JP4206482B2 - Production method of organic clay - Google Patents

Description

This invention relates to a process for the preparation of the organoclay.

  Organoclay is thickened by exfoliating and dispersing the layered structure of 1 nm thick crystals of organic clay in an organic solvent and developing thixotropic properties by forming an association structure between crystals. Widely used in the fields of paints, inks, cosmetics and the like as organic solvent thickeners and rheology control agents. In recent years, talc, carbon black, glass fiber, etc. are added to molten resin in an amount of 30% to 50% by weight, and fillers (in order to improve mechanical properties such as resin strength, elastic modulus, heat distortion temperature, etc.) As an alternative to this conventionally used filler, the layered crystal structure of organoclay in the resin is peeled and dispersed one by one at the nano level. It is also considered as a functional filler capable of exhibiting the same mechanical properties by addition of about 3 to 5% by weight, which is about 1/10 of the above filler.

Ordinary organic clay is a process in which a clay having a layered crystal structure is first sufficiently peeled and dispersed in water, an organic cation is added to and mixed with this clay aqueous dispersion, and the organic cation is adsorbed on the crystal surface. From the process of hydrophobizing to produce organic clay, washing to remove residual cations and moisture of the organic clay, dehydration process, drying process to evaporate the remaining water, and grinding process to turn the massive organic clay into powder It has become. The organoclay produced by such a conventional production method has a reduced interlaminar distance of 20 to 30 mm and an increase in van der Waals attraction between crystals, and a layered structure in which this van der Waals attraction is increased. A great deal of effort must be spent to peel and disperse the organic clay crystals in the resin.

The method of exfoliating and dispersing the layered crystal structure of organoclay in the resin is to increase the distance between the crystals by increasing the amount of organic cation between the crystal layers, to weaken the van der Waals attraction between crystals, A method of improving the compatibility between the crystal surface and the resin by changing the type of the functional group, a method of applying a mechanical kneading force superior to the van der Waals attractive force between the crystals when kneading the molten resin and the organic clay, the resin A method of applying a driving force for intercalating between the crystal layers by modifying the resin itself has been used, but it has not been completely dispersed.

For this reason, as shown in Patent Document 1, the present applicants pre-intercalate an antioxidant, which is a resin additive, between crystal layers of an organic clay, and treat the organic clay with a silane coupling agent. As a result, it was found that heat resistance and dispersibility were improved in the resin, and this was proposed previously.

Japanese Patent Application No. 2003-95257

The present invention is a flame retardant that flame retardants the resin, which is another resin additive of the above antioxidant, an ultraviolet absorber that absorbs 300-400 μm ultraviolet rays and prevents photo-oxidative degradation of the resin, and refines the crystal nucleus. Nucleating agents that can shorten the processing cycle by increasing mechanical properties and dimensional stability such as resin transparency, heat distortion temperature, rigidity, impact strength, and crystallization temperature, copper, iron, cobalt, Heavy metal deactivator that acts on heavy metal ions such as manganese and chromium to form inert metal complex compounds and prevents oxidation degradation catalysis, antibacterial and antifungal antibacterial agents, treated at a certain temperature This is an organic foaming agent that forms a bubble structure in the resin using the generated gas, reduces the friction between the resins, prevents the generation of excessive frictional heat, and the resin and processing machine Adjust the surface slip In addition, it has a layered crystal structure that prevents adhesion and prevents the metal surface from peeling off.An antioxidant that suppresses and prevents the resin from undergoing oxidative degradation due to oxygen in the air and causing quality degradation during production and use. it is an object to provide a method of organoclay the interlayer distance of the organoclay can be obtained easily intercalated sufficient dispersibility in a semi-dry unfolded sufficiently manufacturing.

The inventors of the present invention have intensively studied to solve the above-mentioned problems. As a result, the resin additive is kneaded and compounded with the organic clay. Specifically, when the semi-dry state where the crystal interlayer distance of the organic clay is sufficiently widened. It was found that an organoclay that can be easily intercalated with a new compound can be obtained by kneading the resin additive with the composite.

