KR102398606B1 - A composition for absorption of harmful elements, manufacturing method thereof and cigarette filter prepared therefrom - Google Patents

Abstract

The composition for adsorption of harmful components according to the present invention is a mixture of iron oxide, polyvinyl alcohol, starch, etc., so that the removal efficiency of harmful components including formaldehyde, tar, etc. This is excellent, and it is possible to improve the problem of the detachment of the coating layer.
In addition, the filter made of the composition has high hydrophilicity, has a large number of porous cells, has a very large specific surface area, has excellent mass transfer rate, and can provide high durability and chemical stability.
The filter manufactured with the composition according to the present invention has excellent processability, so it is used as a filter for various tobacco-related products such as tobacco holders, cigars, cigar holders, pipes, water pipes, electronic smokers, cigarettes, and cigarette lighters, as well as conventional cigarettes. can be
The filter made of the composition according to the present invention can be used as a filter for adsorption of harmful substances due to excellent processability.

Description

A composition for adsorbing harmful ingredients, a method for manufacturing the same, and a cigarette filter prepared from the composition {A composition for absorption of harmful elements, manufacturing method thereof and cigarette filter prepared therefrom}

The present invention relates to a composition for adsorbing harmful substances, a method for manufacturing the same, and a cigarette filter prepared with the composition, and in particular, it effectively reduces harmful components in the air such as formaldehyde as well as tobacco harmful components such as nicotine by 95% or more It relates to a composition for adsorbing harmful components that can be removed, a method for manufacturing the same, and a cigarette filter prepared from the composition.

In general, when a cigarette is smoked, various harmful substances are generated according to the combustion of the tobacco. There are more than 4,000 harmful substances generated during smoking, and about 60 compounds known as carcinogens. When a smoker inhales this, the harmful substances accumulate in the human body, thereby causing diseases such as cancer.

In particular, among the above harmful substances, tar contains about 2.0 to 3.3 mg per cigarette, and as a substance generated according to the combustion of tobacco, it is the main cause of carcinogens, so it is necessary to remove or decompose it. Depending on the incomplete load, 2 to 6% of cigarette smoke is composed of carbon monoxide. This carbon monoxide has an affinity for hemoglobin that is 210 times that of oxygen, which can cause hypoxia.

In addition, tobacco generates harmful volatile organic compounds (VOC) such as benzene and formaldehyde, and contains heavy metals such as cadmium, copper, lead, and zinc. .

In order to eliminate these harms of tobacco, the International Health Organization (WHO) has published [WHO Technical Report Series No. 951, The Scientific Basis of Tobacco Product Regulation, World Health Organization (2008)] and Articles 9 (Regulation on Ingredients of Tobacco Products) and Article 10 (Tobacco Products) of the Framework Convention on Tobacco control (FCTC) In order to reduce certain components of tobacco smoke in the Regulations on Product Information Disclosure), recommendations on the disclosure and management of components of tobacco products in ratifying countries were established. WHO recommends reducing certain components, particularly nicotine, acetaldehyde, acrolein, benzene, benzoapyrene, 1,3-butadiene and formaldehyde, to levels below 125% of the median data set. In view of the new international recommendations for the regulation of tobacco products, there is a need for new tobacco smoke filters and materials used to manufacture tobacco smoke filters that can comply with these regulations.

In order to remove the harmful components as described above and solve the above problems, methods have been proposed to include activated carbon, zeolite, loess, etc. in the filter or tobacco part of cigarettes to achieve filtration through adsorption, but in these cases, all It uses only filtration through adsorption using a porous structure, and there is a problem in that it does not reach the level of filtration efficiency set by the WHO.

Republic of Korea Patent Registration No. 10-0676149 (January 24, 2007)

The present invention has been devised to solve the above problems, and in particular, it aims to provide a composition for adsorbing harmful components that can effectively remove more than 95% of harmful components such as nicotine and formaldehyde, and a method for manufacturing the same .

Another object of the present invention is to provide a cigarette filter prepared from the composition.

The present invention relates to a composition for adsorbing harmful substances, a method for preparing the same, and a cigarette filter prepared from the composition.

One aspect of the present invention is

a) dissolving a water-soluble polymer in a solvent to prepare a water-soluble polymer solution;

b) adding iron oxide and polysaccharide to the water-soluble polymer solution;

c) heating the solution of step b);

d) adding an aldehyde and an acid to the solution of step c) adding;

e) heating and curing the solution of step c) to prepare a soft cured body; and

f) neutralizing the cured product with a basic solution;

It relates to a method for preparing a composition for adsorbing harmful components, comprising:

In the present invention, the water-soluble polymer is any one or a plurality selected from polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polyethyleneimine, polyacrylic acid and polyethylene glycol, and the average particle diameter of the iron oxide is 1 to 100 μm. characterized.

