JP2001158828A - Polymer composite composition - Google Patents

Abstract

(57) [Summary] [Object] To provide a polymer composite composition having excellent functions, especially excellent flame retardancy. [Constitution] When a polymer is produced from a polymerizable monomer, particles having a particle diameter of 1 nm to 1000 nm obtained by pulverizing an inorganic porous material supporting the polymerizable monomer are dispersed in the polymer. Polymer composite composition and method for producing polymer composite composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer composite composition. More specifically, the present invention relates to a polymer composite composition having excellent functions.

[0002]

2. Description of the Related Art Thermoplastic resins, thermoplastic rubber polymers,
BACKGROUND ART Polymers such as thermosetting resins have been used in various fields including automobile parts, electric / electronic materials, and building materials because of their excellent impact resistance and mechanical strength. In recent years, various additives have been used in such fields for higher functionality. For example, an organic or inorganic filler is added to improve the strength, or a flame retardant is added to impart flame retardancy, but due to poor dispersion of the additive, the appearance is reduced. There was a problem that it was damaged or the mechanical properties were reduced. To solve this problem, the additive is finely divided to improve the appearance and mechanical properties.However, even if the particle size of the primary particles is small, they are agglomerated during the kneading process with the polymer. However, practically satisfactory materials have not been obtained.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer composite composition which does not have the above-mentioned problems, that is, has an excellent function in view of the above situation. is there.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies on miniaturization of a specific inorganic compound, and as a result, have polymerized a polymerizable monomer in the presence of a specific inorganic porous material to obtain a polymer. Surprisingly, it has been found that it is possible to disperse an inorganic compound in a fine particle in a polymer,
The present invention has been completed. That is, the present invention relates to a method for producing a polymer from a polymerizable monomer, wherein a particle having a particle size of 1 nm to 1000 nm, obtained by pulverizing an inorganic porous material supporting the polymerizable monomer, And a method for producing the polymer composite composition.

Hereinafter, the present invention will be described in detail. The composition of the present invention comprises (A) a specific inorganic porous material, (B) a specific polymerizable monomer supported thereon, pulverized, and polymerized under shear with a specific particle size. It is a dispersed composition.
The component (A) is a component for imparting a function to the produced polymer, and it is possible to impart an advanced function by carrying an additive (C) during polymerization. We have:
It has been found that by making (A) into fine particles in the process of pulverization, an excellent function-imparting effect is exhibited, and the present invention has been completed.

Hereinafter, each component of the present invention will be described in detail. The inorganic porous material used as (A) in the present invention is obtained by firing a hydrated metal such as aluminum hydroxide and magnesium hydroxide or an inorganic compound such as silica together with a pore-forming agent to obtain a porous silicon oxide. Porous body, magnesium oxide porous body, aluminum oxide, etc., and particularly preferred is a microporous body of silicon oxide (fumed silica).

The above-mentioned pore-forming agent is preferably an inorganic salt which melts at 500 to 800 ° C., and together with a precursor of an inorganic porous material,
It is a component that is detached during firing to form pores. The type of the inorganic salt is not particularly limited as long as it is melted at 500 to 800 ° C. As specific examples, KCl, KBr, KN
O ₃ , Ca (NO ₃ ) ₂・ 4H ₂ O, NaPO ₃ , P ₂ O ₅ , NaH ₂ PO ₄ , MoO ₃ , NaMoO ₂ PO
_{And the} like, and particularly preferred are KCl, KBr, KNO ₃ and Ca (NO ₃ ) ₂ .4H ₂ O. The amount of (A) in the composition of the present invention is preferably 0.5%.
01-99% by weight, more preferably 0.1-50% by weight, still more preferably 1-30% by weight, most preferably 3% by weight.
-20% by weight.

The polymerizable monomer used as (B) in the present invention is a structural unit such as a rubbery polymer, a thermoplastic resin, or a thermosetting resin. Specifically, a vinyl monomer is used for a vinyl polymer, and a polyfunctional monomer is used for a condensation polymer. The polymer (B-1) produced from such a polymerizable monomer is a rubbery polymer, a thermoplastic resin, a thermosetting resin, or the like, and examples thereof include the following polymers.