That is, the present invention is a resin additive dissolved or dispersed in an organic solvent in a semi-dried state in advance after the dehydration step in which the distance between the crystal layers of the organic clay is sufficiently widened, that is, before the drying step. adding the combined ones, they are mixed, they were intercalated between crystal layers, dried, and pulverized, thereby obtaining a method for producing an organic clay new compound is intercalated. The resin additives targeted by the present invention are the flame retardant, UV absorber, nucleating agent, heavy metal deactivator, antibacterial agent, organic foaming agent, and lubricant.

According to the present invention, since a resin additive is intercalated in advance between the crystal layers of the organic clay and dispersed in the resin, the resin additive can be dispersed at the nano level in the resin. There is a possibility that an equivalent function can be exerted with an addition amount smaller than the amount of use, and weight reduction of the resin can be expected.

Further, by combining the organic clay and the resin additive, it is possible to expect an effect that combines the function of the functional filler of the organic clay and the function of each resin additive.

Furthermore, since the resin additive is included in the inorganic crystals of the organoclay, the decomposition temperature of the resin additive itself increases, so it can also be used for resins that are softened and melted at high temperatures that could not be handled up to now. Is possible.

Moreover, since the resin additive is gradually released from the crystal layers, that is, since the resin additive also has a sustained release property, effects such as an increase in the durability of the effect of the resin additive can be obtained.

  Hereinafter, the present invention will be described based on examples.

  In practicing the present invention, the clay is first sufficiently peeled and dispersed in water by a conventional method, and then the organic cation dissolved in water or alcohol is 0.5 to 2.0 times the cation exchange capacity of the clay. By adding an amount and ion-exchanging sodium ions and organic cation ions adsorbed on the surface of the clay, the organic cation is adsorbed on the clay surface, and an organic clay having a hydrophobic crystal surface is generated.

Next, a flame retardant dissolved or dispersed in an organic solvent such as methanol, ethanol, toluene, acetone, etc., in a semi-dried organic clay obtained by washing, dehydrating, removing residual cations and moisture, Add various ultraviolet light absorbers, nucleating agents, heavy metal deactivators, antibacterial agents, organic foaming agents, and lubricants to the solid content of the organic clay, mix, dry, grind, and add various resin additives. To obtain an organic clay intercalated between crystal layers.

In the present invention, a flame retardant, an ultraviolet absorber, a nucleating agent, a heavy metal deactivator, an antibacterial agent, an organic foam, dissolved or dispersed in the above-mentioned amount of an organic cation and an organic solvent in a clay aqueous dispersion. An organic clay combined with the same resin additive can be obtained by adding, mixing, drying, and pulverizing a mixture of an agent and a lubricant.

  Here, clays that can be used in the present invention include smectite clays such as montmorillonite, beidellite, hectorite, saponite, stevensite, soconite, nontronite, natural and synthetic clays such as vermiculite, halloysite, and swelling mica. These mixtures can be mentioned.

  Examples of the organic cation that can be used in the present invention include organic cations composed of a quaternary ammonium salt, a phosphonium salt, a sulfonium salt, and a mixture thereof.

  Quaternary ammonium salts include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium, trimethyloctylammonium, trimethyldodecylammonium, trimethyl. Alkyltrimethylammonium ions such as octadecylammonium, dimethyldialkylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium and dimethyldioctadecylammonium, and trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium. , Benzethonium ion having two benzene ring.

  Examples of the flame retardant that can be used in the present invention include halogen-based, phosphorus-based, inorganic-based compounds, and mixtures thereof.

  Examples of halogen flame retardants include tetrabromobisphenol A, 2,2-bis (4-hydroxy-3,5-dibromo-phenyl) propane, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2, Examples thereof include 2-bis (4-hydroxyethoxy-3,5-dibromo-phenyl) propane, decabromodiphenyl oxide, and halogen-containing polyphosphate.

  Phosphorus flame retardants include ammonium phosphate, tricresyl phosphate, triethyl phosphate, tris (β-chloroethyl) phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, triaryl Examples thereof include phosphoric acid esters and nitrogen-containing phosphorus compounds.

  Examples of the inorganic flame retardant include red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, metaborate barrier, aluminum hydroxide, and magnesium hydroxide.