In addition, the starch is characterized in that any one or a plurality selected from starch, carboxymethyl cellulose and carboxymethyl starch.

Also, step c) may be performed at 50 to 180° C. for 30 to 240 minutes.

In the present invention, step d) is with aldehydes It is characterized in that any one or a plurality of acids selected from sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, boric acid, formic acid, acetic acid and carbonic acid is added, and the basic solution is calcium hydroxide, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium silicate , sodium metasilicate, sodium phosphate, and any one or a plurality selected from ammonium hydroxide, the aldehyde is characterized in that any one or a plurality selected from monoaldehyde and dialdehyde.

Another aspect of the present invention relates to a composition for adsorbing harmful components comprising 10 to 30 parts by weight of iron oxide and 30 to 50 parts by weight of polysaccharide based on 100 parts by weight of the water-soluble polymer.

Another aspect of the present invention is a cigarette filter, characterized in that formed by coating or foaming the composition for adsorbing harmful ingredients on a support, wherein the cigarette filter is provided with two different filters adjacent to each other,

a foaming filter formed by foaming the composition for adsorbing harmful components; and

a coating filter in which the composition for adsorbing harmful components is coated on any one or a plurality of supports selected from fabrics, nonwovens and foams;

It is characterized in that it includes.

Another aspect of the present invention relates to a filter for adsorption of harmful components, characterized in that formed by coating or foaming the composition for adsorption of harmful components on a support.

The composition for adsorption of harmful components according to the present invention is a mixture of iron oxide, polyvinyl alcohol, starch, etc., so that the removal efficiency of harmful components including formaldehyde, tar, etc. This is excellent, and it is possible to improve the problem of the detachment of the coating layer.

In addition, the filter made of the composition has high hydrophilicity, has a large number of porous cells, has a very large specific surface area, has excellent mass transfer rate, and can provide high durability and chemical stability.

The filter manufactured with the composition according to the present invention has excellent processability, and is not only related to conventional cigarettes, but also tobacco holders, cigars, cigar holders, pipes, water pipes, electronic smokers, cigarettes, and cigarette-related cigarettes. It can be used as a filter of various types that can remove various products and harmful substances.

Hereinafter, with reference to specific examples, the composition for adsorbing harmful components according to the present invention, a method for manufacturing the same, and a cigarette filter prepared with the composition will be described in detail.

Hereinafter, with reference to specific examples, the embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement them. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In the present invention, the term 'tobacco' refers to a smoking product that can keep a smoking material in fluid contact through a filter, and includes a general cigarette, a cigarette holder, a cigar, a cigar holder, a pipe, a water pipe, an electronic smoker, Cigarettes, cigarette smoke, and the like are included, but are not limited thereto.

In the present invention, the term 'polysaccharide' refers to a polymer in which monosaccharide molecules are chained together, and may be classified into starch, glycogen, and cellulose. The polysaccharide in the present invention includes not only the above substances, but also secondary processed products and derivatives of the above substances.

When the composition for adsorption of harmful components according to the present invention is described through the manufacturing method, the manufacturing method is,

a) dissolving a water-soluble polymer in a solvent to prepare a water-soluble polymer solution;

b) adding iron oxide and polysaccharide to the water-soluble polymer solution;

c) heating the solution of step b);

d) adding an aldehyde and an acid to the solution of step c) adding;

e) heating and curing the solution of step c) to prepare a soft cured body; and

f) neutralizing the cured product with a basic solution;

may include

In the present invention, the water-soluble polymer is a base resin for forming a base material of a foam accommodating iron oxide, which will be described later, or attaching the iron oxide to another substrate, for example, a porous nonwoven fabric or fabric. It is mixed with the powder and does not cause desorption, and an appropriate specific surface area can be formed even after foaming.

The water-soluble polymer is not limited to a type as long as it has the above characteristics, and examples thereof include polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyethyleneimine, polyacrylic acid and polyethylene glycol. The water-soluble polymer may be used alone, but two or more may be mixed and used.

More preferably, polyvinyl alcohol is used as the water-soluble polymer in the present invention. The polyvinyl alcohol is used in various fields such as size and fiber depending on the molecular weight, and it is rare for a polymer to have hydrophilicity and biocompatibility.