[0009] One of the above-mentioned polymers preferably has a glass transition temperature (Tg) of -30 ° C or lower, and if it exceeds -30 ° C, the impact resistance tends to decrease. Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the diene rubbers, isoprene rubber, chloroprene rubber, and polyacrylic rubber. Acrylic rubber such as butyl acrylate, ethylene-propylene copolymer rubber, ethylene-propylene-diene monomer terpolymer rubber (EPD)
M), a crosslinked rubber or a non-crosslinked rubber such as an ethylene-octene copolymer rubber, and a thermoplastic elastomer containing the above rubber component.

Among the above thermoplastic elastomers, styrene-based thermoplastic elastomers are particularly preferable, and a block copolymer comprising an aromatic vinyl unit and a conjugated diene unit;
Or the conjugated diene unit portion is a partially hydrogenated block copolymer, particularly from the viewpoint of thermal stability,
Hydrogenated styrenic thermoplastic elastomers are more preferred. In the present invention, the most preferable thermoplastic resins among the polymers (B-1) are, for example, polystyrene, polyphenylene ether, polyolefin, polyvinyl chloride, polyamide, polyester, polyphenylene sulfide, polycarbonate, polycarbonate, A methacrylate or the like alone or a mixture of two or more can be used. In particular, as the thermoplastic polymer, a polyphenylene ether-based, polystyrene-based, or polycarbonate-based thermoplastic resin is preferable.

The aromatic polycarbonate as one of the thermoplastic resins can be selected from an aromatic homopolycarbonate and an aromatic copolycarbonate. As a production method, a phosgene method in which phosgene is blown into a bifunctional phenolic compound in the presence of a caustic alkali and a solvent, or
For example, there can be mentioned a transesterification method in which a bifunctional phenol compound and diethyl carbonate are transesterified in the presence of a catalyst. The aromatic polycarbonate preferably has a viscosity average molecular weight of 10,000 to 100,000. here,
The bifunctional phenolic compound is 2,2′-bis (4
-Hydroxyphenyl) propane, 2,2′-bis (4
-Hydroxy-3,5-dimethylphenyl) propane,
Bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) butane, 2,2′-bis (4-hydroxy-3, 5-diphenyl) butane, 2,
2'-bis (4-hydroxy-3,5-dipropylphenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1'-bis (4-hydroxyphenyl) ethane Etc., especially 2,
2'-bis (4-hydroxyphenyl) propane [bisphenol A] is preferred. In the present invention, the bifunctional phenolic compounds may be used alone or in combination.

The styrene resin as one of the thermoplastic resins in the above (B-1) is a rubber-modified styrene resin and / or a non-rubber-modified styrene resin, particularly a rubber-modified styrene resin alone or a rubber-modified styrene resin. It is preferable that the resin comprises a styrene-based resin and a non-rubber-modified styrene-based resin. The rubber-modified styrene-based polymer refers to a polymer in which a rubber-like polymer is dispersed in a matrix in a matrix composed of a vinyl aromatic-based polymer, and an aromatic vinyl-based polymer is present in the presence of a rubber-like polymer. The monomer and, if necessary, a vinyl monomer copolymerizable therewith are added to obtain a monomer mixture by a known polymerization method such as bulk polymerization, emulsion polymerization and suspension polymerization.

Another polyphenylene ether of the thermoplastic resin in the above (B-1) has an aromatic ring in the main chain,
They are polymers linked by an ether bond, specifically, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6
-Poly (2,6-dimethyl-1,4-phenylene ether). The additive used as (C) in the present invention is one or more additives selected from organic additives, metals, metal salts, and inorganic compounds.

The amount of (C) in the composition of the present invention is preferably from 0.01 to 99% by weight, more preferably from 0.1 to 50% by weight.
%, More preferably 1 to 30% by weight, most preferably 3 to 20% by weight. The organic additive is an additive for imparting a function to the polymer, for example, a plasticizer,
Heat stabilizer, light stabilizer, flame retardant, colorant, foaming agent, lubricant,
Perfume, smoke suppressant, tackifier, preservative, warming agent, impact resistance improver, repellent, wetting agent, surfactant, emulsifier, destabilizer, coagulant, defoamer, antifreeze, It is an additive such as a creaming agent, a thickener, a heat-sensitive agent, and a foaming agent. Of these, plasticizers, heat stabilizers, flame retardants, and light stabilizers are preferred.

