JP2003268108A - Compatibilizer, plastic material, recycled plastic material and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plastic material using a silicon material having an Si-Si bond as a compatibilizer or modifier, a recycled plastic material and a plastic molding composed of the plastic material. <P>SOLUTION: The compatibilizer comprises a silicon material, preferably a polysilane expressed by the general formula (1): (R<SP>1</SP>R<SP>2</SP>Si)<SB>x</SB>(R<SP>3</SP>Si)<SB>y</SB>(Si)<SB>z</SB>(wherein R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are the same or different and each represents a hydrogen atom, hydroxy group, alkyl group, alkenyl group, alkoxy group, aryl group or silyl group; x, y and z each denotes a number of zero or ≥1 provided that the sum of x, y and z is 5 to 400). The plastic material comprises one or more kinds of polymer and the compatibilizer. The compatibilizer can be applied to a virgin resin or a used resin. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a plastic material using a silicon material having a Si--Si bond as a compatibilizer or a modifier, a recycled plastic material, and a plastic molded body composed of the plastic material. Regarding

[0002]

2. Description of the Related Art In recent years, from the viewpoints of protection of the global environment, effective use of resources, that is, recycling, waste disposal, etc., the reuse and reuse of waste plastic has become an important issue. However, the reuse of plastic products has an extremely large technical problem, and the reuse is almost not performed except for the recycling of PET (PET) bottles. That is, in the prior art, even if it consists of a transparent single resin without additives like PET bottles, and the contents when used are extremely clean, coloring and various physical property deterioration due to viscosity decrease during reuse are avoided. I can't. as a result,
Since recycled products with sufficient performance cannot be obtained as products, considering the recovery cost of used products, the appearance and quality of recycled products, even PET bottles are still a sufficiently practical recycling system. Absent.

Furthermore, when reusing plastic products other than PET bottles, coloring and deterioration of physical properties cannot be avoided because these plastic products contain many additives and consist of various resins. That is, regarding plastic products other than PET bottles, the safety, productivity, and quality of recycled products are insufficient for practical use, and the recycling cost is also high, and a recycling system has not yet been established.

It is difficult to completely separate and collect waste plastics, and a plurality of polymers are usually mixed in the recycling process. Therefore, the polymer properties of the recycled plastic deteriorate. Although a large amount of a plasticizer such as oil is blended during plastic recycling to prevent deterioration of physical properties, it is difficult to restore the original physical properties.

Further, if the plural kinds of polymers mixed at the time of recycling are different polymers which are incompatible with each other, a uniform dispersion cannot be obtained, and the physical properties of the polymer of the recycled plastic are significantly lowered. As described above, since the polymer properties of recycled plastic are low, the recycled plastic can be used only for a limited number of applications where the physical properties are low.

Under such circumstances, the recycling of waste plastic is still at a very low level, which is a major cause of environmental and resource problems.

On the other hand, various plastic products are often required to have flame retardancy. In order to impart flame retardancy to the plastic molded body, it is generally considered to add a flame retardant to the plastic material. However, when a flame retardant is mixed with a plastic material, the physical properties of the plastic are likely to be deteriorated. In particular, if the plastic material contains different polymers that are incompatible with each other, a uniform dispersion of the different polymers cannot be obtained, and the physical properties of the plastic are further significantly deteriorated by blending the flame retardant. The problem of deterioration of physical properties due to the incorporation of the flame retardant becomes more serious in the case of recycled plastic material from waste plastic than in the case of virgin plastic material.

Further, various plastic products are often required to have improved strength, heat resistance, water resistance, warm water resistance, moisture resistance, and other various performances and functions. In such a case, it is possible to mix various inorganic fillers with the plastic material according to various performances and functions. However, when an inorganic filler is added to a plastic material, the physical properties of the plastic are likely to be deteriorated as in the flame retardant.

Under these circumstances, there has been a demand for the development of a technique for imparting flame retardancy without deteriorating the physical properties of the plastic even when the flame retardant is mixed with the plastic material.
Especially when recycling waste plastics and recycling, even when different polymers are mixed, especially even when incompatible different polymers are mixed,
There is a demand for development of a technique that imparts flame retardancy without causing deterioration of polymer physical properties. Further, there is a demand for the development of a technique in which even if various inorganic fillers are mixed with a plastic material, the physical properties of the plastic are not deteriorated and various performances and functions are imparted.

[0010]

Therefore, an object of the present invention is to provide a plastic material using a silicon material having a Si--Si bond as a compatibilizer or modifier, a recycled plastic material, and the above plastic material. It is to provide a configured plastic molded body.

Further, an object of the present invention is to provide a flame-retardant plastic material having high physical properties, a flame-retardant recycled plastic material having high physical properties, and a flame-retardant plastic molded product composed of the plastic material. To do. Another object of the present invention is to provide a plastic material containing an inorganic filler, a recycled plastic material containing an inorganic filler, and a plastic molded product containing an inorganic filler composed of the plastic material. .

[0012]

The present invention includes the following inventions. (1) A compatibilizer made of a silicon material having a Si-Si bond. (2) A silicon material having a Si—Si bond has the general formula (I):

[Chemical 3] (In the formula (I), R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a silyl group, x, y and z each represent a number of 0 or 1 or more, and the sum of x, y and z is 5 to 400), and the compatibilizing agent according to (1).

