KR102320285B1 - Dispersant composition having brillant color of Naphthalene series for latax and method of preparation thereof - Google Patents

Abstract

The present invention provides a bright color naphthalene-based dispersion-based novel composition for latex and a method for preparing the same. The naphthalene-based dispersant of the present invention provides the naphthalene-based dispersant composition having a stable yellowish-brown light color without precipitation, and hydrogen peroxide or sodium hypochlorite or sodium percarbonate is added in an amount of 1 to 5% by weight based on the total weight of the dispersant composition as a decolorant at the end of a manufacturing process.

Description

Dispersant composition having brillant color of Naphthalene series for latax and method of preparation thereof

The present invention relates to a bright color naphthalene-based dispersant composition for latex, and a method for preparing and using the same.

Latex refers to a material in which fine polymer particles are stably dispersed in an aqueous solution. Rubber gloves are used in various fields such as kitchen, food industry, electronic industry, medical and laboratory use. It is roughly classified as being dispersed in the phase. However, protein particles contained in natural rubber purified from rubber trees sometimes exhibit side effects such as allergies and rashes. Rubber gloves prepared by dip-molding a latex composition further blended with has been widely used.

Korean Patent Registration No. 10-1126583 discloses a method for manufacturing rubber gloves without adding sulfur and a vulcanization accelerator to a synthetic latex resin composition for rubber gloves.

Natural latex biosynthesizes latex to protect it from herbivores, and the oily substances secreted when a plant epidermis is injured contain water-soluble protein particles, alkaloids, starch, sugars, oils and fats, tannins, rubber components, etc. Since it is nature-friendly, it is typically used for rubber baby bottles, rubber mattresses, or condoms in addition to rubber gloves. On the other hand, synthetic latex is a dispersion composition of synthetic rubber produced based on high molecular substances such as petrochemical-derived vinyl monomers such as styrene and butadiene. distinguished

Korean Patent Laid-Open Publication No. 10-2008-0046834 discloses that nanoized aluminum hydroxide and silver in a latex composition for rubber gloves that are formulated in 80% by weight or more of synthetic latex, 3.3% by weight or more of sulfur, 0.2% by weight or more of pigment, and 1.5% by weight or more of dispersant (Ag) Disclosed is a method for producing a latex rubber glove having breathability and antibacterial activity prepared by further adding a mixture. In the above invention, etc., the pigment is used to give the color of rubber gloves, and sulfur is used as a vulcanizing means in the latex. Colors that are too light or too dark may not achieve the desired color. Typically, the primary latex composition uses a colored pigment, and the secondary latex solution is white titanium dioxide (TiO ₂ ). In the present invention, as the dispersing agent, nanoized aluminum hydroxide [Al ₂ (OH) ₆ ] or silver (Ag) added to the latex composition was used as a material for uniformly dispersing stearic acid.

Korean Patent Registration No. 10-1070687 discloses a latex-coated cotton glove with reduced unpleasant odor and a manufacturing method thereof, and No. 10-2136823 discloses oil resistance and detergent resistance using a mixed composition of synthetic rubber and natural rubber latex resin. A repeatable latex rubber glove and a manufacturing method thereof are disclosed. The patent because of latex rubber gloves nitrile butadiene latex resin as a raw material of acrylic, styrene butadiene latex, resins, and any two or more of these are used of a natural rubber latex resin need coagulant in the manufacturing process, calcium chloride (CaCl ₂₎ or calcium nitrate [Ca (NO ₃ ) ₂ ] is used with water, and for uniform dipping, alkylphenols and alkyl alcohol ethoxylate nonionic surfactants must be additionally added. Inorganic powders such as talc and clay are additionally required.

In general, a polymer material or a mixture composition of a polymer material is selected and used as a bleaching agent according to the characteristics of the various polymer materials or the mixture composition thereof. Republic of Korea Patent Registration No. 10-1321266 discloses an activated clay obtained by acid treatment of a dihedral smectite clay mineral as a bleaching agent for oils and fats or mineral oils. The activated clay is useful as a bleaching agent for vegetable oils such as soybean oil, pop oil, cottonseed oil, and mineral oils such as sardine oil, herring oil, and saury oil, or turbine oil, machine oil, lubricating oil, and engine oil.