Examples of the plasticizer (C) include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, and diisobutyl phthalate; phthalic acid mixed ester such as butyl benzyl phthalate; Aliphatic dibasic acid esters such as diisodecyl succinate and dioctyl adipate; glycol esters such as diethylene glycol dibenzoate; aliphatic acid esters such as butyl oleate and methyl acetyl ricinoleate; epoxidized soybean oil; epoxidation An epoxy plasticizer such as linseed oil,
In addition, trioctyl trimellitate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate
G, tributyl acetyl citrate, chlorinated paraffin,
Polypropylene adipate, polyethylene sebacate,
Examples include triacetin, tributyrin, toluenesulfonamide, alkylbenzene, biphenyl, partially hydrogenated t-phenyl, camphor and the like.

Examples of the heat stabilizer (C) include metal soap, lead stabilizer, organotin stabilizer, composite stabilizer, epoxy compound and the like. The light stabilizer as (C) is a light stabilizer selected from an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, an active species trapping agent, a light-blocking agent, a metal deactivator, a quencher and the like. Agent. The flame retardant as (C) is an organic silicon-based flame retardant,
One or more flame retardants selected from organic metal salt-based, organic halogen-based, organic phosphorus-based, organic nitrogen-based or organic fibrous flame retardants.

The organic silicon-based flame retardant is silicone,
Polyorgano represented by organic silicate or silica
It is a flame retardant containing a silicon element such as siloxane. Po
Liorganosiloxane is used for oil, resin, rubber
are categorized. Polyorganosiloxanes are monofunctional R
_ThreeSiO_1/2M unit represented by the formula, bifunctional R_TwoTable with SiO
D unit, trifunctional R₁SiO_3/2T unit represented by
, Tetrafunctional SiO_TwoA Q unit represented by
Or aryloxy containing R_Five(R₆O) SiO
_2.0(X unit), (R₇O)_TwoSiO_3.0(Y unit) structure
A linear structure containing a branched structure that can be formed by combining units
Having polyorganosiloxane or three-dimensional network structure
Silicone resin, rubber is high molecular weight type gum
Vulcanizates of linear polydiorganosiloxanes and the like.
Other polyorganosiloxanes include epoxy,
Modified polymer modified with amino, mercapto, methacrylic groups, etc.
Liorganosiloxane or polycarbonate (P
C) -Silicone copolymer, acrylic rubber-silicone
Complex.

The organic metal salt-based flame retardant as the flame retardant in the above (C) is, for example, an organic metal sulfonate such as potassium trichlorobenzenesulfonate, potassium perfluorobutanesulfonate, potassium diphenylsulfon-3-sulfonate. Metal sulfonate, metal sulfate, metal phosphate, metal phosphate, and metal borate are bonded to the aromatic ring of a salt, an aromatic sulfonimide metal salt, or an aromatic group-containing polymer such as a styrene-based polymer or polyphenylene ether. And metal salt-based flame retardants such as polystyrene sulfonic acid alkali metal salts. Such a metal salt-based flame retardant promotes a decarboxylation reaction at the time of combustion, particularly when polycarbonate is used as a polymer, to improve flame retardancy. Further, in the case of the alkali metal polystyrene sulfonate, the metal sulfonate itself becomes a cross-linking point during combustion and greatly contributes to the formation of a carbonized film.

The organic halogen-based flame retardant as the flame retardant in the above (C) includes a halogenated bisphenol, an aromatic halogen compound, a halogenated polycarbonate, a halogenated aromatic vinyl polymer, a halogenated cyanurate resin, Halogenated polyphenylene ether and the like,
Preferably, decabromodiphenyl oxide, tetrabromobisphenol A, tetrabromobisphenol A
Oligomer, brominated bisphenol-based phenoxy resin, brominated bisphenol-based polycarbonate, brominated polystyrene, brominated cross-linked polystyrene, brominated polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, halogen-containing phosphorus Acid esters and fluorine-based resins.