(3) Polysilane has the following formula (II):

[Chemical 4] The compatibilizing agent according to (2), which is a linear polysilane having a structural unit of methylphenylsilane represented by

(4) At least one compatibilizer selected from the group consisting of an ionomer resin-based compatibilizer, a reactive compatibilizer, an elastomer-based compatibilizer, an oxazoline-based compatibilizer, and a copolymer-based compatibilizer. Further including (1)-
The compatibilizer according to any one of (3).

(5) One or more polymers,
A plastic material containing the compatibilizer according to any one of (1) to (4). (6) The plastic material according to (5), which further contains a flame retardant. (7) (5) or (6) further containing an inorganic filler
Plastic material described in.

(8) The plastic material according to any one of (5) to (7), wherein all of the one or more polymers are virgin polymers. (9) The plastic material according to any one of (5) to (7), wherein at least one of the one or more polymers is a used polymer. (10) The plastic material according to (9), wherein all of the one or more polymers are used polymers.

(11) The plastic material according to any one of (5) to (10), wherein the plastic material contains a plurality of kinds of polymers, and the plurality of kinds of polymers include different polymers incompatible with each other. . (12) The plastic material according to any one of (5) to (11), wherein the plastic material includes a plurality of types of polymers, and the plurality of types of polymers include mutually compatible different polymers.

(13) The one or more polymers are
The plastic material according to any one of (5) to (12), which is selected from a thermoplastic polymer and / or a thermosetting polymer.

(14) One or a plurality of polymer materials, at least one of which has been used, including (1) to
A recycled plastic material obtained by blending the compatibilizer according to any one of (4), a flame retardant if necessary, and an inorganic filler as necessary.

(15) A plastic molded body made of the plastic material according to any one of (5) to (14). When a flame retardant is included, it becomes a flame-retardant plastic molding.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a silicon material having a Si--Si bond is used as a compatibilizer. As the silicon material, a linear chain having a Si-Si bond,
It is not particularly limited as long as it is a cyclic, branched or network polysilane compound, but the polysilane represented by the general formula (I) is used.

In the general formula (I), R ¹ , R ² and R
³ may be the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a silyl group.

Examples of the alkyl group include linear, cyclic or branched alkyl groups having about 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methyl, ethyl and n-.
Examples include propyl, iso-propyl, n-hexyl group, cyclohexyl group and the like. Examples of the alkenyl group include a monovalent linear, cyclic or branched alkenyl group having at least one carbon-carbon double bond and having about 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms. , Vinyl, allyl groups and the like. As an alkoxy group,
A linear, cyclic or branched C1-C10 alkoxy group, preferably a C1-C6 alkoxy group, may be mentioned, for example,
Examples include methoxy, ethoxy, n-propyloxy, iso-propyloxy and the like. Examples of the aryl group include a phenyl group and a naphthyl group. The silyl group has about 1 to 10 silicon atoms, preferably 1 to 6 silicon atoms.
The silyl group of The above alkyl group, alkenyl group, alkoxy group, aryl group or silyl group may have at least one substituent, and such substituents include the same alkyl groups, aryl groups,
Functional groups such as alkoxy groups can be mentioned.

R ¹ , R ² and R ³ may be the same or different. Further, R ^{1 s} and / or R ^{2 s} may be different in the structural unit —R ¹ R ² Si—, and R ^{3 s} may be different in the structural unit —R ³ Si—. Such polysilane can be obtained by using different corresponding raw materials (for example, halosilanes).

The molecular terminal of polysilane is present when the structure of polysilane is other than cyclic (linear, branched or network), but the terminal substituent is usually a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group or a silyl group. It is a base.

Polysilanes in which R ¹ , R ² and R ³ are as described above are effective as compatibilizers, but R ¹ , R ²
Those in which at least one of R ³ and R ³ is an aryl group are preferable, and those in which a phenyl group is particularly preferable.

More specific polysilanes include cyclic polydiphenylsilane (5- to 8-membered ring), linear polymethylphenylsilane (terminal trimethylsilyl group), linear polymethylphenylsilane (terminal hydroxyl group), polyphenyl. Examples thereof include silane (terminal hydroxyl group) and polydiphenylsilane / polyphenylsilane copolymer (terminal hydroxyl group).
Among them, linear polymethylphenylsilane, which is a polysilane having a structural unit of methylphenylsilane represented by the formula (II), is preferable, and linear polymethylphenylsilane (terminal hydroxyl group or terminal alkyl group) is More preferable.

In the general formula (I), x, y and z each represent a number of 0 or 1 or more, and the sum of x, y and z is 5 to 5.
It is 400. The number average molecular weight of polysilane is 3
It is about 100 to 100,000, preferably about 500 to 20,000, and more preferably about 500 to 3,000 from the viewpoint of the function as a compatibilizer.

In order to produce these polysilanes, for example, a method of dehalogenating polycondensation of halosilanes using a silicon-containing monomer having a specific structural unit as a raw material and magnesium as a reducing agent ("magnesium reduction method" International Publication Number) WO98 / 29476), a method for dehalogenating polycondensation of halosilanes in the presence of an alkali metal ("kipping method" J. Am. Chem. Soc., 110, 124 (198).
8), Macromolecules, 23, 3423 (1990)), a method of dehalogenating polycondensation of halosilanes by electrode reduction (J.Ch.
em.Soc., Chem.Commun., 1161 (1990), J.Chem.Soc., C
hem.Commun., 897 (1992)), a method for dehydrogenative condensation polymerization of hydrazines in the presence of a metal catalyst (JP-A-4-334).
No. 551), a method by anionic polymerization of disylene cross-linked with biphenyl or the like (Macromolecules, 23, 4494).
(1990)), a method such as ring-opening polymerization of cyclic silanes is adopted.