Although the production method is not limited, the polyvinyl alcohol may be prepared by polymerization of vinyl acetate using various initiators. At this time, the initiator is not limited in the present invention, but azobisisobutyronitrile, benzoyl peroxide and azobisdimethylvaleronitrile may be used, and azobisdimethylvaleronitrile that can be started at a relatively low temperature is used. it is preferable

The molecular weight or saponification degree of the polyvinyl alcohol is not limited in the present invention. In this case, the degree of saponification means the degree to which acetate groups in the molecular chain of the polyvinyl alcohol (PVA) resin are substituted with hydroxyl groups, and even if the molecular weight is the same, it is divided into water-soluble, poorly soluble, and insoluble according to the difference in saponification degree. . That is, as the acetate group having a relatively large functional group is substituted with a hydroxyl group, the distance between molecular chains becomes narrower, and a strong hydrogen bond is formed between the molecular chains by the hydroxyl groups, thereby distinguishing as described above.

Since the degree of saponification of polyvinyl alcohol affects solubility, it is preferable to have a degree of saponification of 99.0 mol% or less, preferably 88.0 to 98.0 mol%, because it can be prepared in a solution state. In addition, the molecular weight may be different depending on polymerization methods such as bulk polymerization and solution polymerization, but polyvinyl alcohol of 10,000 to 200,000 g/mol based on the weight average molecular weight can satisfy moldability and adhesion to other substrates. desirable.

In addition, it is preferable to mix two or more types of polyvinyl alcohol having different molecular weights to increase miscibility and moldability. This increases the compactness of the composition as a polymer with a small molecular weight is interposed between the gaps between the polymers having a relatively high molecular weight, and even when the coating layer is formed, a more even coating layer can be formed due to this compactness.

The molecular weight of the polyvinyl alcohol may be added by mixing, for example, those having a weight average molecular weight of 10,000 to 50,000 g/mol and those having a molecular weight of 100,000 to 150,000 g/mol. At this time, their content is not limited, and can be freely adjusted according to processability and moldability.

In the present invention, the solvent is not limited to the type as long as it can dissolve the water-soluble polymer in water or a polar solvent similar to water. Examples of the solvent include water or a lower alcohol having 1 to 4 carbon atoms.

In the present invention, in step a), the water-soluble polymer is mixed with the solvent to prepare a solution, but the concentration of the water-soluble polymer is preferably mixed so that the water-soluble polymer accounts for 10 to 20% by weight in 100% by weight of the total solution. .

In the present invention, step b) is a step of adding iron oxide, starch and aldehyde to the water-soluble polymer solution.

In the present invention, the iron oxide (α-FeOOH) is a hydroxyl compound of iron, which is a secondary mineral generally generated by weathering at the surface, has pores on the surface, and has many microcracks inside, so the specific surface area is large. It can adsorb various harmful components contained in cigarette smoke. It can remove 90% up to 99% of arsenic, nicotine, tar, and formaldehyde, as well as arsenic, an inorganic harmful component most adsorbed to iron hydroxide.

In the present invention, the manufacturing method of the iron oxide is not limited. For example, the iron oxide is a first neutralization step of adding an alkali compound to a solution containing an iron precursor compound and adjusting the pH to 6.5 to 7.5 to prepare a first mixture; a second neutralization step of adding an alkali compound to the first mixture and adjusting the pH to 9 to 10 to prepare a second mixture; filtering the second mixture to obtain a precipitate; And drying the obtained precipitate at 20 to 80 ℃; can be obtained including.

In the present invention, the type of the iron precursor compound is not limited. Specifically, the iron precursor compound is any one selected from ferric citrate, ferric citrate hydrate, ferrous sulfate heptahydrate, iron oxalate dihydrate, iron acetylacetonate, ferric phosphate dihydrate, ferric hydroxide, and the like. It may be one or plural. Moreover, the said alkali compound is also not limited. For example, sodium hydroxide (NaOH), ammonia, potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc. may be used without limitation.

The iron oxide prepared as described above preferably has an average particle diameter of 1 to 100 μm. In addition, it is preferable that the iron oxide is 200 to 500 m 2 /g.

In the present invention, the iron oxide is preferably added in an amount of 10 to 30 parts by weight based on 100 parts by weight of the water-soluble polymer. When the amount of iron oxide added is less than 10 parts by weight, the effect of adsorption of harmful components according to the addition of iron oxide is insufficient, and when it is added in excess of 30 parts by weight, mechanical properties of the filter after foaming may be greatly reduced.

