JPH09100388A - Polymeric composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a polymeric composite material which has excellent thermal and mechanical properties by incorporating particular two or more polymers contg. a cyclic conjugated diene monomer unit and/or a cyclic olefin monomer unit. SOLUTION: At least two polymers selected from polymers and modified polymers represented by formulae I and II are incorporated to prepare a polymeric composite material useful for the preparation of an elastic fiber, an automatic part and the like. In the formulae I and II, A to F are monomer units constituting the main chain of the polymer and may be arranged in any order; (a) to (f) are wt.% of respective monomer units; the number average mol.wt. of the polymer is 500 to 5,000,000 in terms of that of standard polystyrene; A represents a cyclic olefin monomer unit; B represents a cyclic conjugated diene monomer unit; C represents a chain conjugated diene monomer unit; D represents an aliph. vinyl monomer unit; E represents a polar monomer unit; F represents an ethylene monomer unit; S to X represent a modifying group; a+b+c+d+e+f=100; and 0<s+t+u+v+w<100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer composite material containing two or more kinds of polymers containing a cyclic monomer unit. More specifically, a resin composition containing a polymer containing a cyclic conjugated diene-based monomer unit and / or a cyclic olefin monomer unit, and at least two polymers selected from the group consisting of this modified polymer The present invention relates to a novel polymer composite material which is a resin composition containing a polymer or another polymer which is further compounded in the composition as required.

[0002]

2. Description of the Related Art In the research of polymer materials intended for industrial materials, a great deal of research has been conducted to develop more excellent thermal and mechanical properties, and various kinds of materials have been proposed. These polymer materials are lightweight and have a large degree of freedom in shape, and various characteristics are exhibited depending on their type. Therefore, they are used for automobile parts, electric parts, aviation / space parts, sports / leisure parts. The fields of use are extremely diverse, including the fields of use for household goods and general miscellaneous goods, and their importance has increased dramatically as market demands and scientific and technological advances progress.

However, as one of the most important problems to be solved when these polymeric materials are used in a wider range as industrial materials, their mechanical properties fluctuate remarkably depending on the ambient temperature. That
There was an inherent problem with (organic) polymeric materials. The main cause of this problem is that when the ambient temperature in which the material is used reaches a region above the glass transition temperature (Tg) of the polymer, the polymer chains are converted from the glass state to the rubber state. There is.

Therefore, it is essentially impossible to solve this problem in a polymer material having a single molecular structure, and in order to solve this problem by conventionally combining a plurality of polymer materials, A great deal of research has been done. For example, as one of the specific means for solving this problem, a polymer material is introduced into a single polymer material by complexing or copolymerizing another polymer having a different Tg with the polymer material. Attempts have been vigorously made in the past to improve the mechanical properties (heat rigidity, impact resistance, heat strength, dimensional stability, etc.) of the polymer to obtain a polymer material having little atmospheric temperature dependence.

However, in these prior arts, it is necessary to change the kinds of polymers to be composited into various types according to the purpose of modification, and industrial materials are integrated into as few kinds of polymer materials as possible. It is not always in line with market demands. For this reason, (hydrogenated) conjugated diene-based polymers such as polybutadiene and polyisoprene have a large degree of freedom in designing polymer chains because they are capable of living anionic polymerization, and control of material properties is relatively easy. As a modifier in composite materials, there is a possibility that the addition of rigidity at the time of heat, impact resistance, strength at heat and dimensional stability can be achieved with the same type of material. Active research has been conducted as a component.

However, the market demands for polymer materials are becoming more and more advanced, and higher thermal (melting point,
The development of conjugated diene-based polymeric materials having glass transition temperature, heat distortion temperature, etc.) and mechanical properties (tensile modulus, flexural modulus, etc.) has been strongly desired.

As one of the most effective means for solving this problem, not only a monomer having a relatively small steric hindrance such as butadiene and isoprene, but also a monomer having a large steric hindrance, that is, a cyclic conjugated diene-based monomer is used. To form a cyclic monomer unit in the polymer chain of the conjugated diene polymer by homopolymerizing or copolymerizing the monomer, and further hydrogenating it if necessary,
By improving the structure of the polymer chain of the conjugated diene-based polymer, the polymer of the same system (conjugated diene-based polymer) can have high thermal properties (rigidity / strength) and high impact resistance and dimensional stability. To synthesize a polymer having
By compounding this with other polymers, research activities have been actively carried out to obtain excellent composite materials in which necessary properties are improved only by the polymers of the same system.

However, in the prior art, although a catalyst system showing a polymerization activity which is relatively satisfactory for a monomer having a relatively small steric hindrance such as butadiene or isoprene, a monomer having a large steric hindrance is proposed. That is, a catalyst system having a sufficiently satisfactory polymerization activity for a cyclic conjugated diene-based monomer has not yet been found.

Die Makromoleculare
Chemie. , 163 , 13 (1973)
A cyclohexadiene homopolymer in which 1,3-cyclohexadiene is polymerized with a large amount of an organolithium compound as a catalyst is disclosed. The oligomeric polymer obtained here has a number average molecular weight of only 6,500. Also disclosed is a low molecular weight hydrogenated cyclohexadiene homopolymer (polycyclohexane) hydrogenated with a large excess of paratoluenesulfonyl hydrazide with respect to the carbon-carbon double bond of this polymer.

However, the hydrogenated polymer disclosed herein has a very low molecular weight, and the disclosed hydrogenation method has a serious disadvantage that it is economically disadvantageous because it is a stoichiometric reaction. Have J. Poly
m. Sci. , Polym. Chem. Ed. , 20 ,
901 (1982) discloses a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using an organic sodium compound as a catalyst. The organic sodium compound used here is sodium naphthalene, and a dianion formed from a radical anion is actually a polymerization starting point.

That is, the number average molecular weight of the cyclohexadiene homopolymer reported here is apparently 3
8,700, but the number average molecular weight is substantially 19,3.
Only 50 molecular chains grew in two directions from the polymerization initiation point. Further, the polymerization method disclosed herein is a reaction at an extremely low temperature and has no industrial value.

Makromol. Chem. , 191 ,
2743 (1990) describes a method for polymerizing 1,3-cyclohexadiene using polystyryllithium as a polymerization initiator. In the polymerization method described here, it is taught that transfer reaction accompanied by abstraction of lithium cation and elimination reaction of lithium hydride occur at the same time as the polymerization reaction, and the polymerization reaction is started using polystyryllithium as an initiator. Despite the fact that it was carried out, it was reported that a styrene-cyclohexadiene block polymer was not obtained at room temperature, and only a low molecular weight cyclohexadiene homopolymer was obtained.

Similarly, when polystyryllithium was used as an initiator and blocking was performed at -10 ° C, a block polymer of styrene-cyclohexadiene having a molecular weight of about 20,000 was obtained together with a cyclohexadiene homopolymer with an extremely low yield. It has been reported. However, the copolymer obtained here has not only a very small content of cyclohexadiene block, but also block copolymerization with a chain-like conjugated diene-based monomer, multiblock or triblock or radial block or more. There is no suggestion or teaching about blocks and the like.

U. S. P. No. 4,127,710 discloses a polymer mixture obtained by polymerizing a monomer mixture of 1,3-cyclohexadiene, styrene and butadiene using a polyfunctional initiator. However, in the polymer mixture obtained here, not only is it taught that the yield decreases as the proportion of 1,3-cyclohexadiene in the monomer mixture increases,
High molecular weight cyclohexadiene homopolymers or cyclohexadiene-based block polymers, especially block polymers of triblock or higher, have not been obtained, and there is no suggestion or disclosure of a composite material of cyclohexadiene-based polymers.

U. S. P 4,138,536 discloses a polymer mixture obtained by polymerizing a monomer mixture of 1,3-cyclohexadiene and styrene with a polyfunctional initiator. However, in the polymer mixture obtained here, not only is it taught that the yield decreases as the proportion of 1,3-cyclohexadiene in the monomer mixture increases, but also the high molecular weight cyclohexadiene homo No polymer, or cyclohexadiene-based block polymer, particularly block polymer of triblock or more, has been obtained, and there is no suggestion or disclosure of a composite material of cyclohexadiene-based polymers.

U. S. P 4,179,480 describes a polymer mixture obtained by polymerizing a monomer mixture of 1,3-cyclohexadiene, styrene and butadiene using a polyfunctional initiator and a styrene-butadiene-styrene block copolymer. Compositions are disclosed.

[0017]

However, there is no composition of cyclohexadiene-based polymers among the compositions disclosed herein, and there is no suggestion or teaching regarding a composite material of cyclohexadiene-based block polymers. . That is, in the prior art, an excellent polymer composite material containing a polymer having a cyclic monomer that is sufficiently satisfactory as an industrial material has not yet been obtained.

[0018]

As a result of repeated studies to solve the above problems, the present inventor has succeeded in synthesizing a cyclic monomer-containing polymer that has never been reported before (PCT /
JP94 / 00822, PCT / JP94 / 0097
3). Further, as a result of intensive studies conducted by the present inventors in order to obtain an excellent resin composition containing these polymers, when at least two kinds of these polymers were contained, they were the best as industrial materials. The present invention has been completed by discovering the surprising fact that the characteristics are exhibited.

That is, according to the present invention, the polymer chain is represented by the following formula (I
Polymer composite containing at least two kinds of polymers selected from the group consisting of polymers (hereinafter referred to as polymer I) and modified polymers (hereinafter referred to as modified polymer I) represented by A) and (IB), respectively. Provide the material.

Embedded image [Here, A to F represent monomer units constituting the polymer main chain, and A to F may be arranged in any order. a ~
f is the monomer units A to F based on the total weight of the monomer units A to F
Represents each wt% of F. The standard polystyrene equivalent number average molecular weight of the polymer is 500 to 5,000,000.
Range.

When the polymer represented by the formula (IA) and / or the modified polymer represented by the formula (IB) contains the monomer unit A, at least one of the monomer units A is 1 , 4-bonded to the polymer chain. (A): 1 type or 2 or more types of cyclic olefin type monomer units (B): 1 type or 2 types or more of cyclic conjugated diene type monomer units (C): 1 type or 2 or more types of chain Conjugated diene monomer unit (D): One or more vinyl aromatic monomer units (E): One or more polar monomer units (F): Ethylene monomer Unit, 1 type or 2 or more types of α
An olefinic monomer unit.

A to F satisfy the following relationships. a + b + c + d + e + f = 100, 0 ≦ a, b ≦ 100, 0 ≦ c, d, e, f <100, and a + b ≠ 0 In the formula (IB), S to X represent a modifying group, and each independently represents oxygen (O ), Nitrogen (N), silicon (Si), sulfur (S), phosphorus (P), halogen (F, Cl, Br and I) at least one functional group or an organic compound residue containing a functional group. is there.

S to x are represented by the formula (IB) and are wt% of S to X with respect to the modified polymer, and satisfy the following relationships. 0 <s + t + u + v + w <100, and 0 ≦ s, t, u, v, w <100]

In the above polymer composite material, the monomer unit A is one kind or two or more kinds of cyclic olefin monomer units. The monomer unit A is preferably a 5- to 8-membered cyclic monomer unit represented by the following formula (II), and most preferably a 6-membered cyclic monomer unit represented by the following formula (IV). It is a unit.

Embedded image

[0024]

Embedded image

[In the formulas (II) and (IV), n is 1
Represents an integer of from 4 to 4. Each R ¹ independently represents a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon group, a C ₅ -C ₂₀ aryl group, or a C ₃ -C.
₂₀ cycloalkyl groups, C _{4 to} C ₂₀ cyclodienyl groups, or 5 to 10-membered ring heterocyclic groups containing at least one nitrogen, oxygen or sulfur as a heteroatom, and R ^{2 s} are each independently Hydrogen atom, halogen atom, C ₁
To C ₂₀ alkyl group, C _{2 to} C ₂₀ unsaturated aliphatic hydrocarbon group, C _{5 to} C ₂₀ aryl group, C _{3 to} C ₂₀ cycloalkyl group, C _{4 to} C ₂₀ cyclodienyl group, or 5-
A heterocyclic group having a 10-membered ring and containing at least one nitrogen, oxygen or sulfur as a hetero atom is shown. ]

Specific examples include a cyclopentadiene monomer unit, a cyclohexadiene monomer unit, a cyclooctadiene monomer unit and a derivative unit thereof. Cyclohexadiene monomer units and their derivative units are particularly preferred. When the composite material of the present invention is used in an application / field requiring high thermal / mechanical properties or functionality, the content of the monomer unit A is preferably 1 to 100 wt%, particularly preferably 5-100 wt%, most preferably 10-
It is 100 wt%.

The monomer unit B is one or more cyclic conjugated diene monomer units. The monomer unit B is preferably a 5- to 8-membered cyclic monomer unit represented by the following formula (III), and most preferably a 6-membered cyclic monomer unit represented by the following formula (V). It is a unit of quantity.

Embedded image

[0028]

Embedded image [In Formulas (III) and (V), n, R ¹ and R ²
Is the same as the definition in formula (II). ]

Specific examples include a cyclopentadiene monomer unit, a cyclohexadiene monomer unit, a cyclooctadiene monomer unit and a derivative unit thereof. Cyclohexadiene monomer units and their derivative units are particularly preferred. The total content of the monomer units A and B is not particularly limited because it is set variously depending on its intended use, but is generally 0.001 to 100 wt%, preferably 0.0
1 to 100 wt%, particularly preferably 0.1 to 100 wt
%.

1,2-bond / in monomer units A and B
The ratio (mol%) of 1,4-bonds is preferably 99 /
1-1 / 99, more preferably 95 / 5-5 / 95,
It is particularly preferably 90/10 to 10/90, most preferably 80/20 to 20/80. The monomer unit C is one kind or two or more kinds of chain conjugated diene monomer units. Examples include 1,3-butadiene, isoprene,
It is a monomer unit derived from 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like.

The monomer unit D is one kind or two or more kinds of vinyl aromatic monomer units. Examples include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3.
-A monomer unit derived from dimethylstyrene, divinylbenzene, vinylnaphthalene, vinylanthracene, 1,1-diphenylethylene, m-diisoprenylbenzene, vinylpyridine and the like. The monomer unit E is one or more polar monomer units. For example,
Polar vinyl monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone, and α-methyl acrylate, or ethylene oxide,
It is a monomer unit derived from propylene oxide, cyclic lactone, cyclic lactam, cyclic siloxane, or the like.

The monomer unit F is an ethylene monomer unit or one or more α-olefin monomer units. It is not particularly limited that the monomer units C to F are monomer units derived by hydrogenation, halogenation, alkylation or the like after the completion of the polymerization reaction. The number average molecular weight (in terms of standard polystyrene) of the polymer I and the modified polymer I is 500 to 5,000,000.

When used as a functional material, it is generally 500 to 2,000,000, preferably 50.
0 to 1,000,000, particularly preferably 1,000 to
800,000, most preferably 1,500-50
Most preferably, it is in the range of 10,000. When used as a structural material, the number average molecular weight of the polymer chain is generally 1,000 to 5,000,000, preferably 1,500 to 4,000,000, more preferably 2,
000 to 3,000,000, particularly preferably 2,500
0-2,000,000, most preferably 3,000-
1,000,000.

In view of industrial productivity, the number average molecular weight is desirably 500 to 4,000,000, preferably 500 to 3,000,000, more preferably 500 to 2,000,000, Particularly preferably 500-
1,000,000, most preferably 1,000-50
It is 0000. When the number average molecular weight is less than 500, it becomes thermally unstable and is not preferable as an industrial material. When the number average molecular weight is 5,000,000 or more,
It is not preferable in industrial production because the polymerization time becomes long and the melt viscosity becomes extremely high. The molecular weight distribution (Mw / Mn) of the polymer I and the modified polymer I of the present invention is 1.
01 to 10, preferably 1.03 to 7.0, and particularly preferably 1.05 to 5.0.

The most preferable polymer I is a homopolymer consisting of monomer units B (b = 100), a copolymer consisting of two or more kinds of monomer units B (b = 100), and these polymers. A polymer (a) obtained by subjecting part or all of the carbon-carbon double bonds contained therein to a hydrogenation reaction.
+ B = 100 and a> 0 or a = 100), or a cyclic conjugated diene polymer comprising a monomer unit B and another monomer unit copolymerizable therewith is produced, and then contained in the polymer. Obtained by carrying out a hydrogenation reaction on a part or all of the carbon-carbon double bond (a +)
b <100).