As the organic phosphorus flame retardant as the flame retardant in the above (C), phosphine, phosphine oxide,
Biphosphine, phosphonium salts, phosphinates, phosphates, phosphites and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate , Dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethyl pyrocatechol phosphate and dipyrocatechol hypopositive phosphate.

Here, as the organic phosphorus compound, an aromatic phosphate ester monomer and an aromatic phosphate ester condensate are particularly preferred. The organic nitrogen-based flame retardant as the flame retardant in the above (C) is typically a triazine skeleton-containing compound, and is a component for further improving the flame retardancy as a flame retardant auxiliary of a phosphorus flame retardant. is there. Specific examples thereof include melamine, melam, melem, melon (product of deammonification of three to three molecules of melem at a temperature of 600 ° C. or more), melamine cyanurate, melamine phosphate, succinoguanamine, adipoguanamine, Methylglutalogamine, melamine resin and BT resin can be mentioned, and melamine cyanurate is particularly preferable from the viewpoint of low volatility.

The organic fibrous flame retardant as the flame retardant in the above (C) is a flame retardant used for preventing dripping of fire, and becomes fibrous at the time of addition or processing. Specific examples thereof include aramid fiber, polyacrylonitrile fiber, and fluororesin. Examples of the foaming agent (C) include an azo foaming agent, an N-nitroso foaming agent, and a sulfonyl hydrazide.

Examples of the lubricant as (C) include:
Hydrocarbon lubricants such as paraffin, fatty acid lubricants, fats
Acid amide lubricants, alcohol lubricants, metal soaps, etc.
Can be mentioned. Used as (C) in the present invention
Specific examples of the inorganic compound to be used include aluminum hydroxide
, Magnesium hydroxide, dolomite, hydrotalsa
Light, calcium hydroxide, barium hydroxide, basic carbonic acid
Magnesium, zirconium hydroxide, tin oxide hydrate
Hydrate, aluminum oxide, oxidation of inorganic metal compounds such as
Iron, titanium oxide, manganese oxide, magnesium oxide, acid
Zirconium oxide, zinc oxide, molybdenum oxide, copper oxide
, Bismuth oxide, chromium oxide, tin oxide, ann oxide
Of titanium, nickel oxide, copper oxide, tungsten oxide, etc.
Metal oxides, aluminum, iron, titanium, manganese,
Lead, molybdenum, cobalt, bismuth, chromium, nickel
Metal powder such as copper, tungsten, tin, antimony,
And zinc borate, zinc metaborate, barium metaborate
, Zinc carbonate, magnesium carbonate, calcium carbonate, charcoal
Barium acid or hydrated glass SiO_Two-MgO-H_TwoO, PbO-B_TwoO
_ThreeSystem, ZnO-P_TwoO _Five-MgO system, P_TwoO_Five-B_TwoO_Three-PbO-MgO, P-Sn-O-F
System, PbO-V_TwoO_Five-TeO_TwoSystem, Al_TwoO_Three・ H_TwoO-based, tin halide
And glassy compounds such as lead borosilicate.
These may be used alone or in combination of two or more.

In the present invention, (A) one of the inorganic porous bodies, the additive-supported porous silica body is prepared by dispersing, dissolving, drying and calcining a silica sol, an alkali metal halide and an agent to be substituted in an aqueous solution. It is made by immersing the body in an aqueous solution to remove alkali metal halides. The (A) inorganic porous material thus obtained has a pore size of 1 nm to 1000 nm and a particle size of 10 nm.
Polymerizing the polymerizable monomer under shearing with the polymerizable monomer (A) having a thickness of 0 nm to 1000 nm and (B) a polymerizable monomer, and optionally (C) an additive. (A) easily crushes the inorganic porous material,
The additives are dispersed in the polymer as particles of nm to 1000 nm.

In the composition of the present invention, other additives such as organic / inorganic pigments, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, etc.
A silicone oil, an anti-blocking agent, a foaming agent, an antistatic agent, an antibacterial agent and the like can be added. In the production of the composition of the present invention, a usual rubber or resin polymerization apparatus is used, and a general method can be employed.