In the present invention, the polysaccharide is a polymer in which a plurality of monosaccharide molecules are chain-linked as described above, and may include starch (starch), glycogen, and cellulose depending on the form of the bond. It plays a role in determining the size of the foaming pores.

More preferably, the polysaccharide may be any one or a plurality selected from starch, carboxymethyl cellulose and carboxymethyl starch.

The starch is a tasteless, odorless white powder that does not dissolve in water. The molecular weight of starch is about 50,000 to 200,000, and the specific gravity is about 1.65, so it is precipitated in water. In addition, starch exists in the form of particles, whose basic structure is glucose, 20 to 25% of long-chain amylose, and 75 to 80% of branched amylopectin. consist of.

When these starches are gelatinized by temperature, the structures of amylose and amylopectin are loosened and then destroyed to form a colloidal solution, which increases miscibility with water-soluble polymers and increases viscosity. The gelatinized starch is recrystallized by cooling to form pores in the manufactured filter.

Since starch gelatinization and aging are affected by the size and shape of starch molecules and the type of starch, desired properties of the filter can be adjusted by controlling the type and content of added starch.

Examples of the starch include rice starch, glutinous rice starch, wheat starch, corn starch (corn starch, corn grits), potato starch, tapioca starch, sweet potato starch, arrowroot starch and high amylose starch. In addition to these starches, decomposition products thereof, amylose or amylopectin decomposition products, and processed starches may be mentioned. Examples of the processed starch include oxidized starch such as dicarboxylic acid starch; esterified starches such as acetylated starch; etherified starches such as carboxymethylated starch; cross-linked starch treated with acetaldehyde or phosphoric acid; cationized starches such as those obtained by tertiary amination of starch with 2-dimethylaminoethyl chloride; and the like. Since these starches have different viscosity, molecular structure, properties of starch particles, gelation properties, water solution stability, aging properties, water retention properties, and elasticity depending on the type of raw material or modification method, the working temperature is adjusted according to the starch. It is preferable to do

Among them, it is preferable to use natural starch because it is easy to control the processing temperature and is inexpensive. In particular, when preparing the composition, it is preferable to use corn grits from the viewpoint of easy mixing of materials and good processability such as viscosity control. At this time, the corn grits are generally adjusted to a particle size of 9 to 60 mesh by turning on the endosperm of the corn.

In addition, two or more starches may be mixed in consideration of the characteristics of the filter to be manufactured to variously change the mechanical properties of the filter. For example, if the mechanical strength of the filter is required, natural starch such as rice starch or corn starch, modified starch such as acetyladipic acid crosslinked starch, phosphate crosslinked starch, or alkylated starch is used alone or in combination of two or more types, The effect can be further increased, and when flexibility of the filter is required, it is good to add gelatinized starch, acid-treated starch, roasted starch, oxidized starch, ester starch, etc. to potato starch, sweet potato starch, alone or in combination of two or more.

The carboxymethyl cellulose and carboxymethyl starch are derivatives obtained by reacting conventional cellulose or starch with chloroacetic acid, and are used to form finer pores due to their higher viscosity than general starch. However, in this case, it is recommended to secure the size of the pores by additionally adding a foaming agent because the flow rate through the filter, which is the final product, may be reduced.

The foaming agent is not limited to the addition amount, material, and type as long as it is commonly used in the art. For example, in the case of an inorganic foaming agent, calcium carbonate (CaCO ₃ ), sodium bicarbonate (NaHCO ₃ ), ammonium bicarbonate (NH ₄ HCO ₃ ), ammonium carbonate ((NH ₄ ) ₂ CO ₃ ), ammonium nitrite (NH ₄ NO ₂ ), Sodium hydrogen boride (NaBH ₄ ) and sodium carbonate (Na ₂ CO ₃ ), etc. may be included, and as an organic blowing agent toluene sulfonyl hydrazide, azodicarbonamide (azodicabon amide), dinitrosopenta Methylene tetraamine (dinitroso pentamethylene tetramine), p,p'-oxybisbenzenesulfonyl hydrazide (p,p'-oxybisbenzenesulfonyl hydrazide), p-toluenesulfonylhydrazide (p-toluenesulfonylhydrazide), benzenesulfonyl high and benzenesulfonylhydarazide. These may be used alone or in combination of two or more.