Among these polysilane production methods, the polysilane produced is excellent in purity, molecular weight distribution, compatibility with resin, production cost, production safety, and industrial production method. The "magnesium reduction method" is the most preferable.

Polysilane is likely to exhibit a function as a compatibilizing agent because a part of the Si-Si bond is cleaved by heating at 200 ° C. or higher to generate reaction active species. Therefore, appropriate compatibility can be obtained by heating at the time of melting and kneading with the polymer species. Further, even if the Si-Si bond is not broken, it has a function of improving the uptake of foreign matter and plasticity.

In the present invention, the plastic material contains one or more polymers and the polysilane compatibilizer.

In the present invention, the one or more polymers include, but are not limited to, various thermoplastic polymers, thermosetting polymers, materials including polymeric materials such as rubber, and the like. Plastic polymers are preferred. As the thermoplastic polymer, a commercially available polymer or a newly synthesized polymer can be used.

Specific examples of the polymer material include polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, polybutadiene and acrylonitrile.
Butadiene-styrene copolymer (ABS), polystyrene (PS), ACS resin, AS resin, polybutene resin,
Alkyd resin, amino resin, ASA resin, bismaleimide triazine resin, chlorinated polyether, chlorinated polyethylene, allyl resin, epoxy resin, ethylene-α-olefin copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, ethylene -Vinyl chloride copolymer, EVA resin, FRP, ionomer, methacryl-styrene copolymer, nitrile resin, polyester [polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc.], olefin vinyl alcohol copolymer, petroleum resin , Phenol resin, polyacetal, polyacrylate, polyamide (PA), polyallylsulfone, polybenzimidazole, polybutylene, polycarbonate (PC), polyetheretherketone, polyetherketone, po Ether nitrile, polyether sulfone, polyketone, methacrylic resin, polymethylpentene, polyphenylene ether, polyphenylene sulfide, polysulfone, SAN resin, butadiene-styrene resin, polyurethane, polyvinyl acetal, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, silicone Resin, polyvinyl acetate, xylene resin, cross-linked polyolefin such as cross-linked polyethylene, cross-linked polystyrene, unsaturated polyester resin, urea resin, melamine resin, fluororesin, thermoplastic elastomer, EPDM, CR, BR, nitrile rubber, natural rubber,
Examples thereof include acrylonitrile butadiene rubber and butyl rubber. These are exemplary and also include various other polymers.

Of the above, most of them are of thermoplastic type, and include bismaleimide triazine resin, epoxy resin,
FRP, phenol resin, unsaturated polyester resin, urea resin and melamine resin are thermosetting type. In addition, polyurethane, silicone resin, xylene resin,
There are thermoplastic type and thermosetting type.
For the thermosetting type, it is preferable to use a crushed product. In addition, it is preferable to use a crushed product for crosslinked polyolefin such as crosslinked polyethylene and crosslinked polystyrene.

In the present invention, the above-mentioned polymer may be an unused resin (Virgin resin) or a used recovered resin. That is, the present invention includes a form in which all of the one or more polymers are unused polymers, and a form in which at least one of the one or more polymers is a used polymer, Also included are forms in which all of the one or more polymers are spent polymers. Although not particularly limited, the effect of the present invention is particularly obtained when the recovered resin is included. The recovered resin is often in the form of a mixture of different types of resins, and conventionally, good compatibility was not obtained, but in the present invention, good compatibility is obtained by the inclusion of the polysilane compatibilizer described above, and physical properties are A recycled plastic material is obtained without any deterioration.

In the present invention, in addition to the polysilane compatibilizing agent, an ionomer resin-based compatibilizing agent (A), a reactive compatibilizing agent (B), an elastomer may be added depending on the kind of one or more kinds of polymers. You may mix | blend at least 1 sort (s) of compatibilizer selected from the group which consists of a system compatibilizer (C), an oxazoline compatibilizer (D), and a copolymer system compatibilizer (E). By using these compatibilizers (A) to (E) together, better compatibility may be obtained, and the physical properties of the obtained plastic material may be improved.

In the present invention, the ionomer resin-based compatibilizer (A) includes various types.
A typical ionomer is (a) a polymer having a side chain ionic group partially present in the main chain (side chain type). Another type of ionomer is a polymer (telechelic type) obtained by neutralizing (b) a host polymer or an oligomer having carboxylic acid groups at both ends with a metal ion being neutralized. Another type of ionomer is (c) having a cation in the main chain and having an anion bound thereto (ionene).

[0039]

[Chemical 5]

Counterion to the ionic group of the host polymer
As Li⁺, Na⁺, K⁺Alkali metal Io, etc.
Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺Alkaline earth such as
Metal ion, Zn²⁺, Cu²⁺, Mn²⁺, Ni²⁺, C
o²⁺, Co³⁺, Fe³⁺, Cr³⁺For transition metal ions such as
Can be Also, for cationic host polymers, C
l ^-, Br^-, I^-And the like anions are used.