The hydrogenation rate (mol%) of the carbon-carbon double bond in the cyclic conjugated diene polymer for forming the monomer unit A in the polymer is not particularly limited, but it is generally. 1 to 100 mol% is preferable, and 5 to 1 is more preferable.
00 mol%, particularly preferably 10 to 100 mol%,
Most preferably, it is 20 to 100 mol%. When it is used in an application / field in which particularly high thermal / mechanical properties are required, 50 to 100 mol% is preferable, and 7 is preferable.
It is 0 to 100 mol%, and most preferably 90 mol% or more.

The most preferred modified polymer I is a modified polymer obtained by adding a functional group or an organic compound residue having a functional group to the most preferred polymer I of the present invention. When the polymer I of the present invention is a copolymer, for example, diblock, triblock, tetrablock, multiblock,
Examples include block copolymers such as radial blocks, star blocks, and comb blocks, graft copolymerization, taper copolymerization, random copolymerization, alternating copolymerization, and the like.

When the polymer I is a block polymer I containing a block unit in the polymer chain, the block unit is a block unit composed of a monomer unit A and / or a monomer unit B, A block unit composed of at least one selected from the monomer unit A and / or the monomer unit B and the monomer units C to F can be designed, and various block units can be designed as necessary. A block copolymer can be prepared according to the purpose by polymerizing and binding it.

When the block unit of the present invention contains the monomer unit A and / or the monomer unit B in a part or all of them, they are continuously bonded to each other in order to improve thermal and mechanical properties. The monomer unit A and / or the monomer unit B is preferably 2 or more molecules, more preferably 5 or more molecules, and particularly preferably 10 or more molecules. As an example in which the block polymer I and the modified block polymer I have elastomeric properties (rubber elasticity), a linear block copolymer represented by the following formula (VI) and a radial block copolymer represented by the following formula (VII) There are copolymers. These block polymers, hydrogenated polymers and modified polymers thereof can exhibit elastomeric properties (rubber elasticity).

(X-Y) _l , X- (Y-X) _m , Y- (X-Y) _n ··· (VI) [l and n represent an integer of 2 or more and m is 1 or more. X represents a block unit in which 50 wt% or more of the block unit is composed of the monomer unit B or a monomer unit B and a monomer unit D, and Y is 50 wt of the block unit.
% Represents a block unit composed of the monomer unit C or the monomer unit F] [(Y−X) _n ] _{m + 2} Z, [(X−Y) _n ] _{m + 2} Z, [ (Y−X) _n −Y] _{m + 2} Z, [(X−Y) _n −X] _{m + 2} Z ··· (VII) [m represents an integer of 0 or more and n represents an integer of 1 or more. X and Y are (V
Same as I) formula. Z represents a residue of a polyfunctional coupling agent such as dimethyldichlorosilane, methylene chloride, silicon tetrachloride, tin tetrachloride, epoxidized soybean oil or the like, or a residue of an initiator such as a polyfunctional organic group IA metal compound. ]

As an industrial composite material, the X block may be a block unit containing a 1,3-cyclohexadiene monomer unit, or a 1,3-cyclohexadiene monomer unit and a styrene monomer unit. Alternatively, a block unit containing an α-methylstyrene monomer unit is preferable, and as the Y block, 1,3-butadiene monomer unit, isoprene monomer unit, and 1,3-butadiene monomer unit are hydrogenated. A block unit containing at least one of the monomer unit obtained by hydrogenating isoprene and the monomer unit obtained by hydrogenating isoprene is preferable.

When the Y block is a 1,3-butadiene monomer unit and / or an isoprene monomer unit, the amount of vinyl bond in the Y block can be set arbitrarily and is not particularly limited, but at a low temperature. When characteristics are required, it is preferably 10 to 90 mol%, and more preferably 20 to 80 mol% with respect to the total amount of cis and trans 1,4-bonds and vinyl bonds.

As a block polymer I having typical thermoplastic elastomer properties, which is adopted in the composite material of the present invention, 10 to 60 wt% of X block (particularly composed of 1,3-cyclohexadiene monomer unit) is used. , Preferably 1
5 to 50 wt%, Y block (particularly composed of hydrogenated butadiene monomer unit) 90 to 40 wt%, preferably 8
5 to 50 wt% and the number average molecular weight is 100
There is a triblock polymer I represented by the following formula, which is 0 to 200,000; XYX. The triblock polymer I and the modified polymer I can impart high impact strength when made into a composite material.
The vinyl bond content is 50 mol% or more, preferably 6
When it is set to 0 mol% or more, it exhibits excellent miscibility with an olefin polymer such as polypropylene (PP), so that high mechanical properties can be exhibited.

On the other hand, when the triblock polymer I is used as a composite material having improved toughness and thermal properties, the X block (particularly composed of 1,3-cyclohexadiene monomer unit) is used. 40 to 90 wt%, preferably 45 to 85 wt%, Y block (particularly composed of hydrogenated butadiene monomer unit) 60 to 10 wt%, preferably 55 to 15 wt%, and having a number average molecular weight of 1,
It is preferably 000 to 200,000.

On the other hand, for example, the block polymer I of the present invention
Is a composite material with polystyrene (PSt) or polyphenylene ether (PPE), at least one or more monomer units A and / or monomer units B
A block unit consisting of at least one monomer unit D
It is preferable to employ a block polymer I having a diblock, preferably triblock or higher, in order to improve the mechanical and thermal properties of the composite material. The polymer I used in the composite material of the present invention may be obtained by any conventionally known polymerization method (radical, anion, cation, ring opening, condensation, addition, coordination polymerization, etc.).

Monomer unit A in polymer I of the present invention
May be introduced into the polymer chain by any method. For example, a cyclic conjugated diene-based monomer (hereinafter referred to as “monomer B”) and, if necessary, another monomer copolymerizable therewith (hereinafter referred to as “monomer M”) are polymerized, and then present in the monomer unit B. To introduce the monomer unit A by subjecting the double bond to a hydrogenation reaction or an addition reaction, a method of polymerizing a cyclic olefin-based monomer (hereinafter referred to as monomer A), and other monomer if necessary. There is.

Polymer I used in the composite material of the present invention
Is a dimethyldichlorosilane at the polymer end for the purpose of adjusting the molecular weight or obtaining a star-shaped polymer as necessary.
It is not particularly limited that it is obtained by binding with a known bifunctional or higher functional coupling agent such as methyltrichlorosilane. When synthesizing the polymer I used in the composite material of the present invention, a block unit composed of one or more monomer units B and one or more monomer units B and M are used. There is a method of producing / bonding the block units to be prepared according to the purpose, and carrying out a hydrogenation reaction and the like if necessary.

For example, the monomer B and, if necessary, the monomer M are polymerized, and the monomer M is added from one end or both ends of this polymer.
Of the monomer B and hydrogenating it if necessary; the monomer M is polymerized, and the monomer B is added from one or both ends of the polymer.
And a method of polymerizing the monomer M if necessary, and hydrogenating as necessary; a monomer B and a monomer M if necessary, and then a monomer M, and then a monomer B And a method of sequentially polymerizing the monomer M if necessary, and hydrogenating if necessary; polymerizing the monomer M, polymerizing the monomer B and the monomer M if necessary, and further polymerizing the monomer M. A method of sequentially polymerizing and hydrogenating if necessary;

The end of the diblock unit produced by polymerizing the monomer B and the monomer M if necessary, and then the monomer M is terminated by a known method such as dimethyldichlorosilane or methyltrichlorosilane. Method of binding with a bifunctional or higher functional coupling agent and hydrogenating as necessary; by polymerizing the monomer B and the monomer M if necessary, a terminal modifier such as ethylene oxide or propylene oxide is added to the polymer terminal. A method of introducing a functional group by reacting it, hydrogenating it if necessary, and bonding it with another polymer having a functional group to bond with it; Polymerization of monomer M, ethylene oxide at the polymer end,
A method of introducing a functional group by reacting with a terminal modifier such as propylene oxide, hydrogenating it if necessary, and bonding it with another polymer having a functional group to bond with it;

Monomer B and monomer M having a different polymerization rate are simultaneously polymerized to form a tapered block copolymer,
A method of hydrogenating as required; a method of charging monomers B and M in different composition ratios, polymerizing at the same time and hydrogenating as needed; monomer B is polymerized first, and an arbitrary conversion rate is obtained. In this method, there is a method in which a monomer M having a different polymerization rate is added and polymerized, and then the remaining monomer B is polymerized to form a block copolymer, and hydrogenated if necessary. The most preferred method for polymerizing Polymer I is I
A complex compound is formed by reacting an organometallic compound containing a Group A metal with a complexing agent, and living anion polymerization is performed using the complex compound as a polymerization catalyst, and a hydrogenation reaction is performed if necessary. It is a polymerization method for obtaining a polymer I having an arbitrary molecular weight and a high molecular structure.

The details will be described below. In the most preferred polymerization method of the present invention, the organometallic compound containing a Group IA metal used as a polymerization catalyst is preferably an organolithium compound, an organosodium compound or an organopotassium compound, and particularly preferably an organolithium compound. . Preferred organic lithium compounds include n-butyllithium (n-BuLi) and sec-butyllithium (s-Bu).
Li) and tert-butyllithium (t-BuLi)
It is. The organometallic compound containing a Group IA metal may be one kind or a mixture of two or more kinds as necessary.

The most preferred complexing agent used in the polymerization catalyst is an amine compound. Among the amine compounds, the most preferred amine compound is a tertiary (tertiary) amine compound, especially tetramethylethylenediamine (TMEDA)
And diazabicyclo [2,2,2] octane (DABC
O) is preferred. The amine compound may be one kind or a mixture of two or more kinds as necessary.

As the polymerization catalyst, a particularly preferable combination of the organometallic compound containing a Group IA metal and the complexing agent is n
-Butyllithium (n-BuLi), sec-butyllithium (s-BuLi) and tert-butyllithium (t-BuLi) at least one alkyllithium and tetramethylmethylenediamine (TMM)
DA), Tetramethylethylenediamine (TMED)
A), tetramethylpropylenediamine (TMPD
A), tetramethylhexanediamine (TMHDA) and diazabicyclo [2,2,2] octane (DABC
It is a combination of at least one amine compound selected from O).

The industrially most preferable combination is n-
Butyllithium (n-BuLi) and tetramethylethylenediamine (TMEDA). In the polymerization method of the present invention, a complex compound is formed by reacting an organometallic compound containing a metal of Group IA of the Periodic Table with an amine compound as a complexing agent before the polymerization reaction and used as a polymerization catalyst. Things are preferred.

As a method for adjusting the polymerization catalyst, conventionally known techniques can be used. For example, a method of dissolving an organometallic compound in an organic solvent in a dry inert gas atmosphere and adding a solution of a complexing agent (amine compound) thereto, and a complexing agent (amine compound) in a dry inert gas atmosphere There is a method of dissolving in an organic solvent and adding a solution of an organometallic compound thereto.
The organic solvent used here is appropriately selected according to the type and amount of the organic metal and the type and amount of the complexing agent (amine compound),
It is preferably used after being sufficiently deaerated and dried.

The temperature condition for reacting the organometallic compound with the complexing agent (amine compound) is also generally -100 to
100 ° C. Helium, nitrogen, and argon are preferable as the dry inert gas, and nitrogen or argon is preferably used industrially. As the polymerization method in the polymerization method of the present invention, gas phase polymerization, bulk polymerization, solution polymerization, or the like can be appropriately used. As the polymerization reaction process, for example, a batch system, a semi-batch system, a continuous system or the like can be appropriately used.

As the polymerization solvent for solution polymerization, there are aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents and ether solvents. These polymerization solvents may be used alone or as a mixture of two or more if necessary. A preferred polymerization solvent is n-hexane or cyclohexane, or a mixed solvent thereof. The amount of the polymerization catalyst used is generally 1 × 10 ⁻⁶ mol to ¹ × 10 ⁻¹ mol, preferably 5 × 10 ⁻⁶ mol to 5 × 10 ⁻² mol as a metal atom per 1 mol of the monomer. Is.

The polymerization temperature in the polymerization method of the polymer I is
Generally, -100 to 150 ° C, preferably -80 to 12
0 ° C, particularly preferably -30 to 110 ° C, most preferably 0 to 100 ° C. From an industrial viewpoint, room temperature to 90 ° C is preferable. The time required for the polymerization reaction is usually 48 hours or less, and particularly preferably 1 to 10 hours. The atmosphere in the polymerization reaction system is preferably an inert gas such as nitrogen, argon, helium or the like, particularly an inert gas which is sufficiently dried.

The pressure of the polymerization reaction system is not particularly limited as long as it is within the pressure range sufficient to maintain the monomer and solvent in the liquid phase within the above-mentioned polymerization temperature range. Furthermore, it is necessary to carry out the polymerization reaction while being careful not to mix impurities such as water, oxygen, carbon dioxide gas, etc., which inactivate the polymerization catalyst and the active terminals, into the polymerization system. In the polymerization method of the present invention, the polymerization catalyst used in the polymerization reaction of the polymer I may be one kind or a mixture of two or more kinds, if necessary.

In the polymerization method of the present invention, a known terminal modifier such as halogen gas or carbon dioxide, or a known agent such as polyepoxide or polyisocyanate is used, if necessary, after the polymerization reaction reaches a predetermined polymerization rate. Known branching agents, known coupling agents such as dimethyldichlorosilane, methyltrichlorosilane, and further known polymerization terminators, polymerization stabilizers, or known heat stabilizers, antioxidants, and ultraviolet absorbers. You may add stabilizers, such as.

When the polymer I is a hydrogenated polymer, the most preferable method for producing the hydrogenated polymer is to prepare a hydrogenated polymer in the presence of a hydrogenation catalyst after the polymerization reaction of the polymer I achieves a predetermined polymerization rate. In this method, a part of or all of the carbon-carbon unsaturated bonds contained in the polymer are hydrogenated by a chemical reaction.

For example, the polymerization reaction is stopped by deactivating the polymerization catalyst, the hydrogenation catalyst is added to the same reactor in which the polymerization reaction has been carried out, and hydrogen is introduced to batch-form the hydrogenated polymer. Method of manufacturing; stopping the polymerization reaction by deactivating the polymerization catalyst, transferring the polymer solution to a reactor different from the polymerization reaction, adding a hydrogenation catalyst into the reactor, and introducing hydrogen. There is a method for producing a hydrogenated polymer in a semi-batch manner by the method; a method for continuously producing a hydrogenated polymer by continuously carrying out a polymerization reaction and a hydrogenation reaction in a tube reactor.

The hydrogenation reaction of the present invention is carried out by using the polymer I to be hydrogenated.
And a hydrogenation catalyst in the presence of a hydrogen atmosphere. The method of the hydrogenation reaction in the present invention is generally carried out by keeping the polymer solution under hydrogen or an inert gas atmosphere at a predetermined temperature, adding a hydrogenation catalyst with stirring or without stirring, and then adding hydrogen gas. It is implemented by introducing and pressurizing to a predetermined pressure. In addition, a conventionally known technique can be adopted as a hydrogenation reaction type. For example, any of a batch type, a semibatch type, a continuous type or a combination thereof can be used.

The hydrogenation catalyst that can be used in the hydrogenation reaction of the present invention is a homogeneous hydrogenation catalyst (organic metal) containing at least one metal selected from the group VIA to VIII transition metals or rare earth metals of the periodic table. A compound, an organometallic complex) or a heterogeneous hydrogenation catalyst (solid catalyst), preferably the former homogeneous hydrogenation catalyst or a carrier-type solid catalyst carrying a Group VIII transition metal. They are,
They can be used alone or in combination.

The homogeneous hydrogenation catalyst may be supported on an inorganic compound such as silica, zeolite or crosslinked polystyrene, or an organic polymer compound. Preferable metals contained in the hydrogenation catalyst used in the present invention are titanium, cobalt, nickel, ruthenium, rhodium and palladium. In order for these metals to function as a homogeneous hydrogenation catalyst, ligands such as hydrogen, halogen, nitrogen compounds and organic compounds need to be coordinated or bonded, and the combination thereof is optional, A combination that is soluble in at least a solvent is preferable.

Specific examples of the ligand include hydrogen, fluorine,
Organic compounds containing functional groups such as chlorine, bromine, nitric oxide, carbon monoxide, or hydroxyl, ether, amine, thiol, phosphine, carbonyl, olefin, diene, or non-polar organic compounds containing no functional group. is there. These ligands can be used alone or in combination.

When the hydrogenation catalyst is a homogeneous hydrogenation catalyst containing at least one metal selected from the group VIA to VII transition metals or rare earth metals, it and IA such as alkyllithium, alkylmagnesium, alkylaluminum, etc. It is industrially most preferable to use a composite catalyst composed of an organometallic compound containing at least one metal selected from Group IIA and Group IIIB metals.