In addition, Korean Patent Registration No. 10-2073079 discloses a thermally conductive polymer composition containing various additives in a polymer resin, for example, a phenolic resin such as polypropylene, polyethylene, polyamide, etc. for preparing a light color when the color is dark as a laser marking additive, A brightly colored thermally conductive polymer composition including a thermosetting resin such as urea resin and epoxy resin is disclosed.

However, none of the above documents discloses or suggests a chemical dispersant for realizing a bright color of a resin composition for latex and a composition thereof.

1: Patent No. 1126583 Registered Patent Publication, 2: Patent Laid-Open Publication No. 10-2008-0046834, 3: Patent No. 1070687 Registered Patent Publication, 4: Patent No. 2136823 Registered Patent Publication, 5: Patent No. 1321266 Registered Patent Publication, 6: Patent No. 2073079 Registered Patent Publication.

It is an object of the present invention to provide a bright color naphthalene-based dispersant for latex and a method for preparing the same.

Another object of the present invention is to provide the use of a bright color naphthalene-based dispersant obtained by the above method.

The above object of the present invention comprises the steps of inputting naphthalene or a derivative thereof as a raw material into a reactor as a raw material; heating the naphthalene-based raw material of the above step to 100°C; adding concentrated sulfuric acid to the heated naphthalene-based raw material in the step and mixing; Reheating the mixture of concentrated sulfuric acid and naphthalene-based raw material of the above step to 137 ~ 140 ℃, followed by sulfuration reaction at 137 ~ 140 ℃ for 3 hours; cooling the sulfated reactant obtained in the above step to 107° C. and then performing primary hydrolysis; adding formalin to the cooled intermediate sulfated reaction product obtained in the above step, raising the temperature to 2.2 bar and 128° C., and polycondensation for 6 hours to reach 130° C. and 3.5 bar; After cooling the polycondensation reaction product obtained in the above step to 80 ℃ neutralized so as not to exceed 80 ℃ by slowly adding caustic soda (NaOH); Secondary addition to the polycondensate obtained in the above step; _{The step of performing the first to second cooling in order to remove the mango seed (Na 2} SO ₄ ) generated in the above step to remove the mango leaf precipitated as a desiccant and separating the supernatant as soon as it reaches 10 to 15 °C; ; It is achieved through the step of adding any one of a decolorizing agent selected from hydrogen peroxide, sodium hypochlorite and sodium percarbonate to the liquid obtained in the above step and stirring at 60° C. for 1 hour to obtain and evaluate a naphthalene-based dispersant.

According to the present invention, as a raw material for the naphthalene-based dispersant, naphthalene or the following naphthalene-based derivative may be used. That is, the dispersant raw material used in the present invention includes a salt of 2,3-dihydroxynaphthalene-6-sulfonic acid having the following formula (1) or a mixture thereof.

with the proviso that R is Na ⁺ , Li ⁺ , K ⁺ and NR′ ₄ ⁺ , wherein R′ is independently —H, —CH ₃ , —CH ₂ —CH ₃ , —CH ₂ —CH ₂ —OH. It is a cation selected from the group consisting of. The compounds are useful as dispersants in water and other polar liquids as dispersants in particles comprising at least one component selected from the group consisting of metal oxide particles, particles having a metal oxide surface, and mixtures thereof. Useful dispersants include sodium salt (R = Na ⁺ ), 2,3-dihydroxynaphthalene-6-sulfonic acid sodium salt. A sodium salt used as a coupler in diazo photosensitive paper is commercially available under the trade name "Dihvdroxy R Salt" or "DHR".

A dye is a general term for a colorant for fibers. It is a dyeing material that can dye a color. It is a colored substance that is dissolved in water and airflow, dispersed as a single molecule, and combined with molecules such as fibers to color. In this respect, dyes are distinguished from pigments, which are insoluble in water or oil and which in the form of a powder form an opaque colored film on the surface of an object. However, depending on the object used, the same pigment component may be used as a dye or as a pigment.

Dispersants are variously studied as substances added to make a stable dispersion system in industrial fields such as dyes, paints, and pigments. The present invention provides a naphthalene-based dispersant that can be added for stable dispersion of latex raw materials and dyes added thereto when manufacturing rubber gloves. On the other hand, decolorants (decoloring agents) are substances that remove the water color from the dyeing of textile products colored by dyes. However, bleaching powder is oxidized, and charcoal is absorbed, thereby decolorizing the color of the object.

The present invention provides a method for decolorizing a dark color of a naphthalene-based dispersant into a light color.