The ionomer resin is not particularly limited, but examples thereof include an ethylene-methacrylic acid copolymer ionomer, an ethylene-acrylic acid copolymer ionomer, a propylene-methacrylic acid copolymer ionomer, and a propylene-acrylic acid copolymer. Polymer ionomer, butylene-acrylic acid copolymer ionomer, ethylene-vinyl sulfonic acid copolymer ionomer, styrene-methacrylic acid copolymer ionomer, sulfonated polystyrene ionomer, fluorine-based ionomer, telechelic polybutadiene acrylic acid ionomer, sulfonated Ethylene-propylene-diene copolymer ionomer, hydrogenated polypentamer ionomer, polypentamer ionomer, poly (vinylpyridinium salt) ionomer, poly (vinyl (Trimethylammonium salt) ionomer, poly (vinylbenzylphosphonium salt) ionomer, styrene-butadiene acrylic acid copolymer ionomer, polyurethane ionomer, sulfonated styrene-2-acrylamido-2-methylpropanesulfate ionomer, acid-amine ionomer, fat Examples include group-type ionene and aromatic-type ionene.

These ionomer resins have the effect of compatibilizing different polymers that are incompatible with each other. One of these ionomer resins may be used as a compatibilizer or a modifier for plastic recycling, and two or more thereof may be mixed and used as necessary.

Among these ionomer resins, ethylene-methacrylic acid copolymer ionomers and ethylene-acrylic acid copolymer ionomers are preferably used. These are particularly effective in improving the compatibility between the aliphatic polymer and the aromatic polymer and the compatibility between the polar polymer and the nonpolar polymer. As the ethylene-methacrylic acid copolymer ionomer, more specifically, high-miran 15
54, High-Milan 1555, High-Milan 1557, High-Milan 160
1, high milan 1605, high milan 1650, high milan 165
2, Himiran 1652 SR, Himiran 1652 SB, Himiran 1702, Himiran 1705, Himiran 1706, Himiran 1707, Himiran 1855, Himiran 1856 (above, manufactured by Mitsui DuPont Polychemical Co., Ltd.).

The reactive compatibilizing agent (B) is a polymer having a double bond, a carboxyl group, an epoxy group, etc., and is reacted with one or both of the polymers to be compatibilized in the molding process and grafted. Alternatively, it acts as a compatibilizer by acting as a surfactant based on a block structure (reference: “Polymer alloy”, basics and applications, edited by The Polymer Society of Japan, published in 1993). Examples of the reactive compatibilizer (B) include the following types B1 to B5.

B1 type: ethylene glycidyl methacrylate copolymer (E-GMA; copolymerization weight composition, for example, E / GMA = 100/6 to 12), ethylene glycidyl methacrylate-vinyl alcohol copolymer (E-GM
A-VA; copolymerization weight composition, for example E / GMA / VA =
100 / 3-12 / 8-5), ethylene glycidyl methacrylate-methacrylate copolymer (E-GMA-M
A: copolymer weight composition, for example E / GMA / MA = 100
/ 3 to 6/30) and the like. Specific examples include Sumitomo Chemical's, Bond First E, Bond First 2C; Nippon Polyolefin, Lexpearl RA, Lexpearl ET, Lexpearl RC.

B2 type: ethylene maleic anhydride ethyl acrylate copolymer (E-MAH-EA; manufactured by Sumitomo Chemical Co., Ltd., Bondyne) and the like.

B3 type: ethylene glycidyl methacrylate-acrylonitrile styrene (EGMA-AS;
Copolymer weight composition, eg EGMA / AS = 70/3
0), ethylene glycidyl methacrylate-polystyrene (EGMA-PS; copolymerization weight composition, for example, EGMA
/ PS = 70/30), ethylene glycidyl methacrylate-polymethyl methacrylate (EGMA-PMM)
A, for example, EGMA / PMMA = 70/30). Specific examples include NODI and Modiper.

B4 type: acid-modified polyethylene wax (APEW; manufactured by Mitsui Chemicals, high wax) and the like.

B5 type: COOH-modified polyethylene graft polymer, COOH-modified polypropylene graft polymer and the like.

As the elastomer-based compatibilizer (C),
For example, the following types C1 to C3 may be mentioned. C1
Examples of the type include styrene-ethylene-butadiene copolymer (SEB; manufactured by Asahi Kasei Kogyo, Tuftec). Examples of C2 type include styrene-ethylene-butadiene-styrene copolymer (SEBS; manufactured by Asahi Kasei Corporation). Examples of C3 type include hydrogenated styrene-isopropylene-styrene copolymer (H-SIS).

As the oxazoline-based compatibilizer (D),
For example, the following types D1 to D2 may be mentioned. D1
Examples of the type include bisoxazoline / styrene / maleic anhydride copolymer (OXZ; manufactured by Mikuni Pharmaceutical). As D2 type, bisoxazoline / maleic anhydride modified polyethylene [OXZ (manufactured by Mikuni Pharmaceutical) and PE
(Blend with Sanyo Kasei, Yumex 2000)
Etc. Examples of the D3 type include bisoxazoline / maleic anhydride-modified polypropylene [blend of OXZ (manufactured by Mikuni Pharmaceutical Co., Ltd.) and PP (manufactured by Sanyo Kasei, Umex 1010)].