[0026]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In these examples and comparative examples, the test methods used for evaluating various physical properties are as follows. (1) Particle Size of Inorganic Porous Material The number average particle diameter of each particle was determined by an electron microscope, and was defined as the average particle diameter. That is, each particle is assumed to be a sphere, and the arithmetic average of the major axis and the minor axis is defined as the average diameter of each particle. And 100
The number average particle diameter was determined by arithmetic mean of the average diameters of the individual particles.

(2) Flame retardancy VB (Vertical Bur) conforming to UL-94
The self-extinguishing property was evaluated by the ning method. (1
/ 8 inch thickness test specimen) ○: Self-extinguishing property ×: Totally burned (3) Appearance ◎: Extremely good ○: Good ×: Poor

The following components were used in Examples and Comparative Examples. (B) Additives Commercial additives were used. (1) Methyl phenyl silicone oil (referred to as SI) Examples 1 to 12 Comparative Examples 1 to 4 Commercially available silica sol and KBr were dispersed and dissolved in an aqueous solution, dried at 100 ° C, and calcined at 700 ° C. The silica fired body obtained as described above was immersed in an aqueous solution to remove KBr, thereby obtaining a silica porous body. At that time, various (B) polymerizable monomers or additives were supported. In the above production method, the pore size and particle size of the silica porous material were controlled by controlling the amount ratio of silica sol and KBr, the drying temperature, and the firing temperature. The results are shown in Table 1.

The porous silica thus obtained was mechanically mixed at the ratios shown in Tables 1 and 2 and polymerized at 150 ° C. in a polymerization reactor equipped with a stirrer. From the composition thus obtained, test pieces having a thickness of 1/8 inch were prepared by a compression molding method, and various evaluations were made. Tables 1 and 2 show the results.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

The present invention relates to a polymer composite composition having excellent functions, especially excellent flame retardancy. Since the composition of the present invention has excellent properties, it can be used for automobile parts, automobile interior materials, airbag covers, mechanical parts, electric parts, cables, hoses, belts,
It can be widely used for toys, miscellaneous goods, daily necessities, building materials, sheets, films, and other applications, and plays a large role in the industrial world.

Continued on the front page F term (reference) 4F070 AA18 AC15 AC23 AD03 AE16 FA12 FB06 4J002 AC031 AC061 AC071 AC081 AC091 BB001 BB051 BB151 BC031 BD031 BG041 BG051 CF001 CG001 CH071 CL001 CN001 DE076 DE146 4 016 FD 010 FD 010 FD 010 010 FD 010 010 PA04 PA13

Claims (6)

[Claims] When a polymer is produced from a polymerizable monomer, particles having a particle size of 1 nm to 1000 nm obtained by pulverizing an inorganic porous material supporting the polymerizable monomer are mixed with the polymer. A polymer composite composition dispersed in a polymer. 2. The composite polymer composition according to claim 1, wherein said inorganic porous body is made of silicon oxide and / or aluminum oxide. 3. The inorganic porous material has a pore size of 1 nm to 1000.
nm and a particle size of 100 nm to 1000 nm, and the inorganic porous material supporting the polymerizable monomer is pulverized under shearing to obtain a particle size of 1 nm to 1000 nm.
The method for producing a polymer composite composition according to claim 1, wherein the particles are dispersed in a polymer. 4. The inorganic porous body is a microporous body of silicon oxide (fumed silica).
A method for producing the polymer composite composition according to the above. 5. A silica fired body in which an inorganic porous material is obtained by dispersing, dissolving, drying and firing a silica sol, an alkali metal halide and an agent to be replaced in an aqueous solution, to obtain a metal, a metal salt,
A porous silica body which is immersed in an aqueous solution of an additive selected from inorganic compounds to remove alkali metal halides, and which is carried by replacing the additive with an agent to be replaced. Item 4. The method for producing a polymer composite composition according to Item 3. 6. When a polymer is produced from a polymerizable monomer, particles having a particle size of 1 nm to 1000 nm obtained by pulverizing an inorganic porous material carrying a polymerizable monomer and an additive are: 3. The polymer composite composition according to claim 1, which is dispersed in said polymer.