  Examples of the ultraviolet absorber that can be used in the present invention include salicylic acid series, benzophenone series, benzotriazole series, cyanoacrylate series, and mixtures thereof.

Examples of salicylic acid ultraviolet absorbers include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.

Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2,2′-dihydroxy. Examples include -4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and 2-hydroxy-4-methoxy-5-sulfobenzophenone.

Examples of the benzotriazole ultraviolet absorber include 2 (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2 (2′-hydroxy- 3 ', 5'-di-tert-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy- 3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole.

Examples of cyanoacrylate ultraviolet absorbers include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate.

Examples of the nucleating agent that can be used in the present invention include sodium bis (4-tert-butylphenyl) phosphate, sodium 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, bis (p- Methylbenzylidene) sorbitol, alkyl-substituted dibenzylidenesorbitol, bis (p-ethylbenzylidene) sorbitol.

Heavy metal deactivators that can be used in the present invention include 3- (N-salicyloyl) amino-1,2,4-triazole, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4 ′). -Hydroxyphenyl) propionate] methane.

Antibacterial agents that can be used in the present invention include 10,10′-oxybisphenoxyarsine, N- (fluorodichloromethylthio) -phthalimide, N-dimethyl-N′-N ′-(fluorodichloromethylthio) -sulfamide, 2- And a mixture of methoxycarbonylaminobenzimidazole and zinc compound / organometallic salt compound.

Examples of the organic blowing agent that can be used in the present invention include azodicarbonamide, azobisisobutyronitrile, N 2, N′-dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, p, p′-oxybis (benzenesulfonyl hydrazide). Can be given.

Examples of the lubricant that can be used in the present invention include an aliphatic hydrocarbon lubricant, a higher aliphatic alcohol / higher fatty acid lubricant, a fatty acid amide lubricant, a metal soap lubricant, a fatty acid ester lubricant, and a composite lubricant.

Examples of the aliphatic hydrocarbon lubricant include liquid paraffin having 16 or more carbon atoms, microcrystalline wax, natural paraffin, synthetic paraffin, and polyolefin wax.

Examples of higher aliphatic alcohols and higher fatty acid lubricants include animal oils such as beef tallow and fish oil, vegetable oils such as coconut oil, rapeseed oil, soybean oil and rice bran wax.

Examples of fatty acid amide lubricants include higher fatty acid amides and bisamides.

Examples of the metal soap lubricant include barium stearate, calcium stearate, zinc stearate, aluminum stearate, magnesium stearate and the like.

Examples of fatty acid ester lubricants include higher fatty acid esters of monohydric alcohols and higher fatty acid esters of polyhydric alcohols.

  From the X-ray measurement results, the amount of the resin additive added is less than 5% by weight, and the effect of the resin additive is not exerted, and if it is 20% by weight or more, the resin added cannot be intercalated between the layers of the organic clay. Since the presence of the agent increases, it is 5 to 50% by weight, preferably 10 to 20% by weight, based on the organic clay.

Experimental example 1

(X-ray measurement)
Apparatus: X-ray diffractometer (manufactured by Rigaku Corporation; RAD-IIA)
Tube: Cu-Kα
Tube voltage: 25KV
Tube current: 15 mA
Full scale: 2000 cps
Time constant: 2 sec
Scanning speed: 2 ° / min
Divergence slit: 1 °
Receiving slit: 0.15mm
Scanning range: 40-2 °

(Measurement result)
An X-ray chart of the resin additive (heavy metal deactivator) composite organoclay is shown in FIG.