Examples of the copolymer-based compatibilizer (E) include polyethylene-polyamide graft copolymer (PE
-PA GP), polypropylene-polyamide graft copolymer (PP-PA GP) and the like. Also,
It contains at least one group selected from the group consisting of an alkoxy group, an amino group, a mercapto group, a vinyl group, an epoxy group, an acetal group, a maleic acid group, an oxazoline group and a carboxylic acid group, and has a low melt flow rate of 1 or more. Viscosity copolymer polymers can be mentioned, and specifically, methyl methacrylate-butadiene-styrene resin, acrylonitrile-butadiene rubber, EVA / PVC / graft copolymer, vinyl acetate-ethylene copolymer resin, ethylene-α- Examples thereof include olefin copolymers, propylene-α-olefin copolymers, hydrogenated styrene-isopropylene-block copolymers and the like.

The compounding amount of the compatibilizer may be appropriately determined depending on the type of plastic to be recycled, the type and amount of other polymer mixed therein, or the type and amount of other polymer to be mixed. If the other type of polymer is a polymer of the same family as the main plastic to be recycled (that is, a polymer that is relatively compatible), it is preferable to use a relatively small amount of the compatibilizer.
On the other hand, if the other type of polymer is a polymer that is incompatible with the main plastic to be recycled, it is advisable to use a large amount of the compatibilizing agent as compared with the case of the polymer of the same series. Further, when the amount of the other polymer mixed into the main plastic increases, it is generally necessary to increase the amount of the compatibilizer compounded. The same applies when the polymer is unused.

The amount of the polysilane compatibilizing agent to be blended is appropriately determined from the above viewpoint, but is usually 0.1 parts by weight of polysilane with respect to 100 parts by weight of one or more (recycled or unused) polymers. To 100 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight,
More preferably, 1 to 15 parts by weight is blended. If the amount of polysilane is less than 0.1 part by weight, it is difficult to obtain the compatibilizing effect,
On the other hand, if the amount of polysilane exceeds 100 parts by weight, not only the compatibilizing effect is saturated, but also the heat resistance is lowered and the cost is increased, which is not preferable. In particular, it is necessary to determine the amount of polysilane used in consideration of the productivity and the quality and performance of the target object for each application.

In addition to the polysilane compatibilizer, the other compatibilizers (A), (B), (C), (D) and / or
Or, when (E) is blended, the amount of the other compatibilizer to be blended is
The amount may be 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 1 part by weight of polysilane. However,
The total amount of the compatibilizer used is preferably 100 parts by weight or less based on 100 parts by weight of the one or more kinds of polymers. If the total amount of compatibilizer exceeds 100 parts by weight,
Not only is the compatibilizing effect saturated, the heat resistance decreases and the cost increases, which is not desirable.

In the present invention, specific examples of the polymer to which polysilane is preferably applied include polyolefins such as polyethylene and polypropylene, and recycled plastic materials of one or more kinds of polyolefins, and molded products thereof can be obtained. .

In the present invention, the combination of different polymers incompatible with each other to which the compatibilizing agent is preferably applied includes
Examples include aliphatic polymers and aromatic polymers, polar polymers and non-polar polymers, combinations of polyolefin resins and engineering plastics, and new or recycled plastic materials based on these resins, and molded articles from them are obtained. To be

More specifically, the polyolefin resin mainly includes polypropylene, extremely low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene and the like, and mixtures thereof. Engineering plastics include ABS resin, polyamide, polycarbonate, modified polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyetherimide, polysulfone, polyetherimide, polyacetal polyarylate, polyetheretherketone, polystyrene, polyimide, and mixtures thereof. Is included.

More specifically, for example, PE and PET,
PP and PET, PE and ABS, PP and ABS, PS and A
BS, PC and ABS, PET and ABS, PS and PE, P
S and PP, PS and PET, PC and PE, PC and PP, P
A combination of C and PET and PA and PET can be mentioned. These polymers are well applicable to various polymers recovered after use. Of course, in addition to these, various combinations exist, and it is applicable to not only two kinds of different polymers but also combinations of three or more kinds of different polymers.

Conventionally, in the recycling of these materials, since a waste polymer contains a different polymer, a molded product or material made of recycled plastic having sufficiently high physical properties cannot be obtained. INDUSTRIAL APPLICABILITY According to the present invention, a waste plastic containing a different polymer can be compatibilized, and a recycled plastic material having sufficiently high physical properties and a molded article composed thereof can be obtained.

In the present invention, the plastic material includes
In addition to the compatibilizer, a flame retardant and / or an inorganic filler may be included as a modifier or additive for plastic recycling, if necessary.

The flame retardant is not particularly limited, and various types of flame retardants, that is, a boric acid-based flame retardant compound,
Phosphorus flame retardant compound, inorganic flame retardant compound other than the above boric acid flame retardant compound and phosphorus flame retardant compound, Chisso flame retardant compound, halogen flame retardant compound, organic flame retardant compound and colloidal flame retardant substance Various flame retardants selected from the group consisting of are included.

The inorganic filler is used to improve strength, heat resistance,
To improve water resistance, warm water resistance, and moisture resistance,
Alternatively, it is added to improve various other performances and functions. For example, oxides, hydroxides, carbonates, sulfates,
The plastic material may contain various inorganic fillers selected from silicates, nitrides, carbons, metal powders, ceramic powders and the like.