The amount of the hydrogenation catalyst used is generally 0.1 to 100 in terms of metal atom concentration with respect to the polymer to be hydrogenated.
000 ppm, preferably 1 to 50,000 ppm, more preferably 5 to 10,000 ppm, particularly preferably 10 to 10,000 ppm. When the amount of the hydrogenation catalyst used is small, a sufficient reaction rate cannot be obtained, and when the amount used is large, the reaction rate increases but it is economically disadvantageous, and it is necessary to separate and recover the catalyst. Therefore, the influence of the catalyst residue on the polymer cannot be avoided.

The solvent used in the hydrogenation reaction is preferably inert to the hydrogenation catalyst and soluble in the polymer. Industrially, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents are preferable,
Aliphatic hydrocarbon solvent or alicyclic hydrocarbon solvent,
Alternatively, these mixed solvents are most preferable. From an industrial viewpoint, it is most preferable that the solvent used for the polymerization reaction and the solvent used for the hydrogenation reaction are the same because it is economically advantageous to carry out the hydrogenation reaction subsequent to the polymerization reaction.

The concentration of the polymer in the polymer solution during the hydrogenation reaction is usually 1 to 90 wt%, preferably 2 to 60 wt%.
%, And more preferably 5 to 40 wt%. When the concentration is low, it is economically disadvantageous, and when the concentration is high, the viscosity of the polymer solution increases and the reaction rate decreases, which is not preferable. The temperature of the hydrogenation reaction is generally -78 to 5
The temperature is 00 ° C, preferably -10 to 300 ° C, particularly preferably 20 to 250 ° C. If the reaction temperature is too low, a large reaction rate cannot be obtained, and if the reaction temperature is too high, the hydrogenation catalyst is deactivated or the polymer is deteriorated, which is not preferable.

The pressure of the hydrogenation reaction system in the method for producing the hydrogenated polymer I is 0.1 to 500 kg / cm ² G, preferably 1 to 400 kg / cm ² G, particularly preferably 2 to
It is 3000 kg / cm ² G. If the pressure is too low, a sufficiently high reaction rate cannot be obtained, and if the pressure is too high, the reaction rate increases, but it is not economical because an expensive pressure-resistant reaction device is required as a device, It induces hydrogenolysis of the combined product, which is not preferable. The time required for the hydrogenation reaction can be usually carried out in the range of 5 minutes to 240 hours.

After completion of the hydrogenation reaction, the hydrogenation catalyst can be separated and recovered from the reaction solution by a conventionally known means, if necessary. In the method for producing a hydrogenated polymer I, in order to separate and recover the hydrogenated polymer I from the polymer solution, a conventionally known polymer which is usually used when recovering a polymer from a polymer solution of a known polymer is used. The technology of can be adopted.

For example, a steam coagulation method in which a reaction solution and steam are directly contacted with each other, a reprecipitation method in which a poor solvent for the polymer is added to the reaction solution to precipitate the polymer, and the reaction solution is heated in a container to distill off the solvent. A method of performing pelletization while distilling off the solvent with a vented extruder, charging the reaction solution into warm water, and then performing pelletization while distilling off the solvent and water with a vented extruder. The optimum method can be used depending on the properties of the polymer I and the solvent used.

Further, the polymer I has carbon atoms in its polymer chain.
When it contains a carbon unsaturated bond, a conventionally known addition reaction to the carbon-carbon double bond other than the hydrogenation reaction may be carried out, if necessary. For example, halogen atom, sulfur,
Boron, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon radical, C ₅ -C ₂₀ aryl group, C ₃ -C
₂₀ cycloalkyl groups, C _{4 to} C ₂₀ cyclodienyl groups, or 5 to 10-membered heterocyclic groups containing at least one nitrogen, oxygen or sulfur as a hetero atom,
Or hydroxyl group, thiol group, thiocyanate group, ether group (poxy group, etc.), thioether group, thiocarboxylic acid, formyl group, carboxyl group, carbonyl group, amino group, imino group, nitrosyl group, isocyanate group, sulfonic acid group, phosphorus Acid group, phosphonic acid group, phosphinic acid group, silyl group, or C _{1 to} C ₂₀ alkyl group to which these are bonded, C _{2 to} C ₂₀ unsaturated aliphatic hydrocarbon group, C
_{5 to} C ₂₀ aryl group, C _{3 to} C ₂₀ cycloalkyl group, C _{4 to} C ₂₀ cyclodienyl group, or 5 to 10 membered ring containing at least one nitrogen, oxygen or sulfur as a hetero atom. The addition of at least one substituent selected from a heterocyclic group by a conventionally known reaction using a conventionally known reaction reagent is not particularly limited.

The modified polymer I refers to the polymer I including one or more of oxygen (O), nitrogen (N), silicon (S).
i), sulfur (S), phosphorus (P), halogen (F, C
It is a modified polymer to which a functional group containing at least one element selected from 1, 1, Br and I) or an organic compound residue having a functional group is added.

As a method of adding a functional group or an organic compound residue having a functional group, a conventionally known technique can be used, and the functional group or the organic compound having a functional group can be used by a ene reaction in a solution, a melt or a solid state. Method of adding a residue; Method of adding a functional group or an organic compound residue having a functional group by using a radical reaction in the presence or absence of a radical generator; There is a method of adding an organic compound residue (silyl group) to have; or a method of performing living anionic polymerization to add a functional group or an organic compound residue having a functional group to the polymer terminals (one end, both ends, etc.) .

The addition amount of the functional group or the organic compound residue having a functional group in the modified polymer I is generally 0.001 to 100% by weight, preferably 0.00
5 to 80 wt%, more preferably 0.01 to 50 wt%,
It is particularly preferably 0.05 to 40 wt%, and most preferably 0.1 to 20 wt%.

The preferred functional group added to the polymer I or the functional group contained in the organic compound residue is a hydroxyl group, an ether group, an epoxy group, a carboxylic acid group, an ester group, a carboxylic acid group, an acid anhydride group or an acid group. Halogen compound group, aldehyde group, carbonyl group, amino group, amide group, imide group, imino group, oxazoline group, hydrazine group, hydrazide group, amidine group, nitrile group, nitro group, isocyano group, cyanato group, isocyanato group, silyl group Group, silyl ester group, silyl ether group, silanol group, thiol group, sulfide group, thiocarboxylic acid group, dithiocarboxylic acid group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiocyanato group, isothiocyanato group, thioaldehyde group, A thioketone group, a phosphoric acid group, a phosphonic acid group, and a phosphinic acid group.

Particularly preferred functional groups are hydroxyl group, epoxy group, carboxylic acid group, ester group, carboxylic acid group, acid anhydride group, amino group, amide group, imide group, imino group, oxazoline group, hydrazine group and hydrazide. Base,
They are an isocyano group, a cyanato group, an isocyanato group, a silyl group, a silyl ester group, a silyl ether group, a silanol group, a thiol group, a sulfide group, a thiocarboxylic acid group, and a sulfonic acid group. One or more of these functional groups or organic compound residues having a functional group may be added.

Specific examples of the organic compound serving as the organic compound residue include acrylic acid, methacrylic acid, metal acrylate, metal methacrylate, methyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl acrylate,
Maleic acid, dimethyl maleate, diethyl maleate, succinic acid, dimethyl succinate, diethyl succinate,
Fumaric acid, dimethyl fumarate, diethyl fumarate, itaconic acid, citraconic acid, hymic acid, crotonic acid, mesaconic acid, sorbic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2.
2,1] Hept-5-ene 2,3-dicarboxylic acid, methyl-bicyclo [2,2,1] hept-5-ene 2,3-
Dicarboxylic acid, maleic anhydride, trimellitic anhydride, trimellitic anhydride chloride, succinic anhydride, itaconic anhydride, citraconic anhydride, hymic acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleimide, succinimide , Phthalimide, carbon dioxide, ethylene oxide, propylene oxide, cyclohexane oxide, glycidyl methacrylate, glycidyl acrylate, maleic acid diglycidyl ester, succinic acid diglycidyl ester, fumaric acid diglycidyl ester, p-styrenecarboxylic acid glycidyl ester, styrene-p- Glycidyl ester, 3,
4, -epoxy-1-butene, 3,4-epoxy-3
-Methyl-1-butene, 3,4, -epoxy-1-pentene, 3,4, -epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylalkoxy (methoxy, ethoxy, Butoxy) silane, epoxyalkoxy (methoxy, ethoxy, butoxy, etc.) silane, aminoalkoxy (methoxy, ethoxy, butoxy, etc.) silane, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, trimethoxysilane, triethoxysilane, chlorotrimethoxy Examples thereof include silane, chlorotriethoxysilane, diisocyanate compounds, oxazoline compounds and the like. The industrially most preferable organic compounds are maleic anhydride, glycidyl methacrylate, trichlorosilane, trimethoxysilane and chlorotrimethoxysilane.

The organic compounds having these functional groups may be used alone or in combination. The novel polymer composite material of the present invention is a composition containing at least two polymers selected from the group consisting of polymer I and modified polymer I. Specific examples of the polymer composite material of the present invention include a homopolymer of monomer B (hereinafter referred to as homopolymer B) and monomer B.
And M copolymer (hereinafter, copolymer BM) composition, homopolymer B and hydrogenated copolymer BM composition, hydrogenated homopolymer B and hydrogenated copolymer BM composition Or a composition of these modified polymers.

Further, when the copolymer BM of the present invention is a block copolymer, a composition of homopolymer B and diblock polymer, a composition of homopolymer B and triblock polymer, diblock copolymer A composition of a block polymer and a triblock polymer,
Composition of homopolymer B and hydrogenated diblock polymer, composition of homopolymer B and hydrogenated triblock polymer, composition of hydrogenated homopolymer B and diblock polymer, hydrogenated homopolymer Composition of polymer B and triblock polymer, composition of hydrogenated homopolymer B and hydrogenated diblock polymer, composition of hydrogenated homopolymer B and hydrogenated triblock polymer, hydrogenated diblock A composition of a polymer and a triblock polymer,
Composition of hydrogenated diblock polymer and hydrogenated triblock polymer, homopolymer B, composition of diblock polymer and triblock polymer, homopolymer B, hydrogenated diblock polymer and hydrogenated triblock polymer There are block polymer compositions, hydrogenated homopolymer B, hydrogenated diblock polymers, hydrogenated triblock polymer compositions or modified polymer compositions thereof.

Among these, at least one polymer selected from homopolymer B, hydrogenated homopolymer B or modified polymers thereof and a diblock polymer, triblock polymer, hydrogenated diblock polymer. A composition comprising a polymer, a hydrogenated triblock polymer or at least one polymer selected from these modified polymers is particularly preferable, and selected from homopolymer B, hydrogenated homopolymer B or modified polymers thereof. Most preferred is a composition comprising at least one polymer selected from the group consisting of a triblock polymer, a hydrogenated triblock polymer, and a modified polymer thereof.

The composition of the polymer I and / or the modified polymer I contained in the composition is not particularly limited, but the ratio of the minimum amount of the polymer I to the polymer I and the modified polymer I is such that the polymer I and the modified polymer I have the same proportion.
And 0.1% by weight or more, and more preferably 1% by weight or more, based on the total amount of the modified polymer I. The method for producing the composite material of the present invention is not particularly limited, and any composition can be obtained by applying the polymerization method disclosed in the present invention and the conventionally known technique.

For example, a method for obtaining a composition by separately polymerizing two or more kinds of polymers I by the polymerization method disclosed in the present invention, hydrogenating or modifying them as necessary, and mixing them in a solution state. A composition is prepared by separately polymerizing two or more kinds of polymers I by the polymerization method disclosed in the present invention, hydrogenating or modifying them if necessary, then removing the solvent, and further mixing them in a molten state. Method of obtaining; two or more polymers I separately by the polymerization method disclosed in the present invention
A polymer, and, if necessary, hydrogenated, then desolvated, further modified as necessary, and then mixed in a molten state to obtain a composition;

According to the polymerization method disclosed in the present invention, the monomer B is
To deactivate a part of the polymer terminal, and then to copolymerize the monomer M, and optionally hydrogenate and / or modify it to obtain a composition; the present invention discloses. The monomer M is polymerized by a polymerization method, then the monomer B is copolymerized to deactivate the polymer terminal, and then the monomer B is polymerized again, and if necessary, hydrogenated and / or modified. To obtain a composition by polymerizing the monomer B by the polymerization method disclosed in the present invention to deactivate the polymer terminal, then polymerize the monomer M, and then copolymerize the monomer B. A method of obtaining a composition by polymerizing, and optionally hydrogenating and / or modifying;

According to the polymerization method disclosed in the present invention, the monomer B is
Is polymerized to deactivate a part of the polymer terminal, then the monomer M is polymerized, then the monomer B is polymerized, and if necessary, hydrogenated and / or modified to form a composition. How to get;
After the monomer B is polymerized by the polymerization method disclosed in the present invention to deactivate the polymer terminal, the monomer B is polymerized again, and then the monomer M is polymerized. A method for obtaining a composition by polymerizing, and optionally hydrogenating and / or modifying; polymerizing a monomer B by the polymerization method disclosed in the present invention, then polymerizing a monomer M, and further polymerizing There is a method of obtaining a composition by adding a coupling agent less than the active terminal of (1) and hydrogenating and / or modifying as necessary; and the like, and the method can be appropriately selected depending on the purpose and need.

The novel polymer composite material of the present invention comprises, in addition to the polymer I and the modified polymer I, other polymer (hereinafter,
It may also contain a polymer Q). The proportion of the total amount of the polymer I and the modified polymer I is αwt%, and the proportion of the polymer Q is βwt.
%, The compounding ratio is not particularly limited as it can be arbitrarily set according to the purpose and application, but is generally 1 ≦ α / (α + β) <100, preferably 1 <α / (Α + β) <100, more preferably 2 ≦ α /
(Α + β) ≦ 99, particularly preferably 5 ≦ α / (α + β)
≦ 95. 10 ≦ α / as an industrial composite material
Most preferably, it is in the range of (α + β) ≦ 90.

As the polymer Q, conventionally known thermoplastic resins, cured resins, silicone resins and fluororesins can be used. Of these, thermoplastic resins are preferred. Specific examples of the thermoplastic resin include olefin polymers, styrene polymers,
Conjugated diene polymer, hydrogenated conjugated diene polymer, (meth) acrylate polymer, (meth) acrylonitrile polymer, vinyl halide polymer, ester polymer, ether polymer, amide polymer Examples thereof include coalesce, imide-based polymer, sulfide-based polymer, sulfone-based polymer and ketone-based polymer. Among these, olefin polymers, styrene polymers, conjugated diene polymers, hydrogenated conjugated diene polymers, ester polymers, ether polymers, amide polymers and sulfide polymers are preferable.

The olefin polymer is polyethylene (P
E), ethylene-norbornene (or its derivative)
Copolymer, polypropylene (PP), ethylene-propylene copolymer (EP, EPR), ethylene-propylene-diene copolymer (EPDM), poly-1-butene, poly-1-pentene, poly-1-hexene , Poly-1-octene, polyisobutylene, polymethyl-1-butene,
Poly-4-methyl-1-pentene and the like. The styrene-based polymer is polystyrene (PSt), syndiotactic polystyrene (s-PSt), styrene-acrylic acid copolymer, styrene-maleic anhydride copolymer (SM).
A), ABS resin, AES resin and the like.

The conjugated diene polymer and hydrogenated conjugated diene polymer are polybutadiene (PBd), polyisoprene (PIp), butadiene-isoprene copolymer, styrene-butadiene copolymer (SB, SBS), propylene- Butadiene copolymer, propylene-butadiene copolymer, styrene-isoprene copolymer (SI, SIS),
α-methylstyrene-butadiene copolymer, α-methylstyrene-isoprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, butadiene-methyl methacrylate copolymer, isoprene-methyl methacrylate copolymer Blocks, grafts, taper or random copolymers such as coalesced products, and hydrogenated polymers (SEBS, etc.) of these are also included.

The (meth) acrylate-based polymer includes poly (meth) acrylate (PMMA) and poly (meth) acrylate.
Examples thereof include ethyl acrylate, poly (meth) acrylate, poly (meth) acrylamide, and the like. The (meth) acrylonitrile-based polymer is poly (meth) acrylonitrile or the like. The vinyl halide-based polymer is polyvinyl halide, polyvinylidene halide and the like.