In FIG.
a) is an X-ray chart of organoclay without resin additive. Peaks based on organoclay appeared at 3.0 ° (bottom interval 29.5 mm) and 19.6 °, which are the 001 plane peaks of organoclay.
b) is an X-ray chart of only the heavy metal deactivator (3- (N-salicyloyl) amino-1,2,4-triazole: ADK STAB CDA-1 manufactured by Asahi Denka Kogyo Co., Ltd.). Peaks based on heavy metal deactivators appeared at 8.2 ° and 16.4 °, 25.9 °, 27.5 °, 29.7 °.
c) is an X-ray chart of an organic clay in which 5% by weight of a heavy metal deactivator is combined with the organic clay. The bottom spacing of the organoclay increased from 29.5 mm (3.0 °) without heavy metal deactivator to 36.8 mm (2.4 °), indicating that the heavy metal deactivator intercalated between the crystal layers. Show. A slight peak based on the heavy metal deactivator was observed at 8.2 °, but a peak based almost on the organoclay appeared. This indicates that almost all of the heavy metal deactivator is intercalated between the organoclay crystal layers.
d) is an X-ray chart of an organic clay in which a heavy metal deactivator is combined by 10 wt% with respect to the organic clay. The peak intensity at 8.2 ° was slightly increased. This indicates that the heavy metal deactivator is intercalated between the layers of the organoclay crystal and a small amount that is not intercalated begins to appear outside the crystal layer.
e) is an X-ray chart of an organic clay in which a heavy metal deactivator is combined by 20 wt% with respect to the organic clay. The peak intensity at 8.2 ° further increased, and new peaks based on heavy metal deactivators appeared at 16.4 °, 25.9 °, 27.5 °, and 29.7 °. This indicates the presence of an excessive heavy metal deactivator that cannot be intercalated between the layers of organoclay crystals. Even if more heavy metal deactivators are combined, intercalation between layers of organoclay crystals is not possible. This indicates that it is difficult to

Experimental example 2

  Montmorillonite (Hogel Co., Ltd. Bengel A) 100 g was sufficiently dispersed in 50 ml of water, and 65 g of dimethyl distearyl ammonium chloride (Lion Azo Co., Ltd., Arcard 2HT flakes, solid content concentration 95%) previously dissolved sufficiently in water. A semi-dried organoclay after addition, mixing, washing and dehydration was prepared. Its water content was 60.7% by weight. Various flame retardants (tetrabromobisphenol A: Fireguard FG2000 manufactured by Teijin Chemicals Limited, triaryl phosphate ester: Leophos 35, Leophos 65 manufactured by Ajinomoto Fine Techno Co., Ltd.) Tricresyl phosphate: Clontex TCP manufactured by Ajinomoto Fine Techno Co., Ltd., resorcinol bis (diphenyl phosphate): Leophos RDP manufactured by Ajinomoto Fine Techno Co., Ltd., 5 wt%, 10 wt%, 20 wt. % Was added and mixed, then dried and pulverized to produce a flame retardant composite organoclay.

Experimental example 3

  A semi-dried organic clay was produced in the same manner as in Experimental Example 2. Its water content was 60.7% by weight. Various UV absorbers (2,4-dihydroxybenzophenone: SEESORB100, 2-hydroxy-4-methoxybenzophenone: SEESORB101, 2-hydroxy-4-octoxybenzophenone: SEESORB102) sufficiently dissolved in 50 g of this organic clay in 5 ml of toluene P-tert-butylphenyl salicylate: SEESORB202, 2 (2-hydroxy-5-methylphenyl) benzotriazole: SEESORB701, 2 (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5 Chlorobenzotriazole: SEESORB 703 (all manufactured by Sipro Kasei Co., Ltd.) is added to 5%, 10%, and 20% by weight of the solid content of the organic clay, mixed, then dried and pulverized to combine the UV absorber. Organoclay was made.

Experimental Example 4

  A semi-dried organic clay was produced in the same manner as in Experimental Example 2. Its water content was 60.7% by weight. Nucleating agent (2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate sodium phosphate sufficiently dissolved in 5 ml of methanol in 50 g of this organic clay: ADK STAB NA-11 manufactured by Asahi Denka Kogyo Co., Ltd. ) Was added to and mixed with 5 wt%, 10 wt%, and 20 wt% of the solid content of the organoclay, and then dried and ground to produce a nucleating agent composite organoclay.

Experimental Example 5

A semi-dried organic clay was produced in the same manner as in Experimental Example 2. Its water content was 60.7% by weight. A heavy metal deactivator (3- (N-salicyloyl) amino-1,2,4-triazole: ADK STAB CDA-1 manufactured by Asahi Denka Kogyo Co., Ltd.) dispersed in 50 g of methanol in 5 g of methanol 5 wt%, 10 wt%, and 20 wt% were added and mixed with respect to the amount, and then dried and pulverized to prepare a heavy metal deactivator composite organoclay.