According to the present invention, in addition to the decolorization method of the naphthalene-based dispersant for latex, the naphthalene-based dispersant manufacturing process is improved and Gardner No. Through the process of improving 10 to 11 to 9 to 10, and further adding hydrogen peroxide or sodium hypochlorite to the last step of the naphthalene-based dispersant manufacturing process, Gardner No. 9 to 10 or 8 to 9, and most preferably, the improvement of the naphthalene-based dispersant manufacturing process of the present invention and the additional process of decolorization treatment are combined to give Gardner No. It is characterized in that the brightness of the color is improved by 7 to 8.

According to the present invention, there is an excellent effect of providing a novel and improved naphthalene-based dispersant suitable for improving the color brightness of a resin composition for latex using natural rubber and/or synthetic rubber, and a method for manufacturing the same.

In addition, according to the present invention, there is an effect of using the dispersing agent of the present invention to provide household goods such as latex rubber gloves of various bright colors.

1 is a diagram showing a most preferred embodiment of the present invention;
2 is a photograph showing the color evaluation results of the naphthalene-based dispersant according to the present invention.

Hereinafter, the present invention will be described in detail with reference to the most preferred embodiment so that those of ordinary skill in the art can easily carry out the present invention. However, the examples of the present invention have been described so as to be suitable for those skilled in the art to more fully understand the present invention. Therefore, the embodiment of the present invention can be changed in various forms, and since it is possible to change the numerical value or process in various ways within the scope that does not depart from the right of the present invention, such simple numerical value and process change are the right of the present invention. should be considered within the scope.

In the specification of the present invention, when a part "includes" a certain component, it should be viewed as further including other components, rather than excluding other components, unless there is a particular opposition to the component.

As used herein, the term “step for” refers to the process and does not mean “step for”.

The use of the naphthalene-based dispersant of the present invention may be used in any of the resin compositions for latex. For example, the molding die dipped with the coagulant may be any one selected from the group consisting of an acrylonitrile butadiene rubber latex resin composition, a styrene butadiene rubber latex resin composition, a natural rubber latex resin composition, and two or more of them. For example, the mixed resin composition for manufacturing rubber gloves includes 50 to 150 parts by weight of acrylonitrile butadiene rubber latex; 10 to 30 parts by weight of styrene butadiene rubber latex; and 60 to 100 parts by weight of natural rubber latex.

In the naphthalene-based dispersant of the present invention, the use of a coagulant is first considered before the production of latex, and the concentration of the coagulant is adjusted according to the thickness of the glove, and specifically, 5 to 40% by weight is used. The surfactant used in the latex resin composition for rubber gloves is preferably an alkyl alcohol nonionic surfactant. In addition, the release agent added to the latex resin composition for rubber gloves is not particularly limited, but inorganic powders such as Talc, clay, and light coal may be used, or calcium stearate may be used as an organic compound. In addition, the release agent may be used in a concentration of 0.5 to 2% by weight based on the weight of the coagulant.

The naphthalene-based dispersant of the present invention has not been typically used in the latex resin composition for rubber gloves, but in general, the latex resin composition for rubber gloves further includes at least one material selected from the group consisting of a stabilizer, a vulcanizing agent, and a vulcanization accelerator.

The stabilizer is not particularly limited, but at least one of potassium hydroxide, ammonium hydroxide, potassium laurea [K(C ₁₁ H ₂₃ COO)], sodium doresyl sulfate _{[CH 3} (CH ₂ ), CH _{2 OS0 3} Na] can be used In addition, the vulcanizing agent that can be used to increase the elasticity of the latex resin composition for rubber gloves of the present invention includes sulfur and zinc oxide. In addition, when the vulcanizing agent is liquid, a vulcanization accelerator may be used to prevent coagulation.

In addition, according to the present invention, paracresol dicyclopendadiene, paraffin wax, micro-crystal wax, etc. may be additionally used to prevent aging of the latex resin composition for household goods such as rubber gloves.

Hereinafter, a naphthalene-based dispersant manufacturing process as a preferred embodiment of the present invention will be described with reference to Examples.

1 is a diagram showing the most preferred embodiment in which the process improvement and decolorization process of the present invention are added in parallel.

[Example 1]

After adding 416 g of naphthalene, the temperature was raised to 100° C., and 350 g of concentrated sulfuric acid was slowly added. When the temperature is raised again to reach 137° C., the sulfuration reaction proceeds for 3 hours. At this time, the reaction is maintained at 137 ~ 140 ℃. After completion of the reaction, it is cooled to 107° C., and 398 g of primary process water is added.