In the present invention, the amount of the flame retardant added to one or more kinds of polymer materials is not particularly limited because it depends on the desired flame retardancy, but it is usually based on 100 parts by weight of the polymer material. Flame retardant 0.1-20
By blending 0 part by weight, preferably 1 to 100 parts by weight, good flame retardancy is often obtained.

In the present invention, the amount of the inorganic filler added to one or more kinds of polymer materials is not particularly limited because it varies depending on the desired physical properties, performance, function and type of the inorganic filler, but , Polymer material 1
In many cases, good physical properties, performance, and function can be obtained by adding 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight, of inorganic filler to 100 parts by weight.

In the present invention, when both the flame retardant and the inorganic filler are added, the total amount of the flame retardant and the inorganic filler added to one or more polymer materials is from the viewpoint of dispersibility in the polymer material. The total amount added is preferably up to 200 parts by weight, more preferably up to 100 parts by weight, based on 100 parts by weight of the polymer material.

In the present invention, the plastic material includes
Still other additives, such as antioxidants, antioxidants,
Antiozonants, UV absorbers, light stabilizers, tackifiers, plasticizers, softeners, stabilizers, lubricants, mold release agents, antistatic agents, modifiers, colorants, coupling agents, preservatives, anti-prevention agents. You may mix | blend additives, such as a mold agent, suitably.

By using the compatibilizing agent, any plural kinds of polymers are compatibilized, and if necessary,
Since flame retardants and / or inorganic fillers can be mixed and dispersed, it is possible to recycle polyolefin resins and engineering plastics that have a large amount of waste and are strongly requested to be reclaimed. The advantage of applying the present invention is great in obtaining various molded articles and various materials to which the performance and function of (1) are given.

The compounding method is not particularly limited, and the usual melt-kneading method can be used. For example, kneading may be performed with a kneader such as a roll kneader, a Banbury mixer, an intermix, a single-screw extruder, or a twin-screw extruder. The kneading may be performed using one kind of kneader selected from the above kneaders, or may be performed using two or more kinds of kneaders. For the mixing of the polymer resin, the pre-mixed master chip can be used as it is or can be used by diluting it, or the mixed resin and the compatibilizing agent can be put into an extruder or a molding machine for producing a target molded article. It can also be molded.

In the present invention, a plastic material containing one or more kinds of polymers and the compatibilizing agent is molded by a conventional method into various molded articles. It is also possible to add an additive to the plastic material, if necessary, to form a coating material, a coating material or an adhesive material.

Various molded articles made of the plastic material can be manufactured by a conventional molding method. For example, a hollow or solid extrusion molded product having various sectional shapes such as a tubular shape, a rectangular shape, various injection molded products, blow molded products, a sheet or film extruded from a T-die, or a melt spinning method. Multifilament,
Fibrous structures such as monofilaments, flat yarns, staple fibers, spunbonded nonwoven fabrics, flash-spun nonwoven fabrics, and various foam-molded products can be obtained.

As various materials from the plastic material, at least one surface of a coating material for an organic or inorganic linear material or a twisted string material, a metal plate, a plastic film or sheet, a fiber or pulp non-woven fabric, etc. A coating material such as a coating material or a laminate material, a powder coating material, a water-dispersed coating material, or an organic coating material can be obtained. Also, metal, ceramic,
An adhesive suitable for adhering organic structures or the like, or these mutually, can be obtained.

The present invention is not limited to these, and various molded articles and various products obtained from a plastic material (resin composition) having a good compatibility, which contains one or more polymers and the compatibilizing agent. Materials are included.

When a fibrous structure is obtained by the extrusion method,
Since the fibrous structure is made of very fine fibers and the linear velocity during production is very high, the mixed resin composition is
It is necessary that the shape of phase separation is small and the fluidity is relatively excellent. MFR (melt flow rate: unit g / 10 min) is usually used as a measure of polymer fluidity. In order to obtain good productivity, quality and physical properties, the MFR is usually 0.1 to 10, preferably 0.5 to 7 at the molding temperature.
Is.

Even in this case, it is preferable that MFR1 of the island component is larger than MFR2 of the sea component in the mixed polymer. Preferably the ratio of MFR2 / MFR1 is at most 0.9, more preferably at most 0.8. When MFR2 is larger than MFR1, the extruded state at the time of extruding becomes non-uniform, or non-uniform stretching during stretching, knot formation and the like are deteriorated. As for the MFR value, it is necessary to select an optimum value depending on the production system, production brand, etc.

Further, since the shape of the fiber is very small, the shape of the phase separation in the polymer mixture also greatly affects the productivity, quality and physical properties. As the magnitude of phase separation that does not deteriorate productivity, quality, and physical properties, the ratio of the area (S1) of the minor component (island component) domain to the fiber cross-sectional area (S) (S1 /
S) is 0.3 or less, preferably 0.2 or less, more preferably 0.15 or less. If this ratio exceeds 0.5, productivity is deteriorated due to yarn breakage and quality and physical properties are deteriorated due to yarn unevenness, which is not preferable.

