quality materials, glue, casein and gelatin, fermented mucilages such as pullulan and dextrin, and modified products thereof.

  Semi-synthetic polymers include those obtained by chemical treatment of the above natural polymers, such as starch starch such as carboxyl starch, cationic starch and dextrin, cellulose such as viscose, methylcellulose, ethylcellulose, carboxymethylcellulose and hydroxyethylcellulose. Etc.

  Examples of the synthetic polymer include an addition polymerization polymer, a polymer by condensation polymerization, and a polymer by ring-opening polymerization.

Addition polymerization polymers include polystyrene, polyvinyl chloride, poly (meth) acrylic acid, hydroxyethyl poly (meth) acrylate, dimethylaminoethyl poly (meth) acrylate, and dimethylaminoethyl quaternary poly (meth) acrylate. Compound, poly (meth) acrylamide, polyvinylpyrrolidone, polyvinyl alcohol and the like.
As a method for introducing the functional group II into the above addition polymerization polymer (or a method for adjusting the amount of the functional group), a method of copolymerizing an addition polymerizable monomer having a functional group as a copolymerization component, or a method having a functional group Examples thereof include a method in which a part of the functional group of the copolymer is left alone or inactivated, and a method in which a functional group is introduced by a reaction between a chain end and a terminator having a functional group by living polymerization.

  Examples of the polymer by condensation polymerization and ring-opening polymerization include polyesters, polyester polyols, polyether polyols, polyethers, and polyetheramines.

The compounds of polyesters and polyester polyols can be obtained by condensation polymerization of polyhydric alcohol and polybasic acid by a known method, or by ring-opening polymerization of aliphatic lactones. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, , 6-hexanediol and the like. Polybasic acids include maleic acid, fumaric acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid and Examples thereof include aliphatic or aromatic dicarboxylic acids such as these acid anhydrides, or aromatic polycarboxylic acids such as trimellitic acid, pyromellitic acid, and acid anhydrides thereof. Examples of the aliphatic lactone include γ-caprolactone, δ-caprolactone, ε-caprolactone, γ-valerolactone, δ-valerolactone, ε-valerolactone, and β-methyl-δ-valerolactone.
As the polyester polyol compounds, those having a hydroxyl value of 30 to 250 KOHmg / g are preferably used.

  The compounds of polyesters and polyester polyols can produce a secondary modified product by reacting with the functional group I of the graft copolymer, with the terminal hydroxyl group acting as the functional group II, such as a carboxyl group or a dicarboxylic anhydride group. A secondary modified product can be produced by an esterification reaction. A transesterification reaction can also be used.

Polyether polyol compounds are compounds having hydroxyl groups at both ends, obtained by ring-opening polymerization of cyclic alkylene oxides such as ethylene oxide, propylene oxide, trimethylene oxide, and tetrahydrofuran by a known method. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. The polyether polyols preferably have a hydroxyl value of 30 to 250 KOHmg / g.
In the polyether polyol compound, the terminal hydroxyl group acts as the functional group II and can react with the functional group I of the graft copolymer to produce a secondary modified product.

  Polyether compounds can be obtained by ring-opening polymerization of cyclic alkylene oxide or cyclic alkylene imine. For example, a secondary modified product can be produced by a method of ring-opening polymerization of a cyclic alkylene oxide in the presence of a graft copolymer.

  Polyetheramine compounds are compounds having a main chain skeleton of polyether and having a primary or secondary amino group as a reactive group at one or both ends. Specific examples include Huntsman's Jeffermin M series, D series, and ED series. A terminal modified amino group acts as a functional group II, and can react with the functional group I of the graft copolymer to produce a secondary modified product.

  In addition to the above, a polymer obtained by condensation polymerization, polycondensation, ring-opening polymerization or the like and having a functional group II in the molecular main chain or at the terminal can be used without limitation.

  Depending on the functional polymer, a functional side chain can also be formed by transesterification. In this case, the ratio between the modifier C (polyester modifier) and the graft copolymer is preferably in the range of 20/1 to 1/20 by weight, more preferably 10/1 to 1/10. Preferably it is 4/1-1/4, Most preferably, it is 3/1-1/3. By satisfy | filling the said range, favorable compatibility is obtained also with respect to polyolefin, a polar resin, etc., and favorable adhesiveness and adhesiveness with respect to these are obtained.

The modification with the modifying agent C can be performed by a solution reaction or a melt reaction.
In the case of a solution reaction, the solvent includes aromatic hydrocarbons such as toluene, xylene and mixed xylene; aliphatic hydrocarbons such as n-hexane, n-heptane, isooctane and decane; alicyclic rings such as cyclohexane and methylcyclohexane Formula aliphatic hydrocarbons; halogenated hydrocarbons such as perchlorethylene, chlorobenzene and o-dichlorobenzene; carboxylic acid esters such as methyl acetate and ethyl acetate; alcohols such as ethanol, isopropanol and butanol.
The amount of modifier C used is preferably such that the amount of functional group II of modifier C is in the range of 0.1 to 1.2 moles relative to 1 mole of functional group I.
The reaction temperature is usually 30 to 200 ° C., preferably 40 to 150 ° C., and the reaction time is usually 1 minute to 10 hours, preferably 5 minutes to 5 hours. What is necessary is just to determine the density | concentration of a graft copolymer suitably in the range which can be stirred in a dispersion | distribution or melt | dissolution state in the range of 1 g / liter to 1500 g / liter.
In the case of the melt reaction method, any apparatus that can perform batch-type melt reaction and continuous-type melt reaction can be used without limitation, and for example, it can be performed with an apparatus such as a Banbury mixer, a kneader, or an extruder. The reaction is usually carried out at a temperature higher than the melting point of the polymer, and the reaction time is suitably 1 minute to 3 hours.

  The secondary modification treatment with the modifier C and the resulting modified graft copolymer are exemplified below. An example in which the dibasic acid compound is not used as a monomer for the main chain and the reaction between the functional group I and the functional group II is not a transesterification reaction is as follows.

In the above formula, X represents a functional group I, and Y represents a functional group II. X and Y are specifically groups selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an isocyanate group, and X and Y are different groups. P represents a site excluding the functional group II of the modifier C. W represents —CO—O—, —CO—O—CR ⁴ ₂ —CR ⁵ (OH) —, —CO—NR ⁴ —, —CR ⁵ (OH) —CR ⁶ ₂ —O—, —NR ⁴ —. A group selected from CO—O—, —CR ⁴ (OH) —CR ⁵ ₂ —NR ⁶ —, —NR ⁴ —CO—NR ⁵ —, —CR ⁴ (OH) —CR ⁵ ₂ —O—CO—; is there. R ^{1 to} R ⁶ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different.

The modified graft copolymer of the present invention may be produced by a secondary modification treatment with a low molecular weight compound as shown below. The low molecular weight compound has reactivity with the functional group I, and specifically includes alcohol compounds, carboxylic acid compounds, epoxy compounds, isocyanate compounds, amine compounds, and the like.
Examples of the alcohol compound include monoalcohols having 30 or less carbon atoms such as methanol, ethanol, propanol, and octanol. Examples of the carboxylic acid compound include monocarboxylic acid compounds such as acetic acid and propionic acid. Has other functional groups such as monoepoxy compounds such as ethylene oxide, propylene oxide, 1,2-dimethyl epoxide, 1,1-dimethylepoxyside, epichlorohydrin, epibromohydrin, 9,10-epoxystearic acid, etc. Examples of isocyanate compounds include monoisocyanates such as methyl isocyanate, ethyl isocyanate, isopropyl isocyanate, isobutyl isocyanate, phenyl isocyanate, and α-naphthyl isocyanate. And isocyanate compounds such as monoisocyanate compounds having other functional groups such as nitrophenyl isocyanate, and amine compounds include 1-aminopropane, 1-aminohexane, 1-aminoheptane , Cyclohexylamine, cycloheptylamine, cyclopentylamine, tetrahydronaphthylamine, monoamine compounds such as 1-amino-2-butene, and monoamine compounds having other functional groups such as amino acids.