Experimental Example 6

A semi-dried organic clay was produced in the same manner as in Experimental Example 2. Its water content was 60.7% by weight. An antibacterial agent (organometallic chloride compound: Adeka Royal Guard BC-200 manufactured by Asahi Denka Kogyo Co., Ltd.) dispersed in 50 ml of this organic clay in 5 ml of methanol is 5% by weight, 10% by weight, 20% by weight was added and mixed, and then dried and pulverized to prepare an antibacterial composite organic clay.

Experimental Example 7

A semi-dried organic clay was produced in the same manner as in Experimental Example 2. Its water content was 60.7% by weight. Various organic foaming agents dispersed in 50 ml of this organic clay with 5 ml of methanol (Azodicarbonamide: Einwa Kasei Kogyo Co., Ltd. Vinyl Hall AC # 3C, N, N'-dinitrosopentamethylenetetramine: Eiwa Kasei Kogyo Co., Ltd. Cellular D, p, p'-oxybis (benzenesulfonylhydrazide): Neowabon N # 1000M manufactured by Eiwa Kasei Kogyo Co., Ltd. is added and mixed in an amount of 5 wt%, 10 wt% and 20 wt% based on the solid content of the organic clay. Then, it was dried and pulverized to produce an organic foaming agent composite organic clay.

Experimental Example 8

A semi-dried organic clay was produced in the same manner as in Experimental Example 2. Its water content was 60.7% by weight. A lubricant (acrylate oligomer: ADK STAB FC-112 manufactured by Asahi Denka Kogyo Co., Ltd.) dissolved in 50 ml of acetone in 50 g of this organic clay was added at 5 wt%, 10 wt%, and 20 wt% with respect to the solid content of the organic clay. , And then dried and pulverized to produce a lubricant composite organoclay.

(Comparative example)
Montmorillonite (Hogel Co., Ltd. Bengel A) 100 g was sufficiently dispersed in 50 ml of water, and 65 g of dimethyl distearyl ammonium chloride (Lion Azo Co., Ltd., Arcard 2HT flakes, solid content concentration 95%) previously dissolved sufficiently in water. A semi-dried organoclay after addition, mixing, washing and dehydration was prepared. Its water content was 60.7% by weight. The organic clay was dried and pulverized to produce an organic clay.

(Measurement)
The distance between the bottom surfaces of the crystals of the resin additive composite organic clay of Experimental Example 2-8 and the resin clay without the resin additive of Comparative Example was measured by X-ray diffraction. The results are shown in Tables 1 to 4.

(Measurement result)
Compared with the bottom surface spacing of the organic clay without resin additive of Comparative Example, the bottom surface spacing of the resin additive composite organic clay of Experimental Example 2-8 is increased so that the resin additive is intercalated between the crystal layers of the organic clay. It showed that it was curated.

FIG. 1 is an X-ray chart of a resin additive composite organic clay according to the present invention.

Claims (7)

A method for producing an organic clay, comprising: adding a flame retardant previously dissolved or dispersed in an organic solvent to a semi-dried organic clay, mixing, drying, and pulverizing . A method for producing an organic clay, comprising adding an ultraviolet absorber dissolved or dispersed in an organic solvent in advance to a semi-dried organic clay, mixing, drying, and pulverizing . A method for producing an organic clay, comprising adding a nucleating agent previously dissolved or dispersed in an organic solvent to an organic clay in a semi-dried state, mixing, drying, and pulverizing . A method for producing an organic clay, comprising adding a heavy metal deactivator previously dissolved or dispersed in an organic solvent to a semi-dried organic clay, mixing, drying and pulverizing . A method for producing an organic clay, comprising adding an antibacterial agent previously dissolved or dispersed in an organic solvent to a semi-dried organic clay, mixing, drying, and pulverizing. A method for producing an organic clay, comprising adding an organic foaming agent previously dissolved or dispersed in an organic solvent to a semi-dried organic clay, mixing the mixture, drying and pulverizing . A method for producing an organic clay, comprising adding a lubricant previously dissolved or dispersed in an organic solvent to a semi-dried organic clay, mixing the mixture, drying and grinding .

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