230 g of formalin was added to the intermediate after the sulfation reaction was completed, and the temperature was raised to reach 128° C., and the condensation reaction was carried out for 6 hours. At this time, the pressure is 2.2 bar, and the temperature is gradually increased and the pressure is increased to reach 130°C and 3.5 bar at the end of the condensation reaction.

After completion of the reaction, when cooled to 80° C., 350 g of caustic soda is added. At this time, neutralization occurs and heat is generated. Divide into 5 times so as not to exceed 80°C, and add slowly. After the caustic soda input is completed, 158 g of secondary process water is added.

1 and 2 cooling is carried out to remove the _{sorghum (Na 2} SO ₄ ) generated by neutralization, _{and when it reaches 10 ∼ 15 ℃ (depending on the SO 4} concentration), the precipitated sorghum is removed as a desicant (desicant). , separate the liquid.

According to the present invention, hydrogen peroxide, sodium hypochlorite or sodium percarbonate is added to the prepared liquid sample in an amount of 1 to 5 wt%, most preferably 2.5 wt%, of the total weight of the dispersant composition, 50 to 70 ° C., most preferably 60 ° C. It is preferable to stir for 30 to 100 minutes, most preferably for 1 hour. The product thus obtained becomes the final bright color polynaphthalene-based dispersant (products of Examples 2 to 5) of the present invention.

[Comparative example]

After adding 416 g of naphthalene, the temperature was raised to 127 ° C, and 371 g of concentrated sulfuric acid was added. When the temperature is raised again to reach 158° C., the sulfation reaction proceeds for 3 hours. At this time, the reaction is maintained at 158 ~ 165 ℃. After completion of the reaction, it is cooled to 107° C., and 398 g of primary process water is added.

230 g of formalin was added to the intermediate after the sulfation reaction was completed, and the temperature was raised to reach 128° C., and the condensation reaction was carried out for 6 hours. At this time, the pressure is 2.2 bar, and the temperature is gradually increased and the pressure is increased to reach 130°C and 3.5 bar at the end of the condensation reaction.

After completion of the reaction, when cooled to 80° C., 370 g of caustic soda is added. At this time, neutralization occurs and heat is generated. Divide into 5 times so as not to exceed 80°C, and add slowly. After the caustic soda input is completed, 158 g of secondary process water is added.

1 and 2 cooling is carried out to remove the _{sorghum (Na 2} SO ₄ ) generated by neutralization, _{and when it reaches 10 ∼ 15 ℃ (depending on the SO 4} concentration), the precipitated sorghum is removed as a desicant (desicant). , separate the liquid. The product thus obtained is a comparative product of the final polynaphthalene-based dispersant.

[Example 2] Hydrogen peroxide (H ₂ O ₂ ) Post-treatment

In addition to the conventional final liquid dispersant, _{1 to 5% by weight of hydrogen peroxide (H 2} O ₂ ), most preferably 2.5% by weight, is added, and 50 to 70° C. Most preferably 60° C. for 45 minutes to 100 minutes, most preferably It was possible to obtain a stable naphthalene-based dispersant without precipitation by stirring for 1 hour.

[Example 3] Sodium hypochlorite post-treatment

In addition to the final liquid dispersant product of Comparative Example, 2.5 wt% of sodium hypochlorite was added and stirred at 60° C. for 1 hour to prepare a naphthalene-based dispersant having stability.

[Example 4] Sodium percarbonate post-treatment

In addition to the final liquid dispersant product of Comparative Example, 2.5 wt% of sodium percarbonate was added and stirred at 60°C for 1 hour to prepare a naphthalene-based dispersant having stability without precipitation.

[Example 5] Concurrent use of manufacturing process improvement and additive post-treatment

With respect to the final liquid dispersant product of the present invention of Example 1, hydrogen peroxide or sodium hypochlorite used in Examples 2 to 3 was added in the same manner and stirred to prepare a naphthalene-based dispersant of the present invention.

According to the present invention, hydrogen peroxide, sodium hypochlorite, or sodium percarbonate added to express the bright color is itself a strong redox agent and has antibacterial, antifungal and antiviral disinfecting effects. do. When it is used in a naphthalene-based dispersant having a bright color for latex, it is difficult to achieve the expected effect when the amount is 1% or less, and when it is more than 5%, there is no significant difference in the amount and effect of the addition below that amount, and the treatment temperature is 50℃ Below, the reaction rate is too low, and at 70° C. or higher, the latex rubber is softened, and the expected treatment effect cannot be achieved.