Ester type polymers include polybutylene terephthalate (PBT) and polyethylene terephthalate (PBT).
ET), polycarbonate (PC), polyarylate (PAR), liquid crystal polyester (LCP) and the like. The ether polymer is polyacetal (POM), polyoxyethylene, polyethylene glycol (PEG), polypropylene glycol (PPG), polyphenylene ether (PPE), or the like.

Examples of the amide polymer include nylon 4, nylon 6, nylon 8, nylon 9, nylon 10, nylon 10, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612, nylon 636 and nylon 1212. Aliphatic polyamide and nylon 4
T (T: terephthalic acid), nylon 4I (I: isophthalic acid), nylon 6T, nylon 6I, nylon 12
It is a semi-aromatic polyamide such as T, nylon 12I, nylon MXD6 (MXD: metaxylylenediamine) or a copolymer of an aliphatic polyamide and a semi-aromatic polyamide.
The aliphatic polyamide and the semi-aromatic polyamide may be a mixture.

The imide polymer is a polyimide (PI),
Polyamide imide (PAI), polyether imide (P
EI) and the like. The sulfide polymer is polyphenylene sulfide (PPS) or the like. The sulfone-based polymer is polysulfone (PSF), polyether sulfone (PES), or the like. Ketone polymers are polyetherketone (PEK), polyetheretherketone (PE
EK) and the like.

Specific examples of the cured resin include unsaturated polyesters such as polydiallylphthalate-phenol-formaldehyde copolymers, urea resins such as urea-formaldehyde, melamine resins such as polyallylmelamine and melamine-formaldehyde copolymers, It is a phenol resin such as urethane resin and phenol-formaldehyde copolymer.

The polymer used in the composite material of the present invention is
They can be used alone or in combination. The composite material of the present invention has a hydroxyl group, an epoxy group, a carboxylic acid group, an ester group,
Carboxylate group, acid anhydride group, amino group, amide group, imide group, imino group, oxazoline group, isocyano group, cyanato group, isocyanato group, silyl ester group, silyl ether group, silanol group, thiol group, sulfide group, When the modified polymer I containing one or more functional groups selected from a thiocarboxylic acid group and a sulfonic acid group or an organic compound residue containing the functional group is added, it reacts with this to form a covalent bond. The inclusion of the reaction product with the polymer Q is most preferable for stabilizing the morphology of the composite material containing the polymer Q.

A specific method for producing a reaction product of the modified polymer I and the polymer Q is, for example, a functional group (hydroxyl group, carboxyl group,
Method of forming covalent bond with ester group; Method of forming covalent bond with functional group (hydroxyl group, ether group) of ether polymer; Functional group of amide polymer (amino group, carboxyl group, amide group) ) To form a covalent bond; a method to form a covalent bond with a functional group (thiol group, sulfide group) of the sulfide polymer;

Hydroxyl group, epoxy group, carboxylic acid group, ester group, carboxylic acid group, acid anhydride group, amino group, amide group, imide group, imino group, oxazoline group, isocyano group, cyanato group, isocyanato group, silyl ester Group, a silyl ether group, a silanol group, a thiol group, a sulfide group, a thiocarboxylic acid group, a modified polymer Q having one or more kinds of functional groups selected from sulfonic acid groups or an organic compound residue containing the same. Olefin-based polymer, styrene-based polymer, conjugated diene-based polymer, hydrogenated conjugated diene-based polymer, ether-based polymer, and sulfide-based polymer).

In order to achieve both stability / mechanical properties and molding processability (fluidity) of the obtained composite material, the ratio of the reaction product of modified polymer I and polymer Q is ,
Generally 0.001 to 100 wt%, preferably 0.005 to 90 wt%, and more preferably 0.01 to 7 wt% based on the total amount of the modified polymer I, the polymer Q and the reaction product.
It is 0 wt%, and most preferably 0.01 to 50 wt%.

The composite material containing the polymer Q is prepared by a method of solution blending using a common solvent, an extruder, a kneader,
A composition containing at least two kinds of polymers selected from the group consisting of the polymer I and the modified polymer I is prepared by using a conventionally known method such as a method of melt blending using a bra bander, a bumper mixer or the like. It can be manufactured by compounding the combined Q (alloy blend).

The composite material of the present invention comprises a stabilizer such as a heat stabilizer, an antioxidant and an ultraviolet absorber depending on the purpose and use thereof.
Lubricants, nucleating agents, plasticizers, dyes, pigments, cross-linking agents, foaming agents, antistatic agents, anti-slip agents, anti-blocking agents, mold release agents, organic reinforcing materials (aramid, polyimide, polybenzoxazole, polybenzothiazole, Cellulose, etc., inorganic reinforcing materials (short glass fiber, long glass fiber, glass wool, carbon fiber, metal fiber, rock wool, mineral fibers such as titanium whiskers, talc, mica,
Wollastonite, kaolin, montmorillonite, inorganic fillers such as cement and concrete, etc.) and the like, which may be added to or blended with general polymer materials, may be contained.

Examples of more specific stabilizers which are suitably blended with the composite material of the present invention depending on the purpose and application are shown below. For example, as a phenolic antioxidant, 2,6-
Di-tert-butyl-p-cresol, stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate, stearyl-β- (4-hydroxy-3,
5-di-tert-butylphenol) propionate, distearyl-3,5-di-tert-butyl-4
-Hydroxybenzylphosphonate, 2,4,6-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzylthio) 1,3,5-triazine, distearyl (4-hydroxy-3) -Methyl-5-tert-
Butyl) malonate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-
Methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) p-cresol], bis [3,5-bis (4-hydroxy-3-tert-butyl) Phenyl) butyric] glycolate, 4,4'-butylidene bis (6-tert-butyl-m-cresol), 1,1,
3-tris (2-methyl-4-hydroxy-5-ter
t-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-ter)
t-Butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-)
Hydroxy-4-tert-butyl) benzyl isocyanurate, 1,3,5-tris (3,5-di-tert)
-Butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3,5-
(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,3 5-Tris (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl) isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-
(tert-butyl) phenoxy 1,3,5-triazine, 4,4′-thiobis (6-tert-butyl-m-
Cresol) or 4,4'-butylidene bis (2
Carbonic acid oligoester of -tert-butyl-5-methylphenol (for example, polymerization degree 2, 3, 4, 5, 6, 7,
(8, 9, 10, etc.) and the like, polyhydric phenol carbonic acid oligoesters and the like.

As the sulfur-based antioxidant, dialkylthiodipropionates such as dilauryl, dimistyryl and distearyl and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl and stearyl (eg glycerin and trimethylol). Esters of ethane, trimethylolpropane, pentaneerythritol, trishydroxyisocyanurate (eg pentaneerythritol tetralauryl thiopropionate)
Etc. can be illustrated.

Further, as the phosphorus-based stabilizer, trioctylphosphato, trilaurylphosphite, tristearylphosphite, tridecylphosphite, octyldiphenylphosphite, tris (2,4-di-te).
rt-butylphenyl) phosphite, triphenylphosphite, tris (butoxyethyl) phosphite,
Tris (nonylphenyl) phosphite, distearylpentaneerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-te
rt-Butyl-4-hydroxyphenyl) butanediphosphite, tetraalkyl-4,4′-isopropylidenediphenylphosphite, tetra (tridecyl)-
4,4'-butylidene bis (3-methyl-6-tert
-Butylphenol) diphosphite, tris (3,5
-Di-tert-butyl-4-hydroxyphenyl) phosphite, tris (mono / dinonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) -bis [4 , 4'-butylidene bis (3-methyl-6-te
rt-Butylphenol] -1,6-hexanediol diphosphite, phenyl-4,4′-isopropylidene diphenol-pentaneerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaneerythritol diphosphite Fight, screw (2,6-
Di-tert-butyl-4-methylphenyl) pentaneerythritol diphosphite, tris [4,4′-isopropylidene bis (2-tert-butylphenol)] phosphite, phenyldiisodecyl phosphite, di (nonylphenyl) pentaneerythritol Diphosphite, tris (1,3-distearoyloxyisopropyl) phosphite, 4,4′-isopropylidenebis (2-tert-butylphenol) -di (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10- Examples thereof include phosphaphenanthrene-10-oxide, tetrakis (2,4-ditert-butylphenyl) -4,4′-biphenylenediphosphonite, and the like.

Further, a 6-hydroxycoumarone derivative, for example, various tocophenols of α, β, γ, δ and mixtures thereof, 2- (4-methyl-penter-3-enyl) -6-
2,5-dimethyl substitution product of hydroxycoumarone, 2,
5,8-trimethyl substituted product, 2,5,7,8, -tetramethyl substituted product, 2,2,7-trimethyl-5-tert
-Butyl-6-hydroxycoumarone, 2,2,5-trimethyl-7-tert-butyl-6-hydroxycoumarone, 2,2,5-trimethyl-6-tert-butyl-
6-hydroxycoumarone, 2,2-dimethyl-5-te
Examples thereof include rt-butyl-6-coumarone.

[0107] Further, the following _{formula: P x Al y (OH)} 2x + 3y-2z (Q) z · aH 2 O [P represents at least one metal selected from Mg, Ca or Zn. Q represents an anion other than a hydroxyl group.
x, y, z, and a represent an integer of 0 or more. ] The compound represented by these can be mentioned.

Specifically, Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O Mg ₈ Al ₂ (OH) ₂₀ CO ₃ .5H ₂ O Mg ₅ Al ₂ (OH) ₁₄ CO ₃ .4H ₂ O Mg ₁₀ Al ₂ (OH) ₂₂ (CO ₃ ) ₂ .4H ₂ O Mg ₆ Al ₂ (OH) ₁₆ HPO ₄ .4H ₂ O Ca ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O Zn ₆ Al ₂ ( OH) ₁₆ CO ₃ .4H ₂ O Zn ₆ Al ₂ (OH) ₁₆ SO ₄ .4H ₂ O Mg ₆ Al ₂ (OH) ₁₆ SO ₄ .4H ₂ O Mg ₆ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O 2 and the like can be exemplified. In addition, 3-phenyl-2-benzofuranone, 3-phenyl-5,7-di-tert-
It is also possible to employ stabilizers such as 2-benzoferranone compounds such as butyl-2-bunzofuranone.

On the other hand, as the light stabilizer, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Hydroxybenzophenones such as n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2,4-difodoxybenzophenone; 2
-(2'-hydroxy-3'-tert-butyl-5 '
-Methylphenyl-5-chlorobenzotriazole, 2
-(2'-hydroxy-3 ', 5',-di-tert-
Butylphenyl) -5-chlorobenzotriazole, 2
-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-
Benzotriazoles such as di-tert-amylphenyl) benzotriazole;

Phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t
Benzoates such as ert-butyl-4-hydroxybenzoate; 2,2'-thiobis (4-tert-octylphenol) Ni salt, (2,2'-thiobis (-4
-Tert-octylphenolate) -n-butylamine Ni, nickel compounds such as (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester Ni salt; α-cyano-β-methyl- Substituted acrylonitriles such as β- (p-methoxyphenyl) methyl acrylate; and N′-2-methylphenyl-N
Oxalic acid dianilides such as 2-ethoxy-5-tert-butylphenyl oxalic acid diamide and N-2-ethylphenyl-N′-2-ethoxyphenyl oxalic acid diamide;

Bis (2,2,6,6-tetramethyl-4
-Piperidine) sebacate, poly [6- (1,1,
3,3-Tetramethylbutyl) imino] -1,3,5-
Triazine-2,4-diyl [4- (2,2,6,6-
Tetramethylpiperidyl) imino) hexamethylene],
2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) ethanol and dimethyl-1 succinate
Examples thereof include hindered amine compounds obtained as a condensation product with piperidyl.

Specific lubricants include aliphatic hydrocarbons such as paraffin wax, polyethylene wax and polypropylene wax; capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid and behenic acid. Or higher fatty acids such as; or salts of these metal salts such as lithium, potassium, sodium, calcium and magnesium; fatty alcohols such as palmityl alcohol, cetyl alcohol, stearyl alcohol;

Aliphatic amides such as caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, mistyric acid amide, palmitic acid amide, stearic acid amide; esters of fatty acid and alcohol; fluoroalkylcarboxylic acid or Examples of the metal salts include fluorine compounds such as metal salts of fluoroalkyl sulfonic acid.

Further, specific fillers include glass fiber, metal-coated glass fiber, stainless fiber, aluminum fiber, potassium titanate fiber, titanium whiskers,
Inorganic / organic fibrous fillers such as carbon fiber, Kevlar, ultra high molecular weight polyethylene, talc, calcium carbonate, magnesium hydroxide, calcium oxide, magnesium sulfate,
Examples thereof include powdery, granular, and flake-like inorganic / organic fillers such as graphite, nickel powder, copper powder, silver powder, carbon black, metal-coated glass beads, glass flakes, glass balloons, stainless flakes, and metal-coated graphite.

As the molding / processing method of the composite material of the present invention, solvent casting method, injection molding method, gas assist injection molding method, blow (hollow) molding method, extrusion molding method, compression molding method, melt spinning method, Conventionally known molding methods such as a melt core method, an inflation molding method and a multi-layer molding method can be used. The composite material of the present invention is used as an excellent industrial material (structural material or functional material) in high-performance plastics, general-purpose plastics, special elastomers, thermoplastic elastomers, elastic fibers, sheets, films, tubes, hoses, optical materials, etc. It is preferably adopted.

[0116]

The present invention will be described in more detail below with reference to Examples, Production Examples, Comparative Examples, etc., but the scope of the present invention is not limited to these Examples. Synthetic raw materials: The chemicals used in the production examples of the present invention had the highest purity available. General solvents are degassed according to the usual method, refluxed and dehydrated on an active metal under an inert gas atmosphere,
Then, what was distilled and purified was used.

Number average molecular weight; G.I. P. The values in terms of standard polystyrene measured by the C (gel permeation chromatography) method are shown. <Composition test method> Tensile test (1/8 inch) A test was performed according to ASTM D638. Tensile strength (TS), Tensile elongation (TE) Bending test (1/8 inch) The test was performed according to ASTM D790. Flexural strength (FS), flexural modulus (FM)

Izod Impact Test Tested in accordance with ASTM D256 (25 ° C.) Heat distortion temperature (HDT: ° C.) Tested in accordance with ASTM D648 under conditions of high load 1.82 MPa and low load 0.46 MPa . 1 MPa = 10.20 kg · f / cm ² 1 J / m = 0.102 kg · cm / cm Glass transition temperature (Tg) The value measured by the DSC method using DSC200 manufactured by Seiko Instruments Inc. Indicated.

[0119]

[Production Example 1] <Synthesis of Polymer 1: PCHD (Mn≈10,000)> The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. Introduce 2850 g of cyclohexane into the autoclave and dry nitrogen.
It was kept at room temperature. Then, normal butyl lithium (n
-BuLi) is 15.0mmo in terms of lithium atom
1, tetramethylethylenediamine (TME
DA) 7.5 mmol was added.

After heating the autoclave to 40 ° C.,
1,3-Cyclohexadiene (1,3-CHD) 150
g was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 4 hours. After the completion of the polymerization reaction, dehydration n-heptanol equivalent to Li atom was added to stop the polymerization reaction. [Irganox B215 (0037HX)] manufactured by Ciba-Geigy Co., Ltd. was added to the polymer solution, and the solvent was removed by a conventional method to obtain a CHD homopolymer.

Number average molecular weight (Mn) of the obtained polymer I
Is 11,500, and the molecular weight distribution (Mw / Mn) is 1.28.
Met. Further, the 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer I is 31/69 (mo.
The glass transition temperature (Tg) of the polymer I measured by the DSC method was 131 ° C.

[0122]

Production Example 2 <Synthesis of Polymer 2: PCHD (Mn≈40,000)> Polymerization was performed in the same manner as in Production Example 1 except that 2400 g of cyclohexane and 600 g of 1,3-CHD were used, and a CHD homopolymer was obtained. Got The number average molecular weight (M
n) is 44,000 and the molecular weight distribution (Mw / Mn) is 1.
47. Further, the 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer 2 is 35/65.
(Mol ratio), and the glass transition temperature (Tg) of the polymer 2 measured by the DSC method was 137 ° C.

[0123]

Production Example 3 <Synthesis of Polymer 3: PCHD (Mn≈80,000)> Polymerization was performed in the same manner as in Production Example 1 except that 1800 g of cyclohexane and 1200 g of 1,3-CHD were used, and a CHD homopolymer was obtained. Got The polymer 3 thus obtained had a number average molecular weight (Mn) of 79,800 and a molecular weight distribution (Mw / Mn) of 1.46. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in Polymer 3 is 37/6.
3 (mol ratio), and the glass transition temperature (Tg) of the polymer 3 measured by the DSC method was 143 ° C.