[Use of modified graft copolymer]
As shown below, the modified graft copolymer of the present invention can be used in various applications, and examples of the main form include an aqueous dispersion and a solution.
The aqueous dispersion is obtained by dispersing the modified graft copolymer in water, and is usually in a ratio of 1 to 10 parts by mass of water with respect to 1 part by mass of the modified graft copolymer. Further, a surfactant, a basic substance, a hydrophilic organic solvent, an aqueous resin and the like can be added as necessary.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, Examples include sorbitan fatty acid esters, polyoxyalkylene alkyl ethers, glycerin fatty acid esters, polyoxyethylene alkyl amines, and alkyl alkanol amides. Anionic surfactants include fatty acid salts, alkyl sulfate esters, polyoxyethylene alkyl ether sulfate esters, sodium alkylbenzene sulfonate, sodium alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate Salt, naphthalenesulfonic acid formalin condensate and the like. Examples of the cationic surfactant include quaternary ammonium salt systems such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, stearyltrimethylammonium salt, dialkyldimethylolbenzylammonium salt, and alkylpyridinium salt. Examples of amphoteric surfactants include amino acids such as sodium alkylamino fatty acid, betaines such as alkylbetaine, carboxybetaine, sulfobetaine and phosphobetaine, and amine oxides such as alkylamine oxide. Of these, nonionic surfactants are preferred.
Surfactant may be used individually by 1 type, and 2 or more types may be mixed and used for it. Surfactant is 0.01-50 mass parts normally with respect to 100 mass parts of modified graft copolymers, Preferably it is 0.02-20 mass parts, More preferably, it is 0.02-1 mass parts.

Basic substances include inorganic basic compounds such as sodium hydroxide, potassium hydroxide and sodium carbonate; ammonia, methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, 2-ethyl-2-aminopropanol And the like. By adding a basic substance, the dispersion stability of the modified graft copolymer is improved. As basic substances, amines are preferred.
A basic substance may be used individually by 1 type, and 2 or more types may be mixed and used for it. A basic substance is 0.01-10 mass parts normally with respect to 100 mass parts of modified graft copolymers, Preferably it is 0.1-5 mass parts.

  Examples of the hydrophilic organic solvent include alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol, and ethers thereof. By blending the hydrophilic organic solvent, it is easy to obtain the effect of improving the drying speed and appearance of the aqueous dispersion. Therefore, it is particularly preferably blended for primer and paint applications.

  Examples of the aqueous resin include an aqueous acrylic resin, an aqueous urethane resin, an aqueous epoxy resin, an aqueous alkyd resin, an aqueous phenol resin, an aqueous amino resin, an aqueous polybutadiene resin, and an aqueous silicon resin.

  Other additives may be blended as needed, various stabilizers such as antioxidants, weather resistance stabilizers, heat resistance inhibitors, etc., colorants such as titanium oxide, carbon black, organic pigments, conductive carbon black, Examples thereof include conductivity imparting agents such as ferrite, antiseptics, fungicides, rust inhibitors, thickeners and antifoaming agents. Moreover, in order to improve the wettability with the base material to be applied, a small amount of an organic solvent may be added as necessary.

  When using an aqueous dispersion, it is preferable to heat after application. When the substrate is an olefin polymer, good adhesion can be obtained by heating. Although there is no restriction | limiting in particular in heating temperature, Usually, 50-150 degreeC, Preferably it is 60-130 degreeC. There is no restriction | limiting in particular also about the coating method, A conventionally well-known method, such as the method of apply | coating with a spray, the method of apply | coating with a roller, the method of applying with a brush, can be used.

  The solution of the modified graft copolymer of the present invention can be obtained by using an organic solvent instead of water in the aqueous dispersion. Also in the solution, a surfactant, a basic substance, an aqueous resin and the like can be added.

  The modified graft copolymer of the present invention has a high compatibilizing ability and is preferably used when forming various compositions. Examples of the composition include a coating composition such as a paint, an adhesive, a filler treatment agent, and a compatibilizing agent.

The modified graft copolymer of the present invention can be used as a coating composition such as a paint, and can form a coating film excellent in adhesion and adhesion to a substrate such as a thermoplastic resin.
Examples of the thermoplastic resin as the base material include high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene, polystyrene, and other olefinic homopolymers, ethylene / propylene copolymers. Polymers, olefin copolymers such as ethylene / butene copolymers, propylene / butene copolymers, olefin / diene copolymers such as ethylene propylene rubber (EPDM), polydienes such as polybutadiene, styrene-butadiene-styrene blocks Copolymers with styrene such as copolymer (SBS), styrene butadiene (SB), acrylonitrile styrene copolymer (AS), acrylonitrile butadiene styrene copolymer (ABS), styrene ethylene butylene styrene block copolymer (SEBS) ), Styrene Eth Such emission propylene styrene block copolymer (SEPS) hydrogenated resins, and the like. In particular, a propylene polymer such as polypropylene or an ethylene / propylene copolymer or a composition containing a propylene polymer is preferable.

  Other applications in the paint field include surface treatment of molded products made of polyamide resin, unsaturated polyester resin, polybutylene terephthalate resin, polycarbonate resin and the like.

  Further, the modified graft copolymer of the present invention can be used as a coating composition for undercoat, and is an acrylic resin, polyurethane resin, fatty acid-modified polyester resin, oil-free polyester resin, melamine resin, epoxy resin, polycarbonate resin, polyamide resin, phenol resin. In addition, it can be preferably used when a coating material, a primer, an adhesive or the like mainly composed of an alkyd resin or a polyether resin is applied to a polyolefin molded body. For example, it is possible to improve the adhesion between a coating material containing these resin components and a polyolefin molded body, and to form a coating film excellent in surface smoothness, sharpness, low temperature impact property and the like.

  The coating composition containing the modified graft copolymer of the present invention contains the modified graft copolymer and a solvent or water as essential components. Solvents include aliphatic hydrocarbons (hexane, heptane, octane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), alicyclic hydrocarbons (cyclohexane, methylcyclohexane, etc.), halogenated hydrocarbons (chloroform, etc.) And ethers (tetrahydrofuran, etc.). Moreover, when water is an essential component, the above-mentioned aqueous dispersion can be used. As a method for applying the coating composition, methods such as spray, roll, brush coating, bar coating, and spin coating can be used.

  The modified graft copolymer of the present invention can be used as a component of an adhesive. Examples of the base material for adhesion include the thermoplastic resins exemplified as the base material for the paint. Specifically, for adhesion between polyolefin polymers and adhesion between polyolefin polymers and dissimilar materials. It can be preferably used. Among the polyolefin polymers, propylene polymers such as polypropylene and ethylene / propylene copolymers are particularly preferable, and a composition containing the propylene polymer is also used as a base material for adhesion.

  Examples of different materials include glass, metal (aluminum, iron, brass, stainless steel, copper, metal-plated surface, etc.), ceramic, and natural organic matter (examples of materials include hemp, cotton, kenaf, etc.) Fiber, paper, cardboard), acrylic resin, polystyrene resin, polyvinyl ester resin and saponified product, polyvinyl ether resin, polyvinyl chloride resin, polyurethane resin, polyester resin, melamine resin, epoxy resin, polycarbonate resin, polyamide resin, phenol Examples thereof include synthetic polymers such as resins, alkyd resins, and polyether resins. Examples of the forms of these different materials include films, fibers, molded articles such as nonwoven fabrics, and powders.

  As an adhesion method, a solution or dispersion of the modified graft copolymer is applied (spray, roll, brush coating, bar coating, spin coating, etc.), and the solvent is dried and removed, followed by heat sealing, pressure bonding, and heating. Examples thereof include a method, a method in which a solid modified graft copolymer is sandwiched between adhesive substrates, heat sealing, pressure bonding, and heating.

  The modified graft copolymer of the present invention can be used as a filler treating agent. By using the modified graft copolymer of the present invention, various performances such as rigidity, flame retardancy, earthquake resistance, mass feeling, gloss, and color unevenness elimination can be imparted.