In addition, the polysaccharide may include a derivative having a functional group that is partially or completely different from the hydroxyl group possessed by reacting with various reagents. Examples of the derivative include carboxymethyl cellulose and carboxymethyl starch, cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, cellulose sulfate, methylcellulose, It includes ethyl cellulose, ethyl methyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, etc. In addition, cellulose or starch derivatives reacted with various reagents may be included.

The polysaccharide is preferably added in an amount of 30 to 50 parts by weight based on 100 parts by weight of the water-soluble polymer. When the added amount of the polysaccharide is less than 30 parts by weight, the size of the pores formed after foaming is too small to expect the role of a filter.

Step b) may be performed by adding powdered iron oxide and starch to the water-soluble polymer solution and sufficiently stirring. In this case, mixing may be promoted by accompanying heating, if necessary.

In step b), in addition to the composition, various additives commonly added during filter manufacture, for example, a foaming agent, a filler, an ion exchange resin, a flavoring agent, a drying agent, etc. may be further added.

Examples of the filler include silica, magnesium silicate, aluminum oxide, iron oxide, zeolite, carbon particles, carbon fibers, fibers, glass beads, etc. In addition, various materials usable as fillers of filters may be further included.

Examples of the ion exchange resin include polymers having a backbone such as styrene-divinyl benzene (DVB) copolymer, acrylate, methacrylate, phenol formaldehyde condensate and epichlorohydrin amine condensate. In addition to, the type is not limited as long as it is a monomer or polymer having a plurality of reactive functional groups attached to the main chain backbone.

Examples of the flavoring agent include cloves (cloves), ground cloves, ground clove flowers, cocoa, menthol, cloves, cherry, chocolate, orange, mint, mango, vanilla, cinnamon, tobacco, anethol, licorice, limonene, citrus. , eugenol, and the like, and these may be used alone or in combination of two or more.

In the present invention, the additive amount is not limited, and each additive may have various amounts added within a range that does not impair the purpose of the present invention.

In step c), the solution of step b) is heated to secure thickening stability through swelling of the polysaccharide, and in particular, starch is gelatinized. Iron oxide particles are produced by recombination of starch molecules by increasing the viscosity of the polysaccharide included in the composition. It can prevent precipitation and at the same time promote the formation of pores in the filter.

Step c) may vary depending on the type of polysaccharide, particularly starch, but may be performed at 50 to 180° C., more preferably at 60 to 80° C. for 30 to 120 minutes. The above temperature range is the gelatinization temperature of general natural starch or synthetic starch, and satisfying the above range is preferable to prevent precipitation of iron oxide to evenly disperse the composition in the composition, and to facilitate the formation of pores in the filter.

In addition, after heating the composition, it is preferable to proceed with aging for about 1 hour at the gelatinization temperature in order to improve the dispersibility and stability of the composition. Herein, after step c), it is preferable to continuously maintain the gelatinization temperature by continuing heating the composition during the process in order to prevent a decrease in viscosity due to aging of the starch and immersion of iron oxide by this.

As in step d), in the solution-state composition after the aging of starch has been completed, the pH of the composition is lowered by adding a certain amount of aldehyde and acid as in step d). It decomposes and induces acetal reaction between polyvinyl alcohol and aldehyde.

The aldehyde is for imparting moldability by crosslinking the water-soluble polymer, and the water-soluble polymer undergoes dehydration condensation (acetalization) by reaction with the aldehyde to increase the viscosity.

The aldehydes include, for example, monoaldehydes (eg, formaldehyde, urea, melamine-formaldehyde resins and their homologs, boric acid and other inorganic compounds), dialdehydes (cis-1,3-cyclohexane dicarboaldehyde, trans- 1,3-cyclohexane dicarboaldehyde, cis-1,4-, cyclohexane dicarboaldehyde, trans-1,4-cyclohexane dicarboaldehyde, cis-1,3-cyclooctane dicarboaldehyde, trans-1 (C6-C16)aliphatic dicarboaldehyde such as ,3-cyclooctane dicarboaldehyde), etc.), and the like. good.

The aldehyde is preferably added in an amount of 40 to 60 parts by weight based on 100 parts by weight of the water-soluble polymer. If the amount of iron oxide added is less than 40 parts by weight, crosslinking of the water-soluble polymer is not sufficient, so moldability and mechanical properties may significantly decrease. can be easily broken

Since the acid input in step d) acts as a catalyst for a foaming agent, particularly an inorganic foaming agent such as sodium carbonate, it is