[0124]

[Production Example 4] <Synthesis of Polymer 4: HPCHD (Mn≈10,000)> The interior of a sufficiently dried 4 L high pressure autoclave with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1000 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. Polymer I obtained in Preparation Example 1
1000 g of a 10 wt% cyclohexane solution of 1 was introduced into the autoclave, and 50 g of a solid catalyst in which 5 wt% of palladium (Pd) was carried on barium sulfate (BaSO ₄ ) was added.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is set to 55 kg / cm ^2.
As G, a hydrogenation reaction was performed for 6 hours. After completion of the hydrogenation reaction, as a stabilizer, manufactured by Ciba-Geigy Co. [Irganox B
215 (0037HX)] was added, and desolvation operation was performed according to a conventional method to obtain a hydrogenated CHD homopolymer. The polymer 4 thus obtained had a number average molecular weight (Mn) of 10,600 and a molecular weight distribution (Mw / Mn) of 1.24. ¹ H-NM
The hydrogenation rate of double bonds contained in the polymer to be hydrogenated calculated by R measurement was 100 mol%.

[0126]

[Production Example 5] <Synthesis of Polymer 5: HPCHD (Mn≈80,000)> The interior of a sufficiently dried 5 L high pressure autoclave with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. Polymer 3 obtained in Production Example 3
1,500 g of a 10 wt% cyclohexane solution of the above was introduced into the autoclave, and then titanocene dichloride (T
C) / Diisobutylaluminum hydride (DIB
A hydrogenation catalyst consisting of AL-H) = 1/6 was added so as to be 290 ppm based on the polymer.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, the hydrogen pressure is set to 35 kg / cm ^2.
As G, a hydrogenation reaction was performed for 6 hours. After completion of the hydrogenation reaction, as a stabilizer, manufactured by Ciba-Geigy [Irganox B
215 (0037HX)] was added, and desolvation operation was performed according to a conventional method to obtain a hydrogenated CHD homopolymer. The polymer 5 thus obtained had a number average molecular weight (Mn) of 80,600 and a molecular weight distribution (Mw / Mn) of 1.43. ¹ H-NM
The hydrogenation rate of double bonds contained in the polymer to be hydrogenated calculated by R measurement was 58 mol%.

[0128]

Production Example 6 <Synthesis of Polymer 6: CHD-Bd-CHD (10: 8
0:10)> The inside of a sufficiently dried 5 L high pressure autoclave with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1280 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Then n-Bu
After adding Li in terms of lithium atoms and adding 10.0 mmol, and further adding 5.0 mmol of TMEDA, the mixture was stirred at room temperature for 10 minutes.

After heating the autoclave to 40 ° C.,
60 g of 1,3-CHD was introduced into the autoclave, and 4
Polymerization reaction was performed at 0 ° C. for 2 hours to obtain a CHD homopolymer. Then, 1600 g (Bd480 g) of a 30 wt% cyclohexane solution of butadiene (Bd) was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 2 hours to obtain CHD.
-Bd diblock copolymer was obtained. Furthermore, 1,3-
Introduce CHD60g into the autoclave and
Polymerization reaction was carried out for a time to obtain a CHD-Bd-CHD triblock copolymer. After completion of the polymerization reaction, mo is equal to Li atom
The polymerization reaction was stopped by adding 1 n of dehydrated n-heptanol.

[Irganox B215 (0037HX)] manufactured by Ciba-Geigy Co., Ltd. was added to the polymer solution, and the solvent was desolvated according to a conventional method to obtain CHD-Bd-CH.
The D triblock copolymer was recovered. The polymer 6 thus obtained had a number average molecular weight (Mn) of 61,700 and a molecular weight distribution (Mw / Mn) of 1.19. Further, the 1,2-bond / 1,4-of the cyclic conjugated diene monomer unit in the polymer 6
The binding ratio was 30/70 (mol ratio), and the glass transition temperature (Tg) of the CHD portion of the polymer 6 measured by the DSC method was 129 ° C. The amount of 1,2-vinyl bond of Bd was 68 mol based on the whole Bd portion in the polymer 6.
%Met.

[0131]

Production Example 7 <Synthesis of Polymer 7: CHD-HBd-CHD (10: 8
0:10)> The inside of a sufficiently dried 5 L high pressure autoclave with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 10 wt% cyclohexane solution of polymer 6 obtained in Preparation Example 15
00g was introduced into the autoclave, and then a hydrogenation catalyst adjusted with titanocene dichloride (TC) / n-BuLi = 1/1 was added to the polymer in an amount of 25 in terms of metal atom.
It was added so as to be 0 ppm.

After replacing the inside of the autoclave with hydrogen, 7
The temperature was raised to 5 ° C. Furthermore, the hydrogen pressure is set to 10 kg / cm ² G
As a result, a hydrogenation reaction was performed for 30 minutes. After completion of the hydrogenation reaction,
As a stabilizer, manufactured by Ciba-Geigy [Irganox B21
5 (0037HX)] was added and desolvation operation was performed according to a conventional method to obtain a hydrogenated CHD-Bd-CHD triblock copolymer. Number average molecular weight (Mn) of the obtained polymer 7
Is 60,900, and the molecular weight distribution (Mw / Mn) is 1.20.
Met. The hydrogenation rate of the CHD portion of the polymer to be hydrogenated calculated by ¹ H-NMR measurement was 0%, and the hydrogenation rate of the Bd portion was 100 mol%.

[0133]

Production Example 8 <Synthesis of Polymer 8: CHD-Bd-CHD (25: 5
0:25)> the first 1,3-CHD addition amount, the later 1,
CHD-Bd-CHD was prepared in the same manner as in Production Example 6 except that the amounts of 3-CHD added were 100 g and Bd 200 g, respectively.
A triblock copolymer was obtained. The number average molecular weight (Mn) of the obtained polymer 8 was 45,200, and the molecular weight distribution (Mw
/ Mn) was 1.41. Further, the 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer 6 is 36/64 (mol ratio), and the CHD portion of the polymer 8 measured by the DSC method. Glass transition temperature (T
g) was 136 ° C. The 1,2-vinyl bond content of Bd was 71 mol% with respect to the entire Bd portion in polymer 8.

[0134]

Production Example 9 <Synthesis of Polymer 9: CHD-HBd-CHD (25: 5
0:25)> A hydrogenation reaction was carried out in the same manner as in Production Example 7, except that the polymer 8 obtained in Production Example 8 was used. The polymer 9 thus obtained had a number average molecular weight (Mn) of 43,900 and a molecular weight distribution (Mw / Mn) of 1.52. ¹ H-N
The hydrogenation rate of the CHD portion of the polymer to be hydrogenated calculated by MR measurement was 0%, and the hydrogenation rate of the Bd portion was 100 mo.
1%.

[0135]

Production Example 10 <Synthesis of Polymer 10: HCHD-HBd-HCHD (2
5:50:25)> A hydrogenation reaction was carried out in the same manner as in Production Example 4 except that the polymer 8 obtained in Production Example 8 was used.
The number average molecular weight (Mn) of the obtained polymer 10 was 41,8.
00, the molecular weight distribution (Mw / Mn) was 1.46.
The hydrogenation rates of the CHD part and Bd part of the polymer to be hydrogenated calculated by ¹ H-NMR measurement are both 100 mol%.
Met.

[0136]

Production Example 11 <Synthesis of Polymer 11: CHD-Ip-CHD (16.
5: 67: 16.5)> in the same manner as in Production Example 6 except that the initial 1,3-CHD addition amount and the subsequent 1,3-CHD addition amount were 100 g and isoprene (Ip) 400 g, respectively. CHD-Ip-CHD triblock copolymer was obtained. The number average molecular weight (Mn) of the obtained polymer 11 was 6
3,200, and the molecular weight distribution (Mw / Mn) was 1.31. Further, the 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer 11 is 33/67 (mol
Ratio), and the glass transition temperature (Tg) of the CHD portion of the polymer 11 measured by the DSC method was 132 ° C. With respect to the entire Ip portion in the polymer 11, Ip of 3,
The 4-vinyl bond content was 67 mol%.

[0137]

Production Example 12 <Synthesis of Polymer 12: CHD-HIp-CHD (16.
5: 67: 16.5)> Polymer I obtained in Preparation Example 11
1, the hydrogenation catalyst was TC / DIBAL-H = 1 /
6. The hydrogenation reaction was performed in the same manner as in Production Example 7, except that the reaction temperature was 120 ° C. The number average molecular weight (Mn) of the obtained polymer 12 was 61,800, and the molecular weight distribution (Mw /
Mn) was 1.36. The hydrogenation rate of the CHD portion of the polymer to be hydrogenated calculated by ¹ H-NMR measurement is 3
4 mol%, the hydrogenation rate of the Ip portion was 93 mol%.

[0138]

Production Example 13 <Synthesis of Polymer 13: CHD-Ip-CHD (25: 5
0:25)> Bd was changed to Ip to obtain a CHD-Ip-CHD triblock copolymer in the same manner as in Production Example 8. The number average molecular weight (Mn) of the obtained polymer 13 was 43,500, and the molecular weight distribution (Mw / Mn) was 1.32. Further, the 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer 13 is 35/65 (mo.
1) and the polymer I3 measured by the DSC method.
The glass transition temperature (Tg) of the CHD portion of the above was 134 ° C. The amount of 3,4-vinyl bonds of Ip was 65 mol% with respect to the entire Ip portion in the polymer 13.

[0139]

Production Example 14 <Synthesis of Polymer 14: CHD-HIp-CHD (25:
50:25)> A hydrogenation reaction was carried out in the same manner as in Production Example 12 except that the polymer I3 obtained in Production Example 13 was used. The number average molecular weight (Mn) of the obtained polymer 14 was 4
4,800 and the molecular weight distribution (Mw / Mn) was 1.39. The hydrogenation rate of the CHD portion of the polymer to be hydrogenated was 27 mol% and the hydrogenation rate of the Ip portion was 95 mol% calculated by ¹ H-NMR measurement.

[0140]

Production Example 15 <Synthesis of Polymer 15: HCHD-HIp-HCHD (2
5:50:25)> A hydrogenation reaction was performed in the same manner as in Production Example 10 except that the polymer I4 obtained in Production Example 14 was used. The number average molecular weight (Mn) of the obtained polymer 15 was 4
3,700 and the molecular weight distribution (Mw / Mn) was 1.42. The hydrogenation rates of the CHD portion and the Ip portion of the polymer to be hydrogenated calculated by ¹ H-NMR measurement are both 100 m.
ol%.

[0141]

Production Example 16 <Synthesis of Polymer 16: CHD-St-CHD (16.
5: 67: 16.5)> Cp-St-CH in the same manner as in Production Example 11 except that Ip was changed to styrene (St).
A D triblock copolymer was obtained. Polymer 16 obtained
Had a number average molecular weight (Mn) of 61,100 and a molecular weight distribution (Mw / Mn) of 1.27. In addition, the polymer 16
1,2-bond / 1,4 of cyclic conjugated diene monomer unit in
The binding ratio was 36/64 (molar ratio), and the glass transition temperature (Tg) of the CHD portion of the polymer I6 measured by the DSC method was 137 ° C.

[0142]

Production Example 17 <Synthesis of Polymer 17: HCHD-St-HCHD (1
6.5: 67: 16.5)> The hydrogenation reaction was performed in the same manner as in Production Example 12 except that the polymer 16 obtained in Production Example 16 was used. The number average molecular weight (M
n) is 60,800, and the molecular weight distribution (Mw / Mn) is 1.
23. The hydrogenation rate of the CHD portion of the polymer to be hydrogenated calculated by ¹ H-NMR measurement is 36 mol%,
The hydrogenation rate of the St portion was 0 mol%.

[0143]

Production Example 18 <Synthesis of Polymer 18: CHD-St-CHD (25: 5
0:25)> Bd was changed to St to obtain a CHD-St-CHD triblock copolymer in the same manner as in Production Example 8. The number average molecular weight (Mn) of the obtained polymer 13 was 42,900, and the molecular weight distribution (Mw / Mn) was 1.26. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer 18 is 34/66 (mo.
1) and the polymer 18 measured by the DSC method.
CHD partial glass transition temperature (Tg) was 131 ° C.

[0144]

Production Example 19 <Synthesis of Polymer 19: HCHD-HSt-HCHD (2
5:50:25)> The hydrogenation reaction was performed in the same manner as in Production Example 10 except that the polymer 18 obtained in Production Example 18 was used. The number average molecular weight (Mn) of the obtained polymer 19 was 4
4,300 and the molecular weight distribution (Mw / Mn) was 1.29. The hydrogenation rates of the CHD part and St part of the polymer to be hydrogenated calculated by ¹ H-NMR measurement are both 100 m.
ol%.

[0145]

[Production Example 20] <Synthesis of Polymer 20: Bd-CHD (50:50)> The interior of a sufficiently dried 5 L high pressure autoclave with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2133 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Then, 10.0 mmol of n-BuLi in terms of lithium atom was added, and TMED was further added.
After adding A5.0 mmol, it stirred at room temperature for 10 minutes.

After heating the autoclave to 40 ° C., B
667 g of a 30 wt% cyclohexane solution of d (Bd20
0 g) was introduced into an autoclave and a polymerization reaction was carried out at 40 ° C. for 2 hours to obtain a Bd homopolymer. Furthermore, 1,3
-Introduce CHD200g into the autoclave, and 40 ℃
Polymerization reaction was carried out for 5 hours to obtain a Bd-CHD diblock copolymer. After the completion of the polymerization reaction, dehydration n-heptanol equivalent to Li atom was added to stop the polymerization reaction. [Irganox B215 (0037HX)] manufactured by Ciba-Geigy Co., Ltd. was added to the polymer solution, and the solvent was desolvated according to a conventional method to recover the Bd-CHD diblock copolymer.

The number average molecular weight (M
n) is 40,800, and the molecular weight distribution (Mw / Mn) is 1.
28. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer units in the polymer 20 is 34/66.
(Mol ratio), and the glass transition temperature (Tg) of the CHD portion of the polymer 20 measured by the DSC method is 133.
° C. B with respect to the entire Bd portion in the polymer 20
The 1,2-vinyl bond content of d was 68 mol%.

[0148]

Production Example 21 <Synthesis of Polymer 21: HBd-CHD (50:50)>
A hydrogenation reaction was performed in the same manner as in Production Example 7 except that the polymer 20 obtained in Production Example 20 was used. The number average molecular weight (Mn) of the obtained polymer 21 was 41,400, and the molecular weight distribution (Mw / Mn) was 1.32. The hydrogenation rate of the CHD portion of the polymer to be hydrogenated calculated by ¹ H-NMR measurement was 0%, and the hydrogenation rate of the Bd portion was 100 mol%.

[0149]

Production Example 22 <Synthesis of Polymer 22: Bd-CHD (20:80)>
A Bd-CHD diblock copolymer was obtained in the same manner as in Production Example 20, except that 320 g of 1,3-CHD and 80 g of Bd were changed. The number average molecular weight (Mn) of the obtained polymer 22 was 45,200, and the molecular weight distribution (Mw / Mn) was 1.43. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer 22 is 37 /
63 (mol ratio), and the CHD partial glass transition temperature (Tg) of the polymer 22 measured by the DSC method was 13
8 ° C. For the entire Bd portion in polymer 22,
The 1,2-vinyl bond content of Bd was 71 mol%.

[0150]

Production Example 23 <Synthesis of Polymer 23: HBd-CHD (20:80)>
A hydrogenation reaction was performed in the same manner as in Production Example 7 except that the polymer 22 obtained in Production Example 22 was used. The number average molecular weight (Mn) of the obtained polymer 23 was 43,900, and the molecular weight distribution (Mw / Mn) was 1.46. The hydrogenation rate of the CHD portion of the polymer to be hydrogenated calculated by ¹ H-NMR measurement was 0%, and the hydrogenation rate of the Bd portion was 100 mol%.

[0151]

Production Example 24 <Synthesis of Polymer 24: HBd-HCHD (20:80)
> A hydrogenation reaction was carried out in the same manner as in Production Example 10 except that the polymer 23 obtained in Production Example 23 was used. The number average molecular weight (Mn) of the obtained polymer 23 was 44,400, and the molecular weight distribution (Mw / Mn) was 1.44. ¹ H-NM
The hydrogenation rates of the CHD part and the Bd part of the polymer to be hydrogenated calculated by R measurement were both 100 mol%.