To this end, the composition of the mixed resin is
The ratio of the minor components is preferably at most 30% by weight, more preferably at most 20% by weight, based on the mixed resin. If the minor component is more than 30% by weight, the phase separation morphology of the resin mixture becomes large, and the fibers are likely to be cut or partially deformed, resulting in a decrease in productivity and a decrease in quality and physical properties, which is not preferable.

In the present invention, a fiber structure formed by combining different kinds of polymers, particularly a monofilament and a spunbond, has a structure having a stiffer softer component in addition to a harder fiber portion. There is also a feature of having high physical properties and favorable physical properties.

In injection molding, relatively high fluidity is required, and the MFR is usually 0.1 or more and 50 or less, preferably 30 or less, more preferably 20 or less.

In the case of a sheet, a film or a bottle molded product, it is generally not necessary to reduce the phase separation shape as much as in the fiber, although it depends on the thickness thereof, and the amount of the minor component in the resin composition is preferable. Is at most 40% by weight. If the amount of the minor component exceeds 40% by weight, tearing during molding is likely to occur and the productivity is lowered, and unevenness in the thickness and strength of the film become noticeable, which is not preferable.

Regarding the fluidity of the mixed resin, the optimum value differs depending on the sheet, film and bottle. In bottle molding, it is necessary to adjust the resin composition so that the fluidity becomes relatively small. In bottle molding, the MFR of the resin composition is usually 10 or less, preferably 7 or less, and more preferably 0.5 to 5.

The optimum fluidity of a sheet or film varies depending on the production method thereof. The fluidity of the polymer is relatively low in the sheet and film production by the T-die method, and relatively fluid in the film production by the inflation method. Is preferably large. The MFR of the resin composition in the inflation system is usually 30 or less,
It is preferably 25 or less, more preferably 5 to 20.
The MFR of the resin composition by the T-die method is usually 15 or less, preferably 10 or less, more preferably 1 to 8. Even in this case, as in the case of extrusion molding, regarding the fluidity of the different polymers to be mixed, the fluidity of the island component (M
It is preferable that FR1) is larger than the fluidity of the sea component (MFR2). More preferably, the ratio of MFR2 / MFR1 is 0.9 or less.

If the size of the phase separation in the sheet or film becomes too large, tearing or uneven thickness due to non-uniform stretching, or deterioration of physical properties becomes undesirably large. When the magnitude of the phase separation of the island component in the sheet or film is D1 and the thickness of the sheet or film is D, the ratio of D1 / D is usually at most 0.5, preferably 0.3 or less, more preferably Is 0.2 or less.

Various mixing ratios are possible for other molded products, but in view of productivity, quality and physical properties, the ratio of minor components is preferably at most 45% by weight. Further, the size of phase separation due to the mixing of different kinds of polymers is not necessarily required to be eliminated, but if it is large, productivity, operability, quality, physical properties and the like are adversely affected. Further, in the case of a molded product that requires fusion, one having a low softening point (eg PE) as a large component is preferable, and in a molded product which is flexible and requires high surface hardness and heat resistance, a softening point is a large component. High (eg PE
T) is good.

For each molded article or material, the type of the compatibilizing agent resin is appropriately selected according to the type and blending amount of the one or more types of polymers to be used, and the amount of the compatibilizing agent resin is determined according to the device characteristics. It is necessary to set the optimum range according to the productivity, target quality and physical properties.

[0086]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[Example 1] A waste material of a PE gas pipe (made by Osaka Jushi Kogyo Co., Ltd.) was crushed and washed. This was used as a waste material pulverized product of a PE gas pipe.

100 parts by weight of pulverized waste material of PE gas pipe,
And 1 part by weight of linear polymethylphenylsilane (terminal trimethylsilyl group, number average molecular weight 2700, abbreviation PMPS-R) as a compatibilizer, twin-screw extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., BT-30-L). , L / D = 3
0) was melt-kneaded and extruded into a strand to obtain chips. <Extrusion conditions> Temperature setting: feed 260 ° C, kneading part 300 ° C, head 260 ° C rotation speed: 60 rpm

The obtained chip is injection molded (injection molding machine:
Made by Japan Steel Works, Ltd., N100BII, L / D = 22)
Then, the width of the test piece according to JIS K-6760 is 1 /
2 inches x 8.5 inches long x 1/8 inch thick
Created (A). <Injection molding conditions> Temperature setting: feed 260 ° C., nozzle 280 ° C., mold 60 ° C. Injection pressure: 35-40 kg / cm ²

Regarding the test piece (A), JIS K-676
As a result of a mechanical strength test based on 0, the tensile yield point strength was 20.5 MPa.

[Example 2] As a compatibilizer, 0.5 part by weight of polymethylphenylsilane (terminal trimethylsilyl group, number average molecular weight 2700, abbreviated as PMPS-R) and 0.5 part of Bondfast E (manufactured by Sumitomo Chemical Co., Ltd.) A test piece was prepared in the same manner as in Example 1 except that the parts were used. The tensile yield point strength was 21.2 MPa.

Example 3 As a compatibilizer, 0.5 part by weight of polymethylphenylsilane (terminal trimethylsilyl group, number average molecular weight 2700, abbreviated as PMPS-R) and a bisoxazoline / styrene / maleic anhydride copolymer ( A test piece was prepared in the same manner as in Example 1 except that 0.5 part by weight of Mikuni Pharmaceutical Co., Ltd. was used. Tensile yield strength is 21.2
It was MPa.