Examples of the filler include inorganic fillers and organic fillers.
Examples of the inorganic filler include a spherical filler, a plate-like filler, a fibrous filler, an inorganic flame retardant, and an inorganic pigment.
Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica, pearlite, shirasu balloon, sericite, diatomaceous earth, calcium sulfite, calcined alumina, calcium silicate, and the like. Examples of the plate-like filler include talc and mica. Examples of the fibrous filler include wollastonite, magnesium oxysulfate, potassium titanate fiber, fibrous calcium carbonate, glass fiber, and carbon fiber. Inorganic flame retardants include calcium carbonate, magnesium carbonate, fly ash, dehydrated sludge, natural silica, synthetic silica, kaolin, clay, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, barium sulfate, calcium hydroxide, and hydroxide. Aluminum, alumina, magnesium hydroxide, talc, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite, Aluminum borate, silica balloon, glass flake, glass balloon, silica, iron slag, copper, iron, iron oxide, carbon black, sendust, alnico magnet, magnetic powders such as various ferrites, cement, glass Powder, diatomaceous earth, antimony trioxide, magnesium oxysulfate, hydrated aluminum, hydrated gypsum, alum, and the like. Inorganic pigments include calcium carbonate, carbon black, titanium oxide, chromium oxide, lead white, cadmium pigments, iron oxide, ultramarine, complex oxide pigments (antimony chrome yellow, nickel antimony yellow, aluminum cobalt blue, aluminum chrome cobalt Blue green, copper chrome black, cobalt titanium green, etc.).

Examples of the organic filler include naturally-derived organic fillers, synthetic resin-derived organic fillers, and organic pigments.
Naturally derived organic fillers include wood particles such as wood powder and cotton powder, fir shell powder, fir shell fiber, jute, paper strip, collagen powder, leather powder, protein powder, silk powder, cellophane pieces, etc. Examples include woven fabric and non-woven fabric. Synthetic resin-derived organic fillers include crosslinked rubber powder, plastic powder, thermosetting resin powder, polyester fiber, polypropylene fiber, acrylic fiber, aromatic polyamide fiber, cellulose fiber, nylon fiber, polyester fiber, etc. Woven fabric and non-woven fabric. Examples of organic pigments include azo pigments, phthalocyanine pigments, dyed lakes, condensed polycyclic pigments, nitroso pigments, alizarin lakes, metal complex azomethine pigments, aniline black, alkali blue, and daylight fluorescent pigments.

  The average particle diameter of the spherical filler or plate-like filler is preferably 0.01 to 100 μm, and more preferably 0.1 to 80 μm. If the average particle size is less than 0.01 μm, it is difficult to produce a molded product, and if it exceeds 100 μm, the impact resistance may be lowered. The fiber length of the fibrous filler is preferably 10 μm to 10 mm, more preferably 20 μm to 3 mm. When the fiber length is less than 10 μm, the reinforcing effect is reduced, and when it exceeds 10 mm, molding may be difficult. Moreover, 0.1-50 micrometers is preferable and, as for the diameter of a fibrous filler, 0.2-30 micrometers is more preferable. Moreover, 0.01-100 micrometers is preferable and, as for the average particle diameter of an inorganic type flame retardant, 0.1-20 micrometers is more preferable. If the average particle size exceeds 80 μm, impact resistance and tensile elongation may be reduced. Furthermore, the particle size of the organic filler is preferably 10 to 325 mesh, and more preferably 10 to 20 mesh. If the particle size exceeds 325 mesh, the impact resistance may be reduced. In the case of a fibrous inorganic filler, the fiber length is preferably 10 μm to 10 mm, more preferably 20 μm to 3 mm.

  In the surface treatment, the filler may be blended as it is, but a silane-based, titanate-based, aluminate-based, zircoaluminum-based coupling agent, phosphoric acid-based, fatty acid-based surfactant, fats and oils, wax, You may process with a stearic acid, a silane coupling agent, etc. Such treatment facilitates molding of the composite material, improves the appearance of the product, and may improve the mechanical properties.

The filler can be treated with the modified graft copolymer of the present invention by the following method.
Dry method (method of direct contact between filler and modified graft copolymer)
The filler / modified graft copolymer or the filler / modified graft copolymer / resin is treated with a mixing stirrer, a melt extruder, or the like. Specifically, a mixing roll, an intensive mixer, a Banbury mixer, a kneader, a single screw or a twin screw extruder can be used. Since the modified graft copolymer of the present invention is soft and has a low melting point, for example, kenaf and cellulose fillers can suppress deterioration and yellowing. The temperature condition is in the range of room temperature to 140 ° C., preferably in the range of 60 to 110 ° C., and the time is 1 minute to 5 hours.
Wet method (method of contacting with filler using solution or dispersion of modified graft copolymer)
The modified graft copolymer is dissolved or dispersed in a solvent, and the filler is treated by immersion or the like. Solvents include aliphatic hydrocarbon solvents such as hexane, heptane, and octane, aromatic hydrocarbon solvents such as toluene and xylene, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, and ethers such as tetrahydrofuran. And halogenated hydrocarbon solvents such as chloroform and the like. Examples of the solvent for the dispersion include the above-mentioned solvent and water. Water is preferable from the viewpoint of environmental protection. The method for producing the aqueous dispersion conforms to the method described above.
In the treatment of the filler, the modified graft copolymer is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the filler. Moreover, in the case of a masterbatch, it is preferable that the compounding quantity of a modified graft copolymer shall be 5-400 mass parts with respect to 100 mass parts of inorganic fillers.

The surface-treated filler is melt mixed with the thermoplastic resin according to the purpose.
The thermoplastic resin is preferably an olefin polymer, a styrene elastomer, and an olefin elastomer.
Olefin polymers include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), polypropylene (PP), ethylene-propylene random copolymer or block copolymer. , Polybutene polymers, ethylene-cyclic olefin copolymers, ethylene-octene copolymers, and the like.
Examples of styrene elastomers include styrene-butadiene block copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene block copolymer (SIR), and styrene-isoprene-styrene block copolymer. (SIS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), and the like.
Examples of the olefin elastomer include ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EBR), and ethylene-propylene-diene copolymer rubber (EPDM).
The compounding quantity of a thermoplastic resin is 2-1000 mass parts normally with respect to 1 mass part of the surface-treated filler (filler + modified graft copolymer), Preferably, it is 3-500 mass parts.

The modified graft copolymer of the present invention can be preferably used as a compatibilizing agent, and can improve impact properties, rigidity, flexibility, chemical stability, etc. in the field of composite materials of thermoplastic resins and olefin polymers. it can.
Examples of the olefin polymer and the thermoplastic resin include those exemplified as the base material for coating compositions such as paints, and particularly preferable olefin polymers include polypropylene and polybutene. The blending amount of the thermoplastic resin other than the olefin polymer is preferably 1 to 2000 parts by mass with respect to 100 parts by mass of the olefin polymer.

When using the modified graft copolymer of this invention as a compatibilizing agent, the modified graft copolymer which has the molecular structure of each thermoplastic resin which comprises the composition to be compatibilized is preferable.
For example, when compatibilizing a composition comprising polypropylene and an acrylic resin, it is preferable to use a modified graft copolymer having a polypropylene chain and an acrylic chain such as methyl methacrylate.

  When the modified polyolefin polymer of the present invention is used as a compatibilizer, it is usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin composition (olefin polymer + other thermoplastic resin). The amount is preferably 0.5 to 10 parts by mass.