[0152]

Production Example 25 <Synthesis of Polymer 25: Ip-CHD (50:50)> B
Ip was repeated in the same manner as in Production Example 20 except that d was changed to Ip.
A -CHD diblock copolymer was obtained. The number average molecular weight (Mn) of the obtained polymer 25 was 41,000 and the molecular weight distribution (Mw / Mn) was 1.31. Also, polymer 2
1,2-bond / 1, of the cyclic conjugated diene monomer unit in 5
The 4-bond ratio was 35/65 (mol ratio), and the glass transition temperature (Tg) of the CHD portion of the polymer 25 measured by the DSC method was 132 ° C. I in polymer 25
The amount of 3,4-vinyl bond of Ip is 6 with respect to the entire p portion.
It was 6 mol%.

[0153]

Production Example 26 <Synthesis of Polymer 26: St-CHD (50:50)> B
St was made in the same manner as in Production Example 20 except that d was changed to St.
A -CHD diblock copolymer was obtained. The number average molecular weight (Mn) of the obtained polymer 26 was 43,100 and the molecular weight distribution (Mw / Mn) was 1.27. Also, polymer 2
1,2-bond / 1, of the cyclic conjugated diene monomer unit in 6
The 4-bond ratio was 33/67 (mol ratio), and the glass transition temperature (Tg) of the CHD portion of the polymer 26 measured by the DSC method was 131 ° C.

[0154]

Production Example 27 <Synthesis of Polymer 27: St-HCHD (50:50)>
Using the polymer 26 obtained in Production Example 26, the reaction temperature was 1
The hydrogenation reaction was performed in the same manner as in Production Example 12 except that the temperature was changed to 60 ° C. The number average molecular weight (M
n) is 41,800 and the molecular weight distribution (Mw / Mn) is 1.
33. The hydrogenation rate of the CHD portion of the polymer to be hydrogenated calculated by ¹ H-NMR measurement is 94 mol%,
The hydrogenation rate of the St portion was 0 mol%.

[0155]

Production Example 28 <Synthesis of Polymer 28: CHD-MMA> The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was
It was replaced with dry nitrogen according to a conventional method. Cyclohexane 260
0 g was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 10.0 mmol of n-BuLi in terms of lithium atom was added, and further TMEDA 5.0 mm
After adding ol, the mixture was stirred at room temperature for 10 minutes. After heating the autoclave to 40 ° C, 200 g of 1,3-CHD
Was introduced into an autoclave and a polymerization reaction was carried out at 40 ° C. for 4 hours to obtain a CHD homopolymer.

Further, methyl methacrylate (MMA) 20
0 g was introduced into the autoclave and a polymerization reaction was carried out at 40 ° C. for 5 hours to obtain a CHD-MMA diblock copolymer. After the completion of the polymerization reaction, dehydration n-heptanol equivalent to Li atom was added to stop the polymerization reaction. As a stabilizer in the polymer solution, manufactured by Ciba-Geigy [Irganox B21
5 (0037HX)] was added, and the solvent was removed according to a conventional method to recover the CHD-MMA diblock copolymer.

The number average molecular weight (M
n) is 35,600 and the molecular weight distribution (Mw / Mn) is 1.
It was 88. Further, the 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer 28 is 31/69.
(Mol ratio), and the glass transition temperature (Tg) of the CHD portion of the polymer 28 measured by the DSC method was 131.
° C.

[0158]

Example 1 Polymer 1 (PCHD: Mn≈10,000) / Polymer 7 (CHD-HBd-CHD) = 5/95 (wt%)
15mmφ twin-screw extruder [Laboplast mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)]
Composite material 1 was manufactured by melting and kneading at 220 to 250 ° C. The obtained composite material 1 was compression molded at 280 ° C. to prepare a test piece. The tensile strength (TS) of this composite material is
It is 20.10 MPa and the tensile elongation (TE) is 610%.
Met. C of composite material 1 measured by DSC method
The glass transition temperature (Tg) of the HD portion was 135 ° C.

[0159]

Example 2 Polymer 1 (PCHD: Mn≈10,000) / Polymer 9 (CHD-HBd-CHD) = 5/95 (wt%)
Dry blending was carried out in the ratio of, and a composite material 2 was manufactured in the same manner as in Example 1. The obtained composite material 2 was molded in the same manner as in Example 1 to prepare a test piece. The tensile strength (TS) of this composite material is 24.50 MPa, and the tensile elongation (T
E) was 300%. The glass transition temperature (Tg) of the CHD portion of the composite material 2 measured by the DSC method is 1
39 ° C.

[0160]

Example 3 Polymer 1 (PCHD: Mn≈10,000) / Polymer 12 (CHD-HIp-CHD) = 5/95 (wt)
%) Was dry-blended, and composite material 3 was manufactured in the same manner as in Example 1. The composite material 3 thus obtained was used in Example 1.
A test piece was prepared by molding in the same manner as in. The tensile strength (TS) of this composite material was 22.35 MPa, and the tensile elongation (TE) was 550%. Glass transition temperature (Tg) of CHD portion of composite material 3 measured by DSC method
Was 136 ° C.

[0161]

Example 4 Polymer 1 (PCHD: Mn≈10,000) / Polymer 14 (CHD-HIp-CHD) = 5/95 (wt)
%) And dry blending was performed, and composite material 4 was manufactured in the same manner as in Example 1. The obtained composite material 4 was used in Example 1.
A test piece was prepared by molding in the same manner as in. The tensile strength (TS) of this composite material was 25.13 MPa, and the tensile elongation (TE) was 280%. Glass transition temperature (Tg) of CHD portion of composite material 3 measured by DSC method
Was 136 ° C.

[0162]

Comparative Examples 1 to 4 Polymer 7 (CHD-HBd-CH
D), polymer 9 (CHD-HBd-CHD), polymer 1
2 (CHD-HBd-CHD), polymer 14 (CHD-
HBd-CHD) was molded in the same manner as in Example 1 to prepare a test piece. This simple substance (polymer 7, 9, 12, 1
The tensile strength (TS) of 4) is 12.64 MPa and 2 respectively.
0.59 MPa, 15.74 MPa, 22.53 MPa
And the tensile elongations (TE) are 640%, 320%,
It was 590% and 290%.

[0163]

Example 5 Polymer 1 (PCHD: Mn≈10,000) / Polymer 16 (CHD-St-CHD) = 5/95 (wt%)
Dry blending was carried out at a ratio of, and a composite material 5 was manufactured in the same manner as in Example 1. The obtained composite material 5 was molded in the same manner as in Example 1 to prepare a test piece. The tensile strength (TS) of this composite material is 18.7 MPa, and the tensile elongation (TE)
Was 2%.

The flexural strength (TS) was 45.5 MPa and the flexural modulus (FM) was 3,085 MPa.
The heat distortion temperature (HDT: 1.82 MPa) was 77 ° C., and the glass transition temperature (Tg) of the CHD portion of the composite material 5 measured by the DSC method was 140 ° C.

[0165]

Example 6 Polymer 1 (PCHD: Mn≈10,000) / Polymer 18 (CHD-St-CHD) = 5/95 (wt%)
Dry blending was carried out at a ratio of, and a composite material 6 was manufactured in the same manner as in Example 1. The obtained composite material 6 was molded in the same manner as in Example 1 to prepare a test piece. The flexural strength (TS) of this composite material is 31.8 MPa, and the flexural modulus (F)
M) was 2,953 MPa. Heat distortion temperature (HD
T: 1.82 MPa) was 84 ° C., and the glass transition temperature (Tg) of the composite material 6 measured by the DSC method was 136 ° C.

[0166]

Comparative Examples 5-6 Polymer 16 (CHD-St-CH
D), polymer 18 (CHD-St-CHD) in Example 1
A test piece was prepared by molding in the same manner as in. The tensile strength (TS) of this simple material (polymer 16) is 16.5 MPa.
And the tensile elongation (TE) was 2%. Also,
Bending strength (TS) of polymers 16 and 18 is 41.1M each
Pa and 29.7 MPa, and bending elastic moduli (FM) were 2,864 MPa and 2,89 MPa, respectively. Heat distortion temperature (HDT: 1.82 MPa) is 73 ° C and 78 ° C, respectively
Met.

[0167]

Example 7 Polymer 1 (PCHD: Mn≈10,000) / Polymer 7 (CHD-HBd-CHD) = 5/95 (wt%)
Dry blend at a ratio of
It was dissolved in F) and stirred to form a uniform polymer solution. Next, this solution was reprecipitated with acetone to produce a composite material 7. The obtained composite material 7 was compression molded at 280 ° C. to prepare a test piece. The tensile strength (TS) of this composite material is 2
The tensile elongation (TE) was 2.15 MPa and 650%. The glass transition temperature (Tg) of the composite material 7 measured by the DSC method was 137 ° C.

[0168]

Example 8 Polymer 4 (HPCHD: Mn≈10,000) / Polymer 10 (HCHD-HBd-HCHD) = 5/95
(Wt%) dry blended, 15 mmφ twin-screw extruder [Laboplast mill: manufactured by Toyo Seiki Co., Ltd. (L / D
= 17)] and melt-kneaded at 250 to 280 ° C. to produce composite material 8. The obtained composite material 8 was compression molded at 280 ° C. to prepare a test piece. The tensile strength (TS) of this composite material was 18.6 MPa, and the tensile elongation (TE) was 135%.

[0169]

Example 9 Polymer 1 (PCHD: Mn≈10,000) / Polymer 11 (CHD-Ip-CHD) = 10/90 = 100
Parts by weight, 2 parts by weight of maleic anhydride, Perhexa 25B
Dry blending 0.5 part by weight of [Nippon Yushi Co., Ltd.], and 210 to 250 ° C. in a 15 mmφ twin-screw extruder [Laboplast Mill: Toyo Seiki Co., Ltd. (L / D = 17)].
The mixture was melt-kneaded at a temperature of 1 to obtain a modified composite material 1. This modified composite material 1 was extracted with hot acetone at 80 ° C.
It was vacuum dried at.

When the grafted amount of maleic anhydride was determined with sodium methylate, 1.2 mol% of maleic anhydride was grafted. This modified composite material 1
0 parts by weight, 80 parts by weight of nylon 66 [Leona 1402S: manufactured by Asahi Kasei Kogyo Co., Ltd.] are dry blended to obtain 15 mm.
A test piece was molded by melt-kneading at a temperature of 260 to 280 ° C. in a φ twin-screw extruder [Laboplast Mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)], and then injection-molded at 280 ° C. The strength (TS) was 62.3 MPa and the tensile elongation (TE) was 80%.

The flexural strength (TS) was 76.3 MPa, and the flexural modulus (FM) was 2,250 MPa.
The heat distortion temperature (HDT: 1.82 MPa) was 64 ° C. The Izod impact strength is determined by the N.I. It was B (not broken).

[0172]

COMPARATIVE EXAMPLE 7 Polymer 11 (CHD-Ip-CHD) was added to 1
00 parts by weight, maleic anhydride 2 parts by weight, perhexa 2
0.5B by weight of 5B [manufactured by Nippon Oil & Fats Co., Ltd.], and 210-250 in a 15 mmφ twin-screw extruder [Laboplast Mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)].
Melt kneading was carried out at a temperature of ° C to obtain a modified polymer I. The modified polymer I was extracted with hot acetone and vacuum dried at 80 ° C. When the grafted amount of maleic anhydride was calculated with sodium methylate, it was 1.4 mol%
Of maleic anhydride was grafted.

20 parts by weight of this modified polymer I and 80 parts of nylon 66 [Leona 1402S: manufactured by Asahi Kasei Kogyo Co., Ltd.]
Parts by weight are dry-blended, melt-kneaded in a 15 mmφ twin-screw extruder [Laboplast mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)] at a temperature of 260 to 280 ° C., and then 280
A test piece was molded by injection molding at ° C. The tensile strength (TS) of this composition is 56.2 MPa, and the tensile elongation (TE)
Was 82%. Bending strength (TS) is 72.7 MPa
And the flexural modulus (FM) was 1,930 MPa. The heat distortion temperature (HDT: 1.82 MPa) is 61.
° C. The Izod impact strength is determined by the N.I.
B. (Without breaking).

[0174]

Examples 10 to 11 Compounding composition (wt) of modified composite material 1 (M: PCHD / CHD-Ip-CHD) obtained in Example 9 and nylon 66 [Leona 1402S: Asahi Kasei Kogyo KK] A composite material was produced and evaluated under the same conditions as in Example 9 except that the ratios were set to 30/70 and 50/50, respectively. Table 1 shows the results.

[0175]

Example 12 Polymer 1 (PCHD: Mn≈1) was used in the same manner as in Example 9 except that polymer 25 (Ip-CHD) was used instead of polymer 11 (CHD-Ip-CHD).
10,000) / Polymer 25 (Ip-CHD) = 10/90 (wt
Ratio) to modified composite material 2 and then modified composite material 2 / nylon 66 [Leona 1402S: Asahi Kasei Kogyo KK]
= 20/80 (wt ratio), the composite material compounded was manufactured and evaluated in the same manner as in Example 9. Table 1 shows the results.

[0176]

Examples 13 to 14 Modified composite material 2 (M: PCHD / Ip-CHD) obtained in Example 12 and nylon 66
A composite material was trial-produced and evaluated under the same conditions as in Example 9 except that the compounding composition (wt ratio) with [Leona 1402S: manufactured by Asahi Kasei Co., Ltd.] was changed to 30/70 and 50/50, respectively. Table 1 shows the results.

[0177]

Examples 15 to 17 Polymer 11 (CHD-Ip-CH
Instead of D), polymer 12 (CHD-HIp-CH
Modified composite material 3 was prepared in the same manner as in Example 9 except that D) was used. Modified composite material / nylon 66 [Leona 140
2S: manufactured by Asahi Chemical Industry Co., Ltd.] = 20/80, 30/7
0) and 50/50 (wt ratio) in the composite material of Example 9.
Prototypes and evaluations were made in the same manner as in. Table 1 shows the results.

[0178]

Examples 18 to 20 Polymer 11 (CHD-Ip-CH
The modified composite material 4 was prepared in the same manner as in Example 9 except that the polymer 21 (HBd-CHD) was used instead of D), and the modified composite material 4 / nylon 66 [Leona 1402S: manufactured by Asahi Kasei Kogyo KK]. = 20/80, 30/70, 50/50
A composite material having a (wt ratio) was manufactured and evaluated in the same manner as in Example 9. Table 1 shows the results.

[0179]

[Table 1]

[0180]

Example 21 A composite material 9 composed of polymer 1 (PCHD: Mn≈10,000) / polymer 6 (CHD-Bd-CHD) = 10/90 was produced in the same manner as in example 1, and composite material 9
/ Polypropylene [Asahi Kasei Polypro M1500: Asahi Kasei Kogyo Co., Ltd.] was dry blended at a ratio of 20/80 (wt ratio), and then a 15 mmφ twin-screw extruder [Laboplast Mill: Toyo Seiki Co., Ltd. (L / D = 17)]
The mixture was mixed at a temperature of 230 ° C. and further pelletized to obtain a composite material. The obtained composite material was injection molded at 230 ° C. to form a test piece and evaluated.

The tensile strength (TS) of this composite material was 22.
It was 7 MPa, and the tensile elongation (TE) was 500% or more. The flexural strength (FS) was 37.5 MPa, and the flexural modulus (FM) was 1240 MPa. The heat distortion temperature (HDT: 0.46 MPa) was 98 ° C. The Izod impact strength is determined by the N.I. B. (Without breaking)
Met.

[0182]

Example 22 A composite material 10 was prepared by using Polymer 8 (CHD-Bd-CHD) instead of Polymer 6 in the same manner as in Example 21, except that this was used. Similarly, a composite material (composite material 10 / PP = 20/8
0) was obtained. The tensile strength (TS) of this composite material is 34.
It was 1 MPa and the tensile elongation (TE) was 500% or more. The flexural strength (FS) was 41.3 MPa, and the flexural modulus (FM) was 1423 MPa. The heat distortion temperature (HDT: 0.46 MPa) was 121 ° C.
The Izod impact strength is determined by the N.I. B. (Without breaking).

[0183]

Example 23 Instead of polymer 6, polymer 13 (CHD
-Ip-CHD) except that the composite material 11 was used.
A composite material was obtained in the same manner as in Example 21. The tensile strength (TS) of this composite material was 24.9 MPa, and the tensile elongation (TE) was 500% or more. The flexural strength (FS) is 36.4 MPa, and the flexural modulus (FM) is 1083.
MPa. Heat distortion temperature (HDT: 0.46MP
a) was 92 ° C. The Izod impact strength is determined by the N.I. B. (Without breaking).