Example 4 As a compatibilizer, 0.5 parts by weight of polymethylphenylsilane (terminal trimethylsilyl group, number average molecular weight 2700, abbreviated as PMPS-R) and Himilan 1707Na (manufactured by Mitsui DuPont Polychemical Co., Ltd.) A test piece was prepared in the same manner as in Example 1 except that 0.5 part by weight was used. Tensile yield strength is 21.0MP
It was a.

Comparative Example 1 A test piece was prepared in the same manner as in Example 1 except that the compatibilizer was not used. The tensile yield point strength was 17.4 MPa.

As described above, in the recycled materials of Examples 1 to 4, a higher tensile yield point strength was obtained and practically sufficient strength as compared with Comparative Example 1 in which the compatibilizer was not used. .

[0096]

According to the present invention, there are provided a plastic material having high physical properties, a recycled plastic material having high physical properties, and a plastic molded body made of the plastic material.

The present invention is applicable to heterogeneous polymers that are compatible with each other, but in particular compatibilizes heterogeneous polymers that are incompatible with each other (eg, aliphatic and aromatic polymers, polar and nonpolar polymers). It is especially effective when you want to.

The present invention can be applied to an unused resin and a used recovered resin, but since a recycled plastic material having high physical properties can be obtained in the case of the recovered resin, this recycled plastic material can be used in a wide range of fields. It can be used for various purposes. Thus, the present invention contributes significantly to the recycling of waste plastic.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 83/16 C08L 83/16 101/00 101/00 (72) Inventor Takafumi Kawaguchi Chuo-ku, Osaka City, Osaka Prefecture Hiranocho 4-1-2 Osaka Gas Co., Ltd. (72) Inventor Mariko Kato 4-1-2 Hiranocho Chuo-ku, Osaka-shi, Osaka Prefecture Osaka Gas Co., Ltd. (72) Inventor Hirose Murase Osaka-shi, Osaka 4-1-2 Hiranomachi, Chuo-ku, Osaka Gas Co., Ltd. (72) Inventor Go Fujiki 4-1-2, Hiranocho, Chuo-ku, Osaka-shi, Osaka Osaka F-term (reference) 4F071 AA15X AA21 AA21X AA22X AA29X AA32X AA33X AA34X AA36X AA65 AA75 AA77 AA78 AA88 AB17 AB21 AB24 AB26 AE07 AF01 AF05 AF47 AH19 BC12 4F301 AA11 AA12 AA13 AA14 AA15 AA AA AA 22 A25 AA 29 BF32 CA09 CA13 CA36 CA41 4J002 AA013 AA023 AC013 AC033 BB033 BB05X BB07X BB09X BB10X BB123 BB14X BB20X BB21X BB23X BC033 BC05X BD023 BD103 BE003 BF03X BG06X BG11X BN03X BN07X BN153 CB003 CC033 CC133 CD003 CF013 CF063 CF073 CG003 CH053 CH073 CH093 CK003 CL003 CM02X CM043 CN033 CP003 CP01W DA017 DA067 DE017 DE217 DF017 DG047 DJ007 DM007 FD017 FD136 FD203 4J035 JA01 LA05 LB20

Claims (15)

[Claims] 1. A compatibilizer made of a silicon material having a Si—Si bond. 2. A silicon material having a Si—Si bond,
General formula (I): (In the formula (I), R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkoxy group, an aryl group or a silyl group, x, The compatibilizing agent according to claim 1, wherein y and z each represent a number of 0 or 1 or more, and the sum of x, y, and z is 5 to 400). 3. The polysilane has the following formula (II): The compatibilizing agent according to claim 2, which is a linear polysilane having a structural unit of methylphenylsilane represented by 4. At least one compatibilizer selected from the group consisting of an ionomer resin-based compatibilizer, a reactive compatibilizer, an elastomer-based compatibilizer, an oxazoline-based compatibilizer, and a copolymer-based compatibilizer. The compatibilizing agent according to any one of claims 1 to 3, further comprising: 5. One or more polymers, and 1.
To the compatibilizer according to any one of 4 to 4,
Plastic material. 6. The plastic material according to claim 5, further comprising a flame retardant. 7. The plastic material according to claim 5, further comprising an inorganic filler. 8. All of the one or more polymers are:
The plastic material according to any one of claims 5 to 7, which is a virgin polymer. 9. At least one of the one or more polymers is a used polymer.
7. The plastic material according to any one of 7. 10. The plastic material according to claim 9, wherein all of the one or more polymers are used polymers. 11. The plastic material according to claim 5, wherein the plastic material contains plural kinds of polymers, and the plural kinds of polymers include different polymers incompatible with each other. 12. The plastic material according to any one of claims 5 to 11, wherein the plastic material contains plural kinds of polymers, and the plural kinds of polymers include different kinds of polymers which are compatible with each other. 13. The one or more polymers are selected from thermoplastic polymers and / or thermosetting polymers,
The plastic material according to any one of claims 5 to 12. 14. One or more polymer materials, at least one of which has been used, and a compatibilizer according to any one of claims 1 to 4 and, if necessary, difficulty. A recycled plastic material obtained by blending a combustible agent and, if necessary, an inorganic filler. 15. A plastic molded body made of the plastic material according to claim 5.