[Example 6] Quality evaluation of the dispersant of the present invention

The visual color and precipitate (%) of the naphthalene-based dispersant composition of the present invention _{with various dispersants in purified water (H 2 O) were comparatively evaluated.}

A dispersant is added to water, and the pH of the resulting solution is adjusted to 8.0 to 9.0 using 10% aqueous sodium hydroxide, then alumina particles are added, the pH is readjusted to 8.0 to 9.0, and the resulting mixture is stirred for 1 hour. Aqueous nanoparticle dispersants were prepared and evaluated respectively by placing them in an ultrasonic crushing bath (Branson Model 3510, Danbury, CT, USA) at 60° C. and shaking them by hand 20 and 40 minutes after sonication.

For the sediment, 1 g of the dispersion was added to 9 mL of water at pH 8.0, and the resulting mixture was separated in a centrifuge (Beckman Instruments Centrifuge CS-6) at 3,000 rpm for 30 min. After recovering the supernatant, the precipitate After drying, the weight was measured. The experimental results are shown in Table 1 below.

number dispersant sediment (wt%) visual observation One The present invention (Example 5) 50.1 medium viscosity, tan 2 Tyrone 51.7 low viscosity, white 3 sulmosalicylic acid 64.8 very viscous, white 4 sulfoisophthalic acid 100 solid paste, white 5 Pyrogallol 49.7 low viscosity, black 6 3,4 dihydroxybenzoic acid 54.1 low viscosity, brown 7 2,3 dihydroxybenzoic acid 41.5 low viscosity, green 8 molten asset 53.5 low viscosity, brown

[Example 7] Color evaluation of the dispersant of the present invention

The results of evaluating the color of the naphthalene-based dispersion composition itself according to the present invention are shown in FIG. 2 .

The naphthalene-based dispersant prepared by our company in the conventional method (comparative example) shows a dark brown color as shown on the left of the photograph (Gardner No. 10 to 11 range). On the other hand, the products treated with hydrogen peroxide or sodium hypochlorite showed a bright color (Gardner Nos. 9 to 10 and 8 to 9) as the bleaching effect increased from the second to third from the left. As in Example 1, a process improvement product that simply adjusts the amount of concentrated sulfuric acid input and the sulfation reaction temperature and changes the amount of caustic soda (NaOH) input is Gardner N0. 9 to 10, and the product (Example 4), which was post-treated with any one selected from hydrogen peroxide, sodium percarbonate and sodium hypochlorite at the same time as process improvement, exhibited yellowish-brown color and viscosity of medium viscosity (right side of the photo) See the 2nd and rightmost product photos in ).

Claims (7)

delete delete delete introducing naphthalene or a derivative thereof into a reactor as a raw material; heating the naphthalene-based raw material of the above step to 100°C; adding concentrated sulfuric acid to the heated naphthalene-based raw material in the step and mixing; Reheating the mixture of concentrated sulfuric acid and naphthalene-based raw material of the above step to 137 ~ 140 ℃, followed by sulfuration reaction at 137 ~ 140 ℃ for 3 hours; cooling the sulfated reactant obtained in the above step to 107° C. and then performing primary hydrolysis; adding formalin to the cooled intermediate sulfated reaction product obtained in the above step, raising the temperature to 2.2 bar and 128° C., and polycondensation for 6 hours to reach 130° C. and 3.5 bar; After cooling the polycondensation reaction product obtained in the above step to 80 ℃ neutralized so as not to exceed 80 ℃ by slowly adding caustic soda; Secondary addition to the polycondensate obtained in the above step; performing the first to second cooling to remove the Mango grass generated in the above step to remove the Mangwort precipitated as the instantaneous desiccant at 10 to 15 °C and separating the supernatant; A method for producing a bright color naphthalene-based dispersant for latex, comprising the step of adding a decolorizing agent to the liquid obtained in the above step and stirring. The method according to claim 4, wherein the decolorizing agent is any one selected from hydrogen peroxide, sodium hypochlorite, and sodium percarbonate. The method according to claim 4, wherein the amount of the bleaching agent added is 1 to 5 wt%, and stirring is performed at a temperature of 50 to 70°C for 1 hour. A tan light color naphthalene dispersant prepared according to the method of claim 4 .

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