[0184]

Examples 24 to 25 Composite material 9 / polypropylene obtained in Example 21 [Asahi Kasei Polypro M1500: manufactured by Asahi Kasei Corporation] = 30/70, 50/50 (wt ratio)
A composite material was produced in the same manner as in Example 21 except that
evaluated. Table 2 shows the results.

[0185]

Examples 26 to 27 Composite material 10 obtained in Example 22 (PCHD: Mn≈10,000 / CHD-Bd-CHD)
/ Polypropylene [Asahi Kasei Polypro M1500: Asahi Kasei Kogyo Co., Ltd.] = 30/70, 50/50 (wt ratio) A composite material was manufactured and evaluated in the same manner as in Example 21. Table 2 shows the results.

[0186]

Examples 28 to 29 The composite material 11 obtained in Example 23 (PCHD: Mn≈10,000 / CHD-Ip-CHD).
/ Polypropylene [Asahi Kasei Polypro M1500: Asahi Kasei Kogyo Co., Ltd.] = 30/70, 50/50 (wt ratio) A composite material was manufactured and evaluated in the same manner as in Example 21. Table 2 shows the results.

[0187]

Examples 30 to 31 Polymer 20 (Bd-CHD) and polymer 25 (Ip-CHD) were used, and polymer 1 (PCH
D: Mn≈10,000) / Polymer 20 (Bd-CHD) = 10
/ 90 and polymer I (PCHD: Mn≈10,000) / polymer 25 (Ip-CHD) = 10/90 composite material 1
2, 13 were obtained in the same manner as in Example 21. These composite materials 12, 23 and polypropylene [Asahi Kasei Polypro M1
500: Asahi Kasei Kogyo Co., Ltd.] 20/80 (wt
15mmφ twin-screw extruder [Laboplast mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 1)
7)] at a temperature of 220 to 240 ° C. and further pelletized to obtain a composite material. The obtained composite material is 230 ° C.
Was injection-molded to mold a test piece and evaluated. Table 2 shows the results.

[0188]

Example 32 Polymer 4 (HPCHD: Mn≈10,000) and polymer 15 (HCHD-HIp-HCHD) were used as polymer 4
(HPCHD: Mn≈10,000) / Polymer 15 (HCHD-
HIp-HCHD) = 10/90 (wt ratio) dry blended 100 parts by weight, maleic anhydride 2 parts by weight, Perhexa 25B [manufactured by NOF Corporation]
25 parts in a 15 mmφ twin-screw extruder [Laboplast mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)]
The mixture was kneaded at a temperature of 0 to 280 ° C. to produce a modified composite material 5.

The modified composite material 5 was extracted with hot acetone and vacuum dried at 80 ° C. When the grafted amount of maleic anhydride was determined with sodium methylate, 1.1 mol% of maleic anhydride was grafted. In addition, polypropylene [Asahi Kasei Polypro M15
00: manufactured by Asahi Kasei Kogyo Co., Ltd.],
4 parts by weight of glycidyl methacrylate (GMA) and 0.5 parts by weight of Perhexa 25B (manufactured by NOF CORPORATION) were added, and a 15 mmφ twin-screw extruder [Laboplast Mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)] at a temperature of 200 to 220 ° C., and GMA-modified polypropylene (g-PP)
I got

After removing unreacted GMA by extraction, the amount of glycidyl methacrylate grafted was determined by infrared absorption spectrum analysis. As a result, 0.7% of glycidyl methacrylate was grafted. The above-mentioned modified composite material 5 and GMA-modified PP (g-PP) were mixed with 20/80.
Dry blend at a ratio of (wt ratio), and a 15 mmφ twin-screw extruder [Laboplast mill: manufactured by Toyo Seiki Co., Ltd. (L / D
= 17)] at a temperature of 220 to 240 ° C. and further pelletized to obtain a composite material. 23 of the obtained composite material
The test pieces were molded by injection molding at 0 ° C. and evaluated. Table 2 shows the results.

[0191]

Example 33 Polymer 4 (HPCHD: Mn≈10,000) and polymer 15 (HCHD-HIp-CHD) were used in the same manner as in Example 21 to polymer 4 / polymerization 15 = 10/90.
The composite material 14 which is is obtained. Composite material 14 / Syndiotactic polypropylene (SPP: 230 ° C, 2.1
A 6 kg load MI = 10) = 20/80 (wt ratio) was dry blended, and a composite material was produced and evaluated in the same manner as in Example 31. Table 2 shows the results.

[0192]

[Table 2]

[0193]

Example 34 Instead of polymer 4, polymer 21 (HB
d-CHD) and polymer 1 (PCHD: Mn≈10,000) / polymer 21 (HBd-C) in the same manner as in Example 21.
A composite material 15 with HD) = 10/90 was obtained. Composite Material 14 / High Density Polyethylene [Suntech HDJ24
0: Asahi Kasei Kogyo Co., Ltd.] = 20/80 (wt ratio) dry blended in a 15 mmφ twin-screw extruder [Laboplast Mill: Toyo Seiki Co., Ltd. (L / D = 17)] The mixture was mixed at a temperature of 190 to 200 ° C. and further pelletized to obtain a composite material. The obtained composite material was injection-molded at 200 ° C. to form a test piece and evaluated. Table 3 shows the results.

[0194]

Examples 35 to 36 Polymer 1 (PCHD: Mn≈1
10,000) and polymer 16 (CHD-St-CHD), in the same manner as in Example 1, polymer 1 / polymer 16 = 10/9
A composite material 16 of 0 was obtained. Composite material 16 / polystyrene [Stylon 685: manufactured by Asahi Chemical Industry Co., Ltd.] = 20
/ 80, 30/70 (wt ratio) dry blended, and at a temperature of 230 to 250 ° C in a 15 mmφ twin-screw extruder [Laboplast Mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)]. The mixture was mixed and further pelletized to obtain a composite material. The resulting composite material is injection molded at 250 ° C. to form a test piece,
An evaluation was performed. Table 3 shows the results.

[0195]

Examples 37 to 38 Instead of polymer 16, polymer 2
A composite material was produced and evaluated in the same manner as in Example 35, except that the composite material 17 of 6 (St-CHD) was used. Table 3 shows the results.

[0196]

[Example 39] Using the composite material 16 obtained in Example 35, composite material 16 / acrylonitrile-styrene copolymer [Styrac AS767: manufactured by Asahi Kasei Kogyo KK] =
Dry blend at a ratio of 20/80 (wt ratio), 15
mmφ twin-screw extruder [Laboplast mill: Toyo Seiki Co., Ltd.
(L / D = 17)] at a temperature of 230 to 250 ° C. and further pelletized to obtain a composite material. The obtained composite material was injection-molded at 250 ° C. to form a test piece and evaluated. Table 3 shows the results.

[0197]

[Example 40] In Example 39, instead of the acrylonitrile-styrene copolymer, an acrylonitrile-styrene-butadiene copolymer [Styrac ABS10 was used.
1: Asahi Kasei Kogyo Co., Ltd.] was used and the composite material was manufactured and evaluated in the same manner as in Example 38 except that the composite material 18 was used. Table 3 shows the results.

[0198]

Examples 41 to 42 Composite material 1 obtained in Example 35
6, and composite material 16 / syndiotactic polystyrene (SPS: 280 ° C., 3.80 kg load MI = 2.
5) = 20/80, 30/70 (wt ratio) dry blended, and 270 to 750 in a 15 mmφ twin-screw extruder [Laboplast Mill: Toyo Seiki Co., Ltd. (L / D = 17)].
The mixture was mixed at a temperature of 290 ° C. and further pelletized to obtain a composite material. The obtained composite material was injection-molded at 290 ° C. to form a test piece and evaluated. Table 3 shows the results.

[0199]

Example 43 Polymer 4 (HPCHD: Mn≈10,000) and polymer 24 (HBd-HCHD) were used, and polymer 4 (H
PCHD: Mn≈10,000) / Polymer 24 (HBd-HCH)
D) = 10/90 (wt%) dry blended, and at a temperature of 250 to 280 ° C. in a 15 mmφ twin-screw extruder [Laboplast mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)]. It mixed and obtained the composite material 19. Composite material 19 / high-density polyethylene [Suntech HDJ240: manufactured by Asahi Kasei Kogyo Co., Ltd.] = 20/80 (wt ratio) dry blended, 15 mmφ twin-screw extruder [Laboplast mill:
Manufactured by Toyo Seiki Co., Ltd. (L / D = 17)] 250-28
The mixture was mixed at a temperature of 0 ° C. and further pelletized to obtain a composite material. The obtained composite material was injection-molded at 280 ° C. to form a test piece and evaluated. Table 3 shows the results.

[0200]

[Table 3]

[0201]

Example 44 Polymer 4 (HPCHD: Mn≈10,000) and polymer 10 (HCHD-HBd-HCHD) were used as polymer 4
(HPCHD: Mn≈10,000) / Polymer 10 (HCHD-
HBd-HCHD) = 10/90 (wt ratio) dry blended 100 parts by weight, maleic anhydride 2 parts by weight, Perhexa 25B [manufactured by NOF Corporation]
25 parts in a 15 mmφ twin-screw extruder [Laboplast mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)]
The modified composite material 6 was manufactured by kneading at a temperature of 0 to 280 ° C.

The modified composite material 6 was extracted with hot acetone and vacuum dried at 80 ° C. When the grafted amount of maleic anhydride was determined with sodium methylate, 1.2 mol% of maleic anhydride was grafted. 20 parts by weight of this modified composite material 6, nylon 6
80 parts by weight of 6 [Leona 1402S: Asahi Kasei Kogyo Co., Ltd.] was dry blended, and 260-280 ° C. in a 15 mmφ twin-screw extruder [Laboplast Mill: Toyo Seiki Co., Ltd. (L / D = 17)]. The mixture was mixed at the temperature of 1 and further pelletized to obtain a composite material. The obtained composite material was injection-molded at 280 ° C. to form a test piece and evaluated. Table 4 shows the results.

[0203]

[Example 45] Modified composite material 5 / nylon 66 was used in the same manner as in Example 44, except that the modified composite material 5 obtained in Example 32 was used instead of the modified composite material 6 used in Example 44. [Leona 1402S: manufactured by Asahi Kasei Corporation] =
A composite material having a weight ratio of 20/80 was manufactured and evaluated. Table 4 shows the results.

[0204]

Example 46 Nylon 6 [Amilan CM1017: Toray Industries, Inc.] was used instead of nylon 66 used in Example 44.
[Production] was used to obtain a composite material in the same manner as in Example 44. The obtained composite material was injection-molded at 250 ° C. to form a test piece and evaluated. Table 4 shows the results.

[0205]

Example 47 A composite material was obtained in the same manner as in Example 44, except that nylon 6T [Arlen AE4200: manufactured by Mitsui Petrochemical Industry Co., Ltd.] was used instead of nylon 66 used in Example 44. The obtained composite material was injection-molded at 260 ° C. to form a test piece and evaluated. Table 4 shows the results.

[0206]

[Example 48] Polymer 4 (HPCHD: Mn≈10,000) and polymer 27 (St-HCHD) were used as polymer 4 / polymer 2
Dry blend at a ratio of 7 = 10/90 (wt ratio),
Further, this Brent product / modified polyphenylene ether [Zylon X1010: manufactured by Asahi Kasei Corporation] = 20/80
Dry blend at a ratio of (wt ratio), and a 15 mmφ twin-screw extruder [Laboplast mill: manufactured by Toyo Seiki Co., Ltd. (L / D
= 17)] at a temperature of 230 to 280 ° C. and further pelletized to obtain a composite material. The resulting composite material is 28
The test pieces were molded by injection molding at 0 ° C. and evaluated. Table 4 shows the results.

[0207]

Examples 49 to 50 In the same manner as in Example 48, except that polymer I7 (HCHD-St-HCHD) and polymer I9 (HCHD-HSt-HCHD) were used instead of polymer 27 (St-HCHD). Composite materials were manufactured and evaluated. Table 4 shows the results.

[0207]

[Example 51] The composite material 1 obtained in Example 1 was replaced with 10
0.5 parts by weight of 0 parts by weight of vinyltriethoxysilane [A-151: manufactured by Nippon Unicar Co., Ltd.] are dry blended, and a twin-screw kneader [Laboplastomill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)] was melt mixed at a temperature of 280 to 290 ° C. to obtain modified composite material 7.

Further, the modified composite material 7 / polyacetal (POM) [Tenac 3010: manufactured by Asahi Kasei Corporation]
= 20/80 (wt ratio) dry blended, and 200-220 in a 15 mmφ twin-screw extruder [Laboplast Mill: Toyo Seiki Co., Ltd. (L / D = 17)].
The mixture was melt-mixed at a temperature of ° C and further pelletized to obtain a composite material. The obtained composite material was injection-molded at 220 ° C. to form a test piece and evaluated. Table 4 shows the results.

[0209]

Example 52 Modified composite material 7 obtained in Example 51
Modified Composite 7 / Polybutylene Terephthalate (PBT) [Barox 310: GE Plastics. Japan Co., Ltd.] = 20/80 (wt ratio) dry blended, 15 mmφ twin-screw extruder [Laboplast Mill: Toyo Seiki Co., Ltd. (L / D = 1
7)] was melt mixed at a temperature of 280 to 290 ° C. and further pelletized to obtain a composite material. The obtained composite material is 29
The test pieces were molded by injection molding at 0 ° C. and evaluated. Table 4 shows the results.

[0210]

Example 53 Modified composite material 7 obtained in Example 51
Using the modified composite material 7 / polyphenylene sulfide (PPS) [M2588: manufactured by Toray Phillips Petroleum Co., Ltd.] = 20/80 (wt ratio), dry blended, and 15 mmφ biaxial extrusion Machine [Laboplast Mill: Toyo Seiki Co., Ltd. (L / D = 17)]
Melt-mixed at a temperature of 300 to 320 ° C., and further pelletized to obtain a composite material. The obtained composite material was injection-molded at 310 ° C. to mold a test piece and evaluated. Table 4 shows the results
Shown in

[0211]

[Table 4]

[0212]

Example 54 Modified composite material 7 obtained in Example 51
Using modified composite material 7 / polycarbonate [Panlite L-1250: Teijin Chemicals Ltd.] = 20/80
Dry blend so that the ratio becomes (wt ratio), 15
mmφ twin-screw extruder [Laboplast mill: Toyo Seiki Co., Ltd.
Manufactured (L / D = 17)] at a temperature of 300 to 320 ° C. and further pelletized to obtain a composite material. The obtained composite material was injection-molded at 310 ° C. to mold a test piece and evaluated. Table 5 shows the results.

[0213]

Example 55 Modified composite material 7 obtained in Example 51
Modified composite material 7 / polyarylate [U polymer U-100: manufactured by Unitika Ltd.] = 20/80 (wt.
15mmφ by dry blending so that the ratio becomes
Twin-screw extruder [Laboplast Mill: Toyo Seiki Co., Ltd. (L
/ D = 17)] at a temperature of 320 to 360 ° C., and further pelletized to obtain a composite material. The obtained composite material was injection-molded at 350 ° C. to form a test piece and evaluated. Table 5 shows the results.

[0214]

Example 56 Polymer 4 (HPCHD: Mn≈10,000) and polymer 28 (MMA-HCHD) were dry-blended at a ratio of polymer 4 / polymer 28 = 10/90 (wt ratio) to obtain 15 mmφ. In a twin-screw extruder [Laboplast Mill: manufactured by Toyo Seiki Co., Ltd. (L / D = 17)], the mixture was melt-mixed at a temperature of 230 to 250 ° C. to obtain a composite material 20. Composite material 20
/ Polymethylmethacrylate (PMMA) [Delpet 80N: Asahi Kasei Co., Ltd.] = 20/80 (wt ratio)
15mmφ twin-screw extruder [Laboplast mill: manufactured by Toyo Seiki Co., Ltd. (L / D
= 17)] in a temperature range of 230 to 250 ° C.,
Furthermore, it pelletized and obtained the composite material. The obtained composite material was injection-molded at 240 ° C. to form a test piece and evaluated.
Table 5 shows the results.