  In the case of producing a composition using the modified graft copolymer of the present invention as a compatibilizing agent, a melt kneader or a melt extruder can be used, specifically, a mixing roll, an intensive mixer, a Banbury mixer. A kneader, a single or twin screw extruder, etc. can be used. The kneading temperature is preferably 5 to 150 ° C. higher than the melting point or glass transition temperature based on the composition component having the highest melting point or glass transition temperature. The kneading time is usually preferably 1 minute to 1 hour.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Production Example 1 [Production of Reactive Polypropylene]
(1) Synthesis of Metal Complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was synthesized as follows.
In a Schlenk bottle, 3.0 g (6.97 mmol) of a lithium salt of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene) was dissolved in 50 ml of THF (tetrahydrofuran) and heated to -78 ° C. Cooled down. 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise and stirred at room temperature for 12 hours.
The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried to remove the solvent, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. Obtained (yield 84%).
Next, 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. And 50 ml of ether. The mixture was cooled to −78 ° C., and a hexane solution of n-BuLi (1.54M, 7.6 ml (1.7 mmol)) was added dropwise. After raising to room temperature and stirring for 12 hours, ether was distilled off. The obtained solid was washed with 40 ml of hexane to obtain 3.06 g (5.07 mmol) of the lithium salt as an ether adduct (yield 73%).
The results of measurement by ¹ H-NMR (90 MHz, THF-d ⁸ ) are as follows.
δ: 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (q, 4H, methylene), 6.2- 7.7 (m, 8H, Ar-H)
Under a nitrogen stream, the lithium salt obtained above was dissolved in 50 ml of toluene. The mixture was cooled to -78 ° C, and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to -78 ° C in advance, in toluene (20 ml) was added dropwise thereto. After dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off. The obtained residue was recrystallized from dichloromethane to obtain 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 33 mmol) was obtained (yield 26%).
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are as follows.
δ: 0.0 (s, 18H, trimethylsilyl), 1.02, 1.12 (s, 12H, dimethylsilylene), 2.51 (dd, 4H, methylene), 7.1-7.6 (m, 8H, Ar-H)
(2) Polymerization of propylene To a heat-dried stainless steel autoclave with an internal volume of 1.4 L, 0.4 L of dry heptane and 1.5 ml of a heptane solution of 1.5 mmol of triisobutylaluminum were added and stirred for 10 minutes. Next, 2 ml of 1.5 μmol of heptane slurry of methylanilinium tetrakis (pentafluorophenyl) borate was added, and (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) prepared in (1) above was added thereto. -0.5 ml of heptane slurry containing 1.5 μmol of bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added. 100 ml of hydrogen was weighed at room temperature (25 ° C.) and charged into an autoclave.
Next, the temperature was raised to 80 ° C. while stirring, and propylene gas was introduced up to 0.5 MPa in partial pressure. During the polymerization reaction, propylene gas was supplied by a pressure regulator so as to keep the pressure constant, and polymerization was performed for 40 minutes, followed by cooling, unreacted propylene was removed by depressurization, and the contents were taken out. The contents were air-dried, and further dried under reduced pressure at 80 ° C. for 8 hours to obtain 189.5 g of polypropylene. The polymerization evaluation results are shown in Table 1.

Production Example 2 [Production of Reactive Polypropylene]
In Production Example 1, hydrogen was not used, the temperature was changed to 70 ° C., the propylene partial pressure was 0.55 MPa, and the polymerization time was changed to 47 minutes. As a result, 83.4 g of polypropylene was obtained. The polymerization evaluation results are shown in Table 1.

Production Example 3 [Production of Reactive Polypropylene]
In Production Example 1, the same procedure was performed except that hydrogen was not used and the temperature was changed to 60 ° C. and the polymerization time was 47 minutes. As a result, 35.9 g of polypropylene was obtained. The polymerization evaluation results are shown in Table 1.

Production Example 4 [Production of Reactive Polypropylene]
(1) Synthesis of Metal Complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene)-(indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride was synthesized as follows.
Under a nitrogen stream, 50 ml of ether and 3.5 g (10.2 mmol) of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bisindene were added to a 200 ml Schlenk bottle at -78 ° C. A hexane solution (1.60 mol / liter, 12.8 milliliters) of n-butyllithium (n-BuLi) was added dropwise. After stirring at room temperature for 8 hours, the solvent was distilled off, and the obtained solid was dried under reduced pressure to obtain 5.0 g of a white solid. This solid was dissolved in 50 ml of tetrahydrofuran (THF), and 1.4 ml of iodomethyltrimethylsilane was added dropwise thereto at room temperature. After hydrolysis with 10 ml of water and extraction of the organic phase with 50 ml of ether, the organic phase was dried and the solvent was distilled off. 50 ml of ether was added thereto, and a hexane solution of n-BuLi (1.60 mol / liter, 12.4 ml) was added dropwise at −78 ° C. Then, the mixture was raised to room temperature and stirred for 3 hours, and then the ether was distilled off. The obtained solid was washed with 30 ml of hexane and then dried under reduced pressure. 5.11 g of this white solid was suspended in 50 ml of toluene, and 2.0 g (8.60 mmol) of zirconium tetrachloride suspended in 10 ml of toluene in another Schlenk bottle was added. After stirring at room temperature for 12 hours, the solvent was distilled off, the residue was washed with 50 ml of hexane, and then the residue was recrystallized from 30 ml of dichloromethane to obtain 1.2 g of yellow fine crystals (yield 25%).
(2) Polymerization of propylene In a heat-dried stainless steel autoclave with an internal volume of 5 L, a heptane solution of 2.5 L of dry heptane and 1.4 mmol of triisobutylaluminum, 1.4 ml of methylanilinium tetrakis (pentafluorophenyl) borate15. 2 ml of 4 μmol of heptane slurry was added and stirred for 10 minutes while controlling at 50 ° C.
Further, 3.8 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene)-(indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride of the transition metal compound complex prepared in (1) above. 6 ml of heptane slurry was added.
Further, after 5 ml of hydrogen was added, the temperature was raised to 60 ° C. while stirring, and propylene gas was introduced up to a partial pressure of 0.49 MPa.
During the polymerization reaction, propylene gas was supplied by a pressure regulator so that the pressure became constant, and polymerization was performed for 100 minutes, followed by cooling, removing unreacted propylene by depressurization, and taking out the contents.
The contents were air-dried and further dried under reduced pressure at 80 ° C. for 8 hours to obtain 1100 g of polypropylene. The polymerization evaluation results are shown in Table 1.

Comparative Production Example 1 [Production of terminal saturated polypropylene]
In a nitrogen atmosphere, 400 ml of dry heptane and 2.0 mmol of methylaluminoxane were added to a heat-dried stainless steel autoclave with an internal volume of 1 L and stirred for 10 minutes while controlling at 50 ° C.
Further, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene)-(indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride of the transition metal compound complex prepared in Production Example 4 (1) 0.6 ml of 6 μmol of heptane slurry was added. Further, hydrogen was introduced at a pressure of 0.01 MPa, then the temperature was raised to 60 ° C. while stirring, propylene was introduced, and polymerization was carried out at 0.8 MPa at a total pressure for 60 minutes. After completion of the reaction, the mixture was cooled, unreacted propylene was removed by depressurization, and the contents were taken out.
The contents were air-dried and further dried under reduced pressure at 80 ° C. for 8 hours to obtain 83 g of terminal saturated polypropylene. The results are shown in Table 1.

Comparative Production Example 2 [Production of terminal saturated polypropylene]
In a nitrogen atmosphere, 400 ml of dry heptane and 2.0 mmol of methylaluminoxane were added to a heat-dried stainless steel autoclave with an internal volume of 1 L and stirred for 10 minutes while controlling at 50 ° C.
Furthermore, 0.6 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride of the transition metal compound complex prepared in Production Example 1 (1) 0.6 ml of heptane slurry was charged. Further, after introducing hydrogen at a pressure of 0.05 MPa, the temperature was raised to 60 ° C. while stirring, propylene was introduced, and polymerization was performed at 0.8 MPa at a total pressure for 60 minutes. After completion of the reaction, the mixture was cooled, unreacted propylene was removed by depressurization, and the contents were taken out.
The contents were air-dried and then dried under reduced pressure at 80 ° C. for 8 hours to obtain 95 g of terminal saturated polypropylene. The results are shown in Table 1.

Production Example 5 [Production of Graft Copolymer]
In a separable flask equipped with a stirrer, 30 g of the reactive polypropylene synthesized in Production Example 1 and 37 ml of dehydrated toluene were charged in a nitrogen atmosphere. It melt | dissolved at the temperature of 70 degreeC, stirring. To this, 5.2 g of maleic anhydride and 7.7 g of 1-decene were added and dissolved as monomers for the main chain.
To this, 0.31 g of α, α′-azobisisobutyronitrile (AIBN) dissolved in 15 ml of dehydrated toluene was added over 1 hour. After the addition, it reacted for 6 hours. After completion of the reaction, the solvent toluene was removed under reduced pressure, followed by drying under reduced pressure at 100 ° C. for 24 hours.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured by the GPC method described above.
In order to obtain the graft ratio, the dried polymer was finely dispersed in methyl ethyl ketone, stirred and extracted at room temperature for 2 hours, and then the liquid part was recovered with a centrifuge (21000 rpm, 15 minutes). The solid portion was further extracted and separated twice and dried to recover the polymer.
The results are shown in Table 2.
Moreover, when the NMR measurement of the polymer contained in a liquid part was implemented, since the chain | strand based on the raw material polypropylene was detected, it has shown that the graft body exists also in a soluble part.
Similarly, in the NMR analysis of the copolymer of maleic anhydride / decene-1 / reactive polypropylene, 94.4% of the terminal vinylidene group of the reactive polypropylene before the reaction is consumed after the copolymerization. Was confirmed. From this, it was shown that the side chain is a polypropylene chain having a weight average molecular weight of 37200, with the maleic anhydride / decene-1 copolymer as the main chain.

Production Example 6 [Production of Graft Copolymer]
In a separable flask equipped with a stirrer, 100 g of the reactive polypropylene synthesized in Production Example 1 and 215 ml of dehydrated toluene were charged in a nitrogen atmosphere. It melt | dissolved at the temperature of 70 degreeC, stirring. Acrylic acid 22.5 g and 2-hydroxyethyl acrylate 4.0 g were added to this and dissolved.
To this, 0.50 g of α, α′-azobisisobutyronitrile (AIBN) dissolved in 20 ml of dehydrated toluene was added over 1 hour. After the addition, it reacted for 6 hours. After completion of the reaction, the solvent toluene was removed under reduced pressure, followed by drying under reduced pressure at 100 ° C. for 24 hours. The results are shown in Table 2.

Production Example 7 [Production of Graft Copolymer]
In a separable flask equipped with a stirrer, 600 g of the reactive polypropylene synthesized in Production Example 4 and 1000 ml of dehydrated toluene were charged in a nitrogen atmosphere. It melt | dissolved at the temperature of 70 degreeC, stirring. To this, 91.3 g of methyl acrylate and 134 g of glycidyl methacrylate were added and dissolved.
To this, 1.50 g of α, α′-azobisisobutyronitrile (AIBN) dissolved in 60 ml of dehydrated toluene was added over 1 hour. After the addition, it reacted for 6 hours. After completion of the reaction, the solvent toluene was removed under reduced pressure, followed by drying under reduced pressure at 100 ° C. for 24 hours. The results are shown in Table 2.

Production Example 8 [Production of Graft Copolymer]
The same procedure as in Production Example 5 was conducted except that the reactive polypropylene obtained in Production Example 1 was replaced with the reactive polypropylene obtained in Production Example 2. The results are shown in Table 2.

Production Example 9 [Production of Graft Copolymer]
The same procedure as in Production Example 5 was carried out except that the reactive polypropylene obtained in Production Example 1 was replaced with the reactive polypropylene obtained in Production Example 3. The results are shown in Table 2.

Production Example 10 [Production of Graft Copolymer]
The same procedure as in Production Example 5 was carried out except that the reactive polypropylene obtained in Production Example 1 was replaced with the reactive polypropylene obtained in Production Example 4. The results are shown in Table 2.

  In addition, the composition of the polymers of Production Examples 5 to 10 shown in Table 2 is calculated from the absorption based on the carbonyl group for the monomers other than 1-decene by infrared absorption spectrum analysis, and the 1-decene content is calculated from the NMR analysis. did. The yield, monomer content, weight average molecular weight, and molecular weight distribution are values of the copolymer from which unreacted monomers have been removed, and the graft ratio is determined from the solvent-insoluble portion determined by solvent washing by the method described above. Were determined.

Comparative production example 3 [Production of maleic anhydride-modified product]
In a separable flask with a stirrer, 50 g of polypropylene synthesized in Comparative Production Example 1 and 93 g of dehydrated toluene were charged in a nitrogen atmosphere. It melt | dissolved at the temperature of 110 degreeC, stirring. 4 g of maleic anhydride was added to this and dissolved. To this, 1.4 g of t-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, Perbutyl I) dissolved in 15 ml of dehydrated toluene was added. After the addition, it reacted for 7 hours. After completion of the reaction, the mixture was cooled to room temperature, poured into a large amount of acetone, and the acetone-insoluble portion was filtered and washed to recover the polymer.
(Maleic anhydride content is 2.4 wt%, Mw is 43500)
In this reaction, the terminal saturated polypropylene of the raw material undergoes a modification reaction to reduce the molecular weight. This is a reaction in which maleic anhydride is added while the modification reaction is accompanied by decomposition, indicating that the structure and formation mechanism of the graft copolymer of the present application are different.

Comparative Production Example 4 [Production of maleic anhydride-modified product]
In a separable flask with a stirrer, 50 g of polypropylene synthesized in Comparative Production Example 2 and 93 g of dehydrated toluene were charged in a nitrogen atmosphere. It melt | dissolved at the temperature of 110 degreeC, stirring. 4 g of maleic anhydride was added to this and dissolved. To this, 1.4 g of t-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, Perbutyl I) dissolved in 15 ml of dehydrated toluene was added. After the addition, it reacted for 7 hours. After completion of the reaction, the mixture was cooled to room temperature, poured into a large amount of acetone, and the acetone-insoluble portion was filtered and washed to recover the polymer.
(Maleic anhydride content is 2.4 wt%, Mw is 100,000)
As described above, the molecular weight was lowered as in Comparative Production Example 3.

Example 1
A flask equipped with a stirrer was equipped with a cooling tank, a dropping funnel and a thermometer, and 15 g of the graft copolymer (maleic anhydride / 1-decene-g-polypropylene) of Production Example 5 and 60 ml of toluene were charged and dissolved at 100 ° C. . Under an air stream, 0.4 g of 2-hydroxyethyl acrylate, 0.04 g of hydroquinone monomethyl ether and 0.6 g of dimethylbenzylamine were added and reacted at 100 ° C. for 3 hours. As a result of sampling a polymer component equivalent to 0.2 g and measuring an infrared absorption spectrum, it was confirmed that the total amount of 2-hydroxyethyl acrylate was added. After completion of the reaction, 30 ml of toluene was added and the temperature was controlled at 70 ° C. After adding 20 g of styrene, 0.2 g of α, α′-azobisisobutyronitrile (AIBN) was added thereto, and graft polymerization reaction was carried out at the same temperature for 6 hours, and then 0.2 g of AIBN was added. The reaction was carried out at 90 ° C. for 2 hours. As a result, a toluene solution of the modified graft copolymer was obtained. A part of the reaction mixture was collected from this solution, and after removing the solvent and unreacted monomers, it was further dried at 90 ° C. under reduced pressure for 8 hours. The weight increased by secondary modification is the amount of polystyrene produced (W3), and the secondary modification rate is indicated by [W3 / (W4 + W3)] × 100 (%) from the raw material (graft copolymer of Production Example 5) weight (W4). It was. The results are shown in Table 3.

Example 2
A flask equipped with a stirrer was equipped with a cooling tank, a dropping funnel and a thermometer, and 15 g of the graft copolymer (maleic anhydride / 1-decene-g-polypropylene) of Production Example 5 and 60 ml of toluene were charged and dissolved at 100 ° C. . Under an air stream, 0.5 g of glycidyl methacrylate, 0.04 g of hydroquinone monomethyl ether, and 0.1 g of 1,8-diazabicyclo [5.4.0] -7-undecenoic acid were added and reacted at 100 ° C. for 5 hours. As a result of sampling a polymer component equivalent to 0.2 g and measuring an infrared absorption spectrum, it was confirmed that the total amount of glycidyl methacrylate was added. After completion of the reaction, 30 ml of toluene was added and the temperature was controlled at 70 ° C. After adding 20 g of styrene, 0.2 g of α, α′-azobisisobutyronitrile (AIBN) was added thereto, and graft polymerization reaction was carried out at the same temperature for 6 hours, and then 0.2 g of AIBN was added. The reaction was carried out at 90 ° C. for 2 hours. As a result, a toluene solution of the modified graft copolymer was obtained. The results are shown in Table 3.

Example 3
A flask equipped with a stirrer was equipped with a cooling pad, a dropping funnel and a thermometer, and 50 g of the graft copolymer (acrylic acid / 2-hydroxyethyl acrylate-g-polypropylene) of Production Example 6 and 200 ml of dehydrated toluene were charged and dissolved at 100 ° C. I let you. Under a dry air stream, 2.1 g of 2-methacryloyloxyethyl isocyanate and 0.12 g of hydroquinone monomethyl ether were added and reacted at 110 ° C. for 5 hours. As a result of sampling an equivalent of 0.2 g of a polymer component and measuring an infrared absorption spectrum, it was confirmed that the total amount of 2-methacryloyloxyethyl isocyanate was added. After completion of the reaction, 100 ml of toluene was added and the temperature was controlled at 70 ° C. After adding 100 g of styrene to this, 0.67 g of α, α′-azobisisobutyronitrile (AIBN) was added, and the graft polymerization reaction was carried out at the same temperature for 6 hours, and then 0.6 g of AIBN was added. The reaction was carried out at 90 ° C. for 2 hours. As a result, a toluene solution of the modified graft copolymer was obtained. The results are shown in Table 3.

Example 4
In Example 3, the procedure was carried out in the same manner except that 50 g of styrene and 50 g of methyl methacrylate were used instead of 100 g of styrene. The results are shown in Table 3.

Example 5
A flask equipped with a stirrer was equipped with a cooling bowl, a dropping funnel and a thermometer, and 50 g of the graft copolymer (methyl acrylate / glycidyl methacrylate-g-polypropylene) of Production Example 7 and 200 ml of dehydrated toluene were charged and dissolved at 100 ° C. . Under a dry air stream, 2.1 g of 2-methacryloyloxyethyl isocyanate and 0.12 g of hydroquinone monomethyl ether were added and reacted at 110 ° C. for 5 hours. As a result of sampling an equivalent of 0.2 g of a polymer component and measuring an infrared absorption spectrum, it was confirmed that the total amount of 2-methacryloyloxyethyl isocyanate was added. After completion of the reaction, 100 ml of toluene was added and the temperature was controlled at 70 ° C. After adding 100 g of methyl methacrylate to this, 0.67 g of α, α′-azobisisobutyronitrile (AIBN) is added, and a graft polymerization reaction is carried out at the same temperature for 6 hours, and then 0.6 g of AIBN is added. The reaction was carried out at 90 ° C. for 2 hours. As a result, a toluene solution of the modified graft copolymer was obtained. The results are shown in Table 3.

Example 6
A flask equipped with a stirrer was equipped with a cooling pad, a dropping funnel and a thermometer, and 15 g of the graft copolymer (maleic anhydride / 1-decene-g-polypropylene) of Production Example 8 and 60 ml of toluene were charged and dissolved at 100 ° C. . Under an air stream, 0.52 g of glycidyl methacrylate, 0.04 g of hydroquinone monomethyl ether and 0.1 g of 1,8-diazabicyclo [5.4.0] -7-undecenoic acid were added and reacted at 100 ° C. for 5 hours. As a result of sampling a polymer component equivalent to 0.2 g and measuring an infrared absorption spectrum, it was confirmed that the total amount of glycidyl methacrylate was added. After completion of the reaction, 30 ml of toluene was added and the temperature was controlled at 70 ° C. After adding 30 g of methyl methacrylate to this, 0.2 g of α, α′-azobisisobutyronitrile (AIBN) is added, and the graft polymerization reaction is carried out at the same temperature for 6 hours, and then 0.2 g of AIBN is added. The reaction was carried out at 90 ° C. for 2 hours. As a result, a toluene solution of the modified graft copolymer was obtained. The results are shown in Table 3.

Example 7
In Example 6, instead of methyl methacrylate, 30 g of acrylic acid was used, and a toluene solution of 0.2 g of AIBN was added dropwise over 1 hour, and then a graft polymerization reaction was carried out for 6 hours. Further, 0.2 g of AIBN was added and reacted at 90 ° C. for 2 hours. As a result, a toluene solution of the modified graft copolymer was obtained. The results are shown in Table 3.

Example 8
A flask equipped with a stirrer was equipped with a cooling bowl, a dropping funnel and a thermometer, and 10 g of the graft copolymer (maleic anhydride / 1-decene-g-polypropylene) of Production Example 9 and 60 ml of toluene were charged and dissolved at 100 ° C. . Under an air stream, 0.4 g of glycidyl methacrylate, 0.06 g of hydroquinone monomethyl ether, and 0.15 g of 1,8-diazabicyclo [5.4.0] -7-undecenoic acid were added and reacted at 100 ° C. for 5 hours. As a result of sampling a polymer component equivalent to 0.2 g and measuring an infrared absorption spectrum, it was confirmed that the total amount of glycidyl methacrylate was added. After completion of the reaction, 30 ml of toluene was added, and the temperature was controlled at 70 ° C. After adding 20 g of methyl methacrylate to this, 0.2 g of α, α′-azobisisobutyronitrile (AIBN) was added, and graft polymerization reaction was carried out at the same temperature for 6 hours, and then 0.2 g of AIBN was added. The reaction was carried out at 90 ° C. for 2 hours. As a result, a toluene solution of the modified graft copolymer was obtained. The results are shown in Table 3.

Example 9
A flask equipped with a stirrer was equipped with a cooling tank, a dropping funnel, and a thermometer, and 8 g of the graft copolymer (maleic anhydride / 1-decene-g-polypropylene) of Production Example 10 and 50 ml of toluene were charged and dissolved at 100 ° C. . Under an air stream, 0.2 g of glycidyl methacrylate, 0.02 g of hydroquinone monomethyl ether and 0.05 g of 1,8-diazabicyclo [5.4.0] -7-undecenoic acid were added and reacted at 100 ° C. for 5 hours. As a result of sampling a polymer component equivalent to 0.2 g and measuring an infrared absorption spectrum, it was confirmed that the total amount of glycidyl methacrylate was added. After completion of the reaction, 30 ml of toluene was added, and the temperature was controlled at 70 ° C. After adding 20 g of methyl methacrylate to this, 0.2 g of α, α′-azobisisobutyronitrile (AIBN) was added, and graft polymerization reaction was carried out at the same temperature for 6 hours, and then 0.2 g of AIBN was added. The reaction was carried out at 90 ° C. for 2 hours. As a result, a toluene solution of the modified graft copolymer was obtained. The results are shown in Table 3.

Example 10
In Example 9, it replaced with methyl methacrylate and implemented similarly except using 20g of styrene. The results are shown in Table 3.

Example 11
In Example 9, it implemented similarly except having used 20 g of vinyl acetate instead of methyl methacrylate. The results are shown in Table 3.

Example 12
In Example 9, it implemented similarly except having used 20 g of acrylic acid instead of methyl methacrylate. The results are shown in Table 3.

Example 13
A flask equipped with a stirrer was equipped with a cooling tank, a dropping funnel, and a thermometer, 10 g of the graft copolymer (maleic anhydride / 1-decene-g-polypropylene) of Production Example 9, and 5 g of polyester polyol P-2010 (manufactured by Kuraray). , Toluene 50 ml and dimethylbenzylamine 0.3 g were charged and reacted at 110 ° C. for 6 hours. After completion of the reaction, an almost transparent modified graft copolymer solution was obtained. A portion of the sample was sampled, the solvent toluene was removed under reduced pressure, and an infrared absorption spectrum analysis was performed. It was confirmed that the polyester polyol reacted because the absorption corresponding to maleic anhydride near 1785 cm ⁻¹ was reduced. .

Example 14
A flask equipped with a stirrer was equipped with a cooling tank, a dropping funnel and a thermometer, 10 g of the graft copolymer (maleic anhydride / 1-decene-g-polypropylene) of Production Example 9 (maleic anhydride 11.4 mmol), 50 ml of toluene. Was dissolved. To this, 11.4 g (equivalent to 11.4 mmol amine) of methoxypoly (oxyethylene-oxypropylene) -2-propylamine [Polyetheramine M-1000 molecular weight 1000 manufactured by Huntsman Co., Ltd.] was added and reacted at 110 ° C. for 4 hours. did.
The solvent toluene was distilled off under reduced pressure to obtain 21 g of a modified graft copolymer. As a result of infrared absorption spectrum analysis of the modified graft copolymer, it was confirmed that the polyetheramine had reacted since the absorption corresponding to maleic anhydride in the vicinity of 1785 cm ⁻¹ disappeared.

Example 15
A flask equipped with a stirrer was equipped with a cooling pad, a dropping funnel and a thermometer, and 10 g of maleic anhydride / 1-decene-g-polypropylene of Production Example 9 (11.4 mmol of maleic anhydride) and 50 ml of toluene were added and dissolved. 10 g of terminal amino group-containing polystyrene produced by living anionic polymerization [polystyrene equivalent weight average molecular weight (Mw) = 25000, Mw / Mn = 1,15] was added thereto and reacted at 110 ° C. for 4 hours.
The solvent toluene was distilled off under reduced pressure to obtain 20 g of a secondary modified polymer. As a result of infrared absorption spectrum analysis of the secondary modified polymer, it was confirmed that the terminal amino group reacted with maleic anhydride because the absorption intensity corresponding to maleic anhydride in the vicinity of 1785 cm ⁻¹ was lowered.

Example 16
A flask equipped with a stirrer was equipped with a cooling tank, a dropping funnel, and a thermometer, and under a nitrogen atmosphere, 100 ml of dehydrated toluene, 0.44 g (corresponding to 2.85 mmol) of 2-methacryloyloxyethyl isocyanate, and 30 g of methyl methacrylate were added. While controlling at 80 ° C., 0.2 g of α, α′-azobisisobutyronitrile (AIBN) was added and copolymerization was carried out for 6 hours. After completion of the reaction, 10 g of the graft copolymer (maleic anhydride / 1-decene-g-polypropylene) of Production Example 9 (11.4 mmol of maleic anhydride) and 0.12 g of hydroquinone monomethyl ether were added to the polymer solution. The reaction was carried out for 5 hours at ° C. As a result of sampling a polymer component equivalent to 0.2 g and measuring an infrared absorption spectrum, it was confirmed that the total amount of 2-metaquinoyloxyethyl isocyanate residue was added.
After completion of the reaction, 30 ml of toluene was added, and the temperature was controlled at 70 ° C. To this, 5 g of terminal OH-containing polybutadiene [R45HT manufactured by Idemitsu Kosan Co., Ltd.] was added, 0.05 g of triethylenediamine and 0.02 g of tin octenoate were further added, and the reaction was carried out at the same temperature for 6 hours. As a result, a toluene solution of the modified graft copolymer was obtained.

Comparative Example 1
A flask equipped with a stirrer was equipped with a cooling tank, a dropping funnel and a thermometer, and 8.3 g of maleic anhydride-modified polypropylene of Comparative Production Example 3 and 50 ml of toluene were charged and dissolved at 100 ° C. Under an air stream, 0.2 g of glycidyl methacrylate, 0.02 g of hydroquinone monomethyl ether and 0.05 g of 1,8-diazabicyclo [5.4.0] -7-undecenoic acid were added and reacted at 100 ° C. for 5 hours. As a result of sampling a polymer component equivalent to 0.2 g and measuring an infrared absorption spectrum, it was confirmed that the total amount of glycidyl methacrylate was added. After completion of the reaction, 30 ml of toluene was added and the temperature was controlled at 70 ° C. After 20 g of acrylic acid was added thereto, 20 ml of a toluene solution of 0.2 g of α, α′-azobisisobutyronitrile (AIBN) was added dropwise over 1 hour, and then a graft polymerization reaction was carried out for 6 hours. Further, 0.2 g of AIBN was added and reacted at 90 ° C. for 2 hours. As a result, a toluene dispersion solution of the secondary modified polymer was obtained.

Comparative Example 2
A flask equipped with a stirrer was equipped with a cooling pad, a dropping funnel and a thermometer, and 50 g of maleic anhydride-modified polypropylene of Comparative Production Example 4 and 200 ml of toluene were charged and dissolved at 100 ° C. Under an air stream, 1.73 g of glycidyl methacrylate, 0.04 g of hydroquinone monomethyl ether, and 0.1 g of 1,8-diazabicyclo [5.4.0] -7-undecenoic acid were added and reacted at 100 ° C. for 5 hours. As a result of sampling a polymer component equivalent to 0.2 g and measuring an infrared absorption spectrum, it was confirmed that the total amount of glycidyl methacrylate was added. After completion of the reaction, 100 ml of toluene was added and the temperature was controlled at 70 ° C. To this was added 100 g of methyl methacrylate, 20 ml of a toluene solution of 0.5 g of α, α′-azobisisobutyronitrile (AIBN) was added dropwise over 1 hour, and then a graft polymerization reaction was carried out for 6 hours. Further, 0.5 g of AIBN was added and reacted at 90 ° C. for 2 hours. As a result, a toluene dispersion solution of the secondary modified polymer was obtained.

Comparative Example 3
A flask equipped with a stirrer was equipped with a cooling tank, a dropping funnel and a thermometer, and 20 g of maleic anhydride-modified polypropylene of Comparative Production Example 4 and 80 ml of toluene were charged and dissolved at 100 ° C. Under an air stream, 0.69 g of glycidyl methacrylate, 0.02 g of hydroquinone monomethyl ether, and 0.05 g of 1,8-diazabicyclo [5.4.0] -7-undecenoic acid were added and reacted at 100 ° C. for 5 hours. As a result of sampling a polymer component equivalent to 0.2 g and measuring an infrared absorption spectrum, it was confirmed that the total amount of glycidyl methacrylate was added. After completion of the reaction, 100 ml of toluene was added and the temperature was controlled at 70 ° C. After 40 g of acrylic acid was added thereto, 20 ml of a toluene solution of 0.3 g of α, α′-azobisisobutyronitrile (AIBN) was added dropwise over 1 hour, and then a graft polymerization reaction was carried out for 6 hours. Further, 0.3 g of AIBN was added and reacted at 90 ° C. for 2 hours. As a result, a toluene dispersion solution of the secondary modified polymer was obtained.

[Evaluation of adhesion performance 1]
(1) Preparation of solution for adhesion The secondary modified polypropylene of Example 12 and Comparative Example 1 and the polypropylene produced in Comparative Production Example 1 were dissolved in tetrahydrofuran at 60 ° C. using the amounts shown in Table 4 to obtain an adhesion solution A. -D was prepared.
(2) Application of adhesive solution to PP substrate A polypropylene sheet having a length of 10 cm and a width of 8 cm was washed with acetone, and the above-mentioned adhesive solution was concentrated at a concentration of 0.5 ml / 7.5 cm ² (2.5 × 3 cm). Was applied to one end portion (8 × 3 cm) of the sheet and dried in an oven at 40 ° C. for 1 hour and at 65 ° C. for 2 hours. This polypropylene sheet was cut to a width of 2.5 cm.
Polypropylene sheet: Idemitsu Unitech Co., Ltd. Super Pure Array SG-140TC Thickness 0.3mm
(3) Manufacture of adhesive body The polypropylene sheet obtained in (2) above and the acetone-washed polypropylene sheet SG-140TC having the same shape or glass plate are combined with each other through an adhesive layer, and heated at 130 ° C using a hot press at 20 ° C. After preheating for 2 seconds, fusion was performed at a pressure of 0.5 Mpa for 40 seconds. This was lightly sandwiched between 25 ° C. cooling presses and cooled to room temperature. The prepared test piece was allowed to stand at room temperature for one week, and then the adhesive strength was measured.
As the glass plate, a slide glass 1201 (length: 7.6 cm, width: 2.6 cm, thickness: 0.15 to 0.14 cm) manufactured by AS ONE Co., Ltd. was used.
(4) Measurement of adhesive strength A T peel test was performed at a tensile speed of 50 mm / min. For the measurement, an autograph (DSC-200) manufactured by Shimadzu Corporation was used to determine the peel adhesive strength from the maximum stress. Moreover, the average of the measured value of 3 test pieces was used for the measured value. The results are shown in Table 4.

[Evaluation of dispersion performance]
(1) Production of PP / PMMA resin composition 35 g of polypropylene (manufactured by Prime Polymer Co., Ltd., J3000GV), 5 g of polymethyl methacrylate (manufactured by Hiroshima Wako Co., Ltd.), 1 g of secondary modified polypropylene obtained in Example 6 and phenol 0.04 g of the system antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals) was mixed well in advance. A batch kneader (Toyo Seiki Co., Ltd., Labo Plast Mill) was charged, and melt kneading was carried out for 10 minutes at a temperature of 200 ° C. and a rotation speed of 100 revolutions / minute.
A composition was produced using the secondary modified polypropylene obtained in Comparative Example 2 instead of the secondary modified polypropylene obtained in Example 6 above.
(2) Evaluation of PP / PMMA Composition A flat plate was molded using a 5 cm × 5 cm × 0.4 cm mold at a temperature of 200 ° C. using a hot press. The one using the secondary modified polypropylene obtained in Example 6 had a glossy appearance and good dispersibility. On the other hand, those using the secondary modified polypropylene obtained in Comparative Example 2 had poor dispersion on the surface of the flat plate and low gloss.

[Adhesion performance evaluation 2]
(1) Preparation of Adhesive Water Dispersion The secondary modified polypropylene of Example 7 and Comparative Example 3 and the polypropylene produced in Comparative Production Example 1 were dissolved in tetrahydrofuran at 60 ° C. using the amounts shown in Table 5. To this solution, 20 ml of ion-exchanged water was added dropwise with stirring at a temperature of 40 ° C. for 1 hour. Further, the solvent was distilled off while adjusting the degree of vacuum at 40 ° C. until the volume became 25 ml, thereby preparing aqueous dispersions A to D for adhesion.
(2) Application of water dispersion for adhesion to PP base material A polypropylene sheet having a length of 10 cm and a width of 8 cm was washed with acetone, and the above-mentioned water dispersion for adhesion was 0.5 ml / 7.5 cm ² (2.5 × 3 cm). Was applied to one end portion (8 × 3 cm) of the sheet at a concentration of 5 ° C. and dried in an oven at 50 ° C. for 2 hours and at 90 ° C. for 6 hours. This polypropylene sheet was cut to a width of 2.5 cm.
Polypropylene sheet: Idemitsu Unitech Co., Ltd. Super Pure Array SG-140TC Thickness 0.3mm
(3) Production of Adhesive and Measurement of Adhesive Strength Adhesive was produced by the method described in Evaluation of Adhesive Performance 1 (3) and (4), and the adhesive strength between polypropylenes was measured. The results are shown in Table 5.

  According to the present invention, there is provided a modified graft copolymer having a sufficiently long polyolefin chain length and a high modification amount. The modified graft copolymer has a good affinity for different materials such as polyolefins and polar substances. Therefore, the modified graft copolymer of the present invention and the composition containing the modified graft copolymer are useful as components for compatibilizers, adhesives, paints and the like.

Claims (11)

A modified graft copolymer obtained by modifying a functional group of a graft copolymer, wherein the graft copolymer satisfies the following (a) to (e), and the functional group is a carboxylic acid anhydride residue: Is a functional group selected from a group, carboxyl group, hydroxyl group, epoxy group, amino group, isocyanate group, and ester group, and as a side chain formed by the reaction of the functional group , a carboxylic anhydride residue, a carboxyl group, an ester A modified graft copolymer having a side chain having at least one group selected from the group consisting of a group, an amide group, an amino group, a hydroxyl group and a phenyl group .
(A) Graft ratio is 1-150 mass%
(B) The weight average molecular weight measured by GPC is 500 to 400,000.
(C) Molecular weight distribution (Mw / Mn) is 1.5-4
(D) The main chain is a polymer chain containing a monomer unit having a functional group (e) The side chain is a kind of homopolymer chain selected from α-olefins having 3 to 28 carbon atoms or two or more kinds of co-polymer chains. It is either a polymer chain or a copolymer chain consisting of an ethylene unit having 50 to 50% by mass of an α-olefin unit having 3 to 28 carbon atoms and an ethylene unit, and a mesopentad fraction [mmmm] of 30 to 80 mol. % Polymer chain The graft copolymer is formed by a copolymerization reaction between a reactive polyolefin satisfying the following (A) to (C) and a monomer that forms the main chain of the graft copolymer. 2. The modified graft copolymer according to 1.
(A) 0.5 to 1.0 terminal unsaturated group per molecule (B) Mesopentad fraction [mmmm] is 30 to 80 mol%
(C) One type of homopolymer or two or more types of copolymers selected from α-olefins having 3 to 28 carbon atoms, or α-olefins having 3 to 28 carbon atoms in which ethylene is 50% by mass or less. One or more monomers and a copolymer of ethylene The monomer that forms the main chain of the graft copolymer has the formula (III)

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms, and R ² represents a formula of (IV) to (VII)

Any one of the groups represented by R ³ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group having 1 to 12 carbon atoms including any one of an oxygen atom, a nitrogen atom and a silicon atom, and R ⁴ represents a hydrogen atom or A hydrocarbon group having 1 to 12 carbon atoms, R ⁵ having a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an epoxy group, an amino group, an isocyanate group, a hydroxyl group, or a carboxyl group; A group having 1 to 12 carbon atoms is shown. n is an integer of 0-5. ]
The monomer represented by this is 1 type or 2 types or more (However, the case where it consists only of the monomer whose R < ² > is group represented by the (IV) type | formula) is Claim 1 or 2 Modified graft copolymer. Monomers forming the main chain of the graft copolymer are [I] acrylic acid and derivatives thereof, [II] methacrylic acids and derivatives thereof, [III] vinyl esters and derivatives thereof, [IV] styrene and derivatives thereof The modified graft copolymer of Claim 3 which is 1 type, or 2 or more types chosen from (However, the case which consists only of [IV] styrene and its derivative (s)) . The modified graft copolymer according to claim 1 or 2 , wherein the monomer forming the main chain of the graft copolymer is one or more selected from the following group A and one or more selected from the following group B. .
Group A; [V] maleic anhydride and its substituents, [VI] maleic acid and its esters, [VII] maleimide and its substituents Group B; compounds represented by the following formula (VIII)

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms, and R ⁶ represents a hydrocarbon group having 1 to 28 carbon atoms, or formulas (IV) to (VII)

Any one of these groups is shown. R ³ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a group having 1 to 12 carbon atoms including any one of an oxygen atom, a nitrogen atom and a silicon atom, and R ⁴ represents a hydrogen atom or A hydrocarbon group having 1 to 12 carbon atoms, R ⁵ having a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an epoxy group, an amino group, an isocyanate group, a hydroxyl group, or a carboxyl group; A group having 1 to 12 carbon atoms is shown. n is an integer of 0-5. ] An aqueous dispersion or solution containing the modified graft copolymer according to any one of claims 1 to 5 . The composition containing the modified graft copolymer in any one of Claims 1-5 . The coating composition containing the modified graft copolymer in any one of Claims 1-5 . An adhesive containing the modified graft copolymer according to any one of claims 1 to 5 . The filler processing agent containing the modified graft copolymer in any one of Claims 1-5 . Compatibilizing agents containing modified graft copolymer according to any one of claims 1-5.