[0215]

Example 57 Polymer 1 (PCHD: Mn≈10,000) and polymer 2 (PCHD: Mn≈40,000) were dry blended at a ratio of polymer 1 / polymer 2 = 10/90 (wt ratio). 100 parts by weight of the mixture, 2 parts by weight of maleic anhydride, and 0.5 parts by weight of Perhexa 25B [manufactured by NOF CORPORATION], and a 15 mmφ twin-screw extruder [Laboplast Mill: manufactured by Toyo Seiki Co., Ltd. ( L / D = 17)] in a temperature range of 250 to 280 ° C., and the mixture was melted and kneaded to obtain a modified composite material 8. The modified composite material 8 was extracted with hot acetone and vacuum dried at 80 ° C.

When the grafted amount of maleic anhydride was determined with sodium methylate, it was found that 1.5 mol% of maleic anhydride was grafted. 20 parts by weight of the modified composite material 8 and 80 parts by weight of nylon 66 [Leona 1402S: manufactured by Asahi Chemical Industry Co., Ltd.] are dry blended to obtain 15 mmφ.
Twin-screw extruder [Laboplast Mill: Toyo Seiki Co., Ltd. (L
/ D = 17)] at a temperature of 260-280 ° C.,
Furthermore, it pelletized and obtained the composite material. The obtained composite material was compression molded at 280 ° C. to form a test piece and evaluated.
Table 5 shows the results.

[0219]

Example 58 Polymer 1 (PCHD: Mn≈10,000) and polymer 3 (PCHD: Mn≈80,000) were dry blended at a ratio of polymer 1 / polymer 3 = 10/90 (wt ratio). A modified composite material 9 was obtained in the same manner as in Example 57 except that the used one was used (the amount of maleic anhydride added was 1.8 mol).
%). Furthermore, modified composite material 9 / nylon 66 [Leona 1
402S: manufactured by Asahi Kasei Kogyo Co., Ltd.] was dry-blended to obtain a composite material in the same manner as in Example 57. The obtained composite material was compression molded at 280 ° C. to form a test piece and evaluated. Table 5 shows the results.

[0218]

Example 59 A polymer 4 (HPCHD: Mn≈10,000) and a polymer 5 (HPCHD: Mn≈80,000) were dried at a ratio of polymer 4 / polymer 5 = 10/90 (wt ratio%). Blending was carried out in the same manner as in Example 57 to obtain modified composite material 10 (the amount of maleic anhydride added is 0.8 mol%). Furthermore,
Modified Composite 10 / Nylon 6 as in Example 57
6 [Leona 1402S: Asahi Kasei Corporation] = 20 /
A composite material of 80 (wt ratio) was obtained. The obtained composite material was compression molded at 280 ° C. to form a test piece and evaluated. Table 5 shows the results.

[0219]

[Table 5]

[0220]

INDUSTRIAL APPLICABILITY The composite material of the present invention contains at least two kinds of polymers selected from the polymer I and the modified polymer I, so that the excellent thermal and It is possible to develop mechanical properties. It is also possible to mix inorganic reinforcements as needed, making it an excellent industrial material (functional material, structural material), high-performance plastic, general-purpose plastic, special elastomer, thermoplastic elastomer, elastic fiber, sheet, Films, tubes, hoses, optical materials, insulating agents, lubricants, plasticizers, separation membranes, permselective membranes, microporous membranes, functional membranes, functional films (conductive films, photosensitive films, etc.), functional beads (molecules) Sieves, polymer catalysts, polymer catalyst substrates, etc.), automobile parts, electrical parts, aerospace parts, railway parts, marine parts, electronic parts, battery parts, electronics-related parts, multimedia-related parts, plastic battery materials, the sun Battery parts, functional fibers, functional sheets, machine parts, medical device parts, pharmaceutical packaging materials, sustained release packaging materials, pharmacological substance supporting substrates, plugs Cement-based material, food containers, general packaging materials, can be used for clothing, sports and leisure goods, general goods supplies, tires, belts, as a modifying agent, and the like of other resin. INDUSTRIAL APPLICABILITY The novel composite material of the present invention, although it is an olefin-based polymer material, can be widely applied to the main fields of application of polymer materials, and is therefore suitably adopted as an excellent industrial material.

 ─────────────────────────────────────────────────── --Continued from the front page (31) Priority claim number Japanese Patent Application No. 6-311103 (32) Priority date Hei 6 (1994) November 21 (33) Priority claim country Japan (JP) (31) Priority Claim Number Japanese Patent Application No. 6-309410 (32) Priority Date No. 6 (1994) November 21 (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-309411 (32) Priority Hihei 6 (1994) November 21 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-309412 (32) Priority Day Hei 6 (1994) November 21 (33) ) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-311104 (32) Priority date Hei 6 (1994) November 21 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-311105 (32) Priority date No. 6 (1994) November 21 (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-3111152 (32) )priority Hei 6 (1994) November 21 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 6-311153 (32) Priority Day Hei 6 (1994) November 21 (33) Priority claiming country Japan (JP) (31) Priority claiming number Japanese Patent Application No. 6-311154 (32) Priority date Hei 6 (1994) November 21 (33) Priority claiming country Japan (JP) (31) Priority Patent claim number Japanese patent application No. 6-286902 (32) Priority date No. 6 (1994) November 21 (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese patent application No. 7-194415 (32) Priority Day 7 (1995) July 31 (33) Priority claiming country Japan (JP)

Claims (27)

[Claims] 1. A polymer composite material having a polymer chain containing at least two polymers selected from the group consisting of polymers represented by the following formulas (IA) and (IB) and modified polymers. . Embedded image [Here, A to F represent monomer units constituting the polymer main chain, and A to F may be arranged in any order. a ~
f is the monomer units A to F based on the total weight of the monomer units A to F
Represents each wt% of F. The standard polystyrene equivalent number average molecular weight of the polymer is 500 to 5,000,000.
Range. When the polymer represented by the formula (IA) and / or the modified polymer represented by the formula (IB) contains the monomer unit A, at least one of the monomer units A is 1,4-
It is linked to the polymer chain by a bond. (A): 1 type or 2 or more types of cyclic olefin type monomer units (B): 1 type or 2 types or more of cyclic conjugated diene type monomer units (C): 1 type or 2 or more types of chain Conjugated diene monomer unit (D): One or more vinyl aromatic monomer units (E): One or more polar monomer units (F): Ethylene monomer Unit, 1 type or 2 or more types of α
An olefinic monomer unit. A to F satisfy the following relationships. a + b + c + d + e + f = 100, 0 ≦ a, b ≦ 100, 0 ≦ c, d, e, f <100, and a + b ≠ 0 In the formula (IB), S to X represent a modifying group, and each independently represents oxygen (O ), Nitrogen (N), silicon (Si), sulfur (S), phosphorus (P), halogen (F, Cl, Br and I) at least one functional group or an organic compound residue containing a functional group. is there. s to x are represented by the formula (IB) and are wt% of S to X with respect to the modified polymer, and satisfy the following relationships. 0 <s + t + u + v + w <100, and 0 ≦ s, t, u, v, w <100] 2. The polymer composite material according to claim 1, wherein a = 100 in at least one of formulas (IA) and (IB). 3. The polymer composite material according to claim 1, wherein b = 100 in at least one of formulas (IA) and (IB). 4. The polymer composite material according to claim 1, wherein in at least one of formulas (IA) and (IB), a + b = 100 and a> 0. 5. The polymer composite material according to claim 1, wherein 0 <a + b <100 in at least one of formulas (IA) and (IB). 6. A block copolymer according to at least one of formulas (IA) and (IB), wherein the polymer main chain has a block unit containing a monomer unit A and / or a monomer unit B. The polymer composite material according to claim 1, which has a structure. 7. A block copolymer according to at least one of formulas (IA) and (IB), wherein the polymer main chain has a block unit composed of only a monomer unit A and a monomer unit B. The polymer composite material according to claim 6, which has a structure. 8. A block copolymer according to at least one of formulas (IA) and (IB), wherein the polymer main chain has a block unit composed of only a monomer unit A or a monomer unit B. The polymer composite material according to claim 6, which has a structure. 9. In at least one of the formulas (IA) and (IB), the polymer main chain has a block copolymer structure having a block unit composed of only a monomer unit A. The polymer composite material according to claim 8, wherein 10. In at least one of the formulas (IA) and (IB), the polymer main chain has a block copolymer structure having a block unit composed of only the monomer unit B. The polymer composite material according to claim 8, wherein 11. At least one of the polymers represented by formulas (IA) and (IB) and the modified polymer is a polymer composed of only monomer units A and / or monomer units B. The polymer composite material according to claim 1, wherein at least one of the other is a block copolymer having a block unit containing a monomer unit A / or a monomer unit B. 12. At least one of the polymers represented by the formulas (IA) and (IB) and the modified polymer is a polymer composed of only the monomer unit A and / or the monomer unit B. The polymer according to claim 11, wherein at least another one is a block copolymer having two or more block units containing the monomer unit A / or the monomer unit B. Composite material. 13. At least one of the polymers represented by formulas (IA) and (IB) and the modified polymer is a polymer composed of only monomer units A and / or monomer units B. And at least one other is a triblock copolymer having two or more block units containing a monomer unit A / or a monomer unit B. Molecular composite material. 14. In at least one of formulas (IA) and (IB), the monomer unit A is a monomer unit represented by the following formula [II], and the monomer unit B is I
The polymer composite material according to any one of claims 1 to 13, which is a monomer unit represented by the formula [II]. Embedded image Embedded image [In the formulas [II] and [III], n represents an integer of 1 to 4. R ¹ is independently a hydrogen atom, a halogen atom, or C
₁ -C ₂₀ alkyl, C ₂ -C unsaturated aliphatic hydrocarbon group of _20, C ₅ -C ₂₀ aryl group, C ₃ -C ₂₀ cycloalkyl group, cyclodienyl group of C ₄ -C _20, Or 5
It is a heterocyclic group which is a 10-membered ring and contains at least one nitrogen, oxygen or sulfur as a hetero atom, and R ² is each independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, C ₂ To C ₂₀ unsaturated aliphatic hydrocarbon groups, C _{5 to} C
₂₀ aryl groups, C ₃ -C ₂₀ cycloalkyl groups, C ₄
To C ₂₀ cyclodienyl group or a 5 to 10-membered heterocyclic group containing at least one nitrogen, oxygen or sulfur as a hetero atom. ] 15. In at least one of formulas (IA) and (IB), the monomer unit A is a monomer unit represented by the following (IV), and the monomer unit B is The polymer composite material according to claim 14, which is a monomer unit represented by formula (V). Embedded image Embedded image [In the formulas (IV) and (V), each R ² has the same definition as in the formula [II]. ] 16. A monomer unit A contained in a polymer chain
And / or the monomer unit B comprises 1,2-bonds and 1,4
-Linked to the polymer chain by a bond, 1,2-bond and 1,
1 to 99 mo of 1,2-bond relative to the total amount of 4-bond
It exists in the range of 1%, It is characterized by the above-mentioned.
One polymer composite material according to any one of 1. 17. The polymer composite according to claim 16, wherein the 1,2-bond is present in the range of 5-95 mol% with respect to the total amount of the 1,2-bond and the 1,4-bond. material. 18. The polymer composite according to claim 17, wherein the 1,2-bond is present in the range of 10 to 90 mol% with respect to the total amount of the 1,2-bond and the 1,4-bond. material. 19. In formula (IB), S to X are each independently a hydroxyl group, an ether group, an epoxy group, a carboxylic acid group, an ester group, a carboxylate group, an acid anhydride group, an acid halogen compound group, an aldehyde group. , Carbonyl group, amino group, amide group, imide group, imino group, oxazoline group,
Hydrazine group, hydrazide group, amidine group, nitrile group, nitro group, isocyano group, cyanato group, isocyanato group, silyl group, silyl ester group, silyl ether group, silanol group, thiol group, sulfide group, thiocarboxylic acid group, dithiocarboxylic group A functional group selected from an acid group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a thiocyanato group, an isothiocyanato group, a thioaldehyde group, a thioketone group, a phosphoric acid group, a phosphonic acid group, and a phosphinic acid group, or a functional group. The polymer composite material according to any one of claims 1 to 13, which is an organic compound residue contained therein. 20. In formula (IB), S to X are each independently a hydroxyl group, an epoxy group, a carboxylic acid group, an ester group, a carboxylic acid group, an acid anhydride group, an amino group, an amide group, an imide group, or imino. Group, oxazoline group, hydrazine group, hydrazide group, isocyano group, cyanato group, isocyanato group, silyl group, silyl ester group, silyl ether group, silanol group, thiol group, sulfide group, thiocarboxylic acid group, sulfonic acid group 14. The polymer composite material according to claim 1, wherein the polymer composite material is a functional group containing a functional group, or an organic compound residue containing a functional group. 21. A polymer represented by formulas (IA) and (IB) and a polymer represented by formulas (IA) and (IB), respectively, in which the ratio of the minimum amount of the polymer in the modified polymer is represented by formulas (IA) and (IB), respectively. And 1% by weight or more with respect to the total amount of the modified polymer, The polymer composite material according to claim 1. 22. A polymer represented by formulas (IA) and (IB), which further contains a polymer other than the polymers represented by formulas (IA) and (IB) and the modified polymer, respectively. 2. The polymer composite material according to claim 1, wherein the total content of the modified polymer is at least 1 wt% or more based on the total amount of the polymer, the modified polymer and the other polymer. 23. The polymer composite material according to claim 22, wherein the other polymer is a thermoplastic resin or a curable resin. 24. The polymer composite material according to claim 23, wherein the other polymer is a thermoplastic resin. 25. The thermoplastic resin is an olefin polymer, a styrene polymer, a conjugated diene polymer, a hydrogenated conjugated diene polymer, a (meth) acrylate polymer,
From (meth) acrylonitrile-based polymer, vinyl halide-based polymer, ester-based polymer, ether-based polymer, amide-based polymer, imide-based polymer, sulfide-based polymer, sulfone-based polymer, ketone-based polymer The polymer composite material according to claim 24, which is at least one polymer selected from the group consisting of: 26. At least one of S to X in the formula (IB) is a hydroxyl group, an epoxy group, a carboxylic acid group, an ester group, a carboxylate group, an acid anhydride group, an amino group, an amide group, an imide group or an imino group. , Oxazoline group, isocyano group, cyanato group, isocyanato group, silyl ester group,
At least one functional group selected from the group consisting of silyl ether group, silanol group, thiol group, sulfide group, thiocarboxylic acid group, and sulfonic acid group, or an organic compound residue containing the functional group (IB) formula In at least one of the modified polymer represented by a hydroxyl group, a carboxyl group and an ester-based polymer containing at least one functional group selected from the group consisting of an ester group, a hydroxyl group and
/ Or an ether polymer containing an ether group, an amide polymer containing at least one functional group selected from the group consisting of an amino group, a carboxyl group and an amide group, and a thiol group and / or a sulfide group At least one of the other polymers selected from the group consisting of sulfide polymers, the functional group of the modified polymer or at least one of the organic compound residues, and at least one of the other polymers. The reaction product obtained by reacting one of them is a polymer represented by the formulas (IA) and (IB), a modified polymer, another polymer, or 0.001 to the total weight of the reaction product. 26. The polymer composite material according to claim 25, which is present in the range of 100 wt%. 27. At least one of S to X in the formula (IB) is a hydroxyl group, an epoxy group, a carboxylic acid group, an ester group, a carboxylate group, an acid anhydride group, an amino group, an amide group, an imide group or an imino group. , Oxazoline group, isocyano group, cyanato group, isocyanato group, silyl ester group,
Modification represented by formula (IB), which is a functional group selected from the group consisting of silyl ether group, silanol group, thiol group, sulfide group, thiocarboxylic acid group, and sulfonic acid group, or an organic compound residue containing a functional group At least one type of polymer and hydroxyl group, epoxy group, carboxylic acid group, ester group, carboxylic acid group, acid anhydride group, amino group, amide group, imide group, imino group, oxazoline group, isocyano group, cyanato group, isocyanato group , Silyl ester group,
A modified olefin polymer having at least one functional group selected from the group consisting of a silyl ether group, a silanol group, a thiol group, a sulfide group, a thiocarboxylic acid group, and a sulfonic acid group, or an organic compound residue containing a functional group. , Modified styrene polymer, modified conjugated diene polymer,
Containing at least one other modified polymer selected from the group consisting of a modified hydrogenated conjugated diene-based polymer, a modified ether-based polymer and a modified sulfide-based polymer;
B) A reaction product of at least one of the functional group and the organic compound residue of the modified polymer represented by the formula and another modified polymer is represented by the formulas (IA) and (IB), respectively. 26. The polymer composite material according to claim 25, which is present in an amount of 0.001 to 100 wt% based on the total weight of the composite material of the polymer, the modified polymer, the other polymer, and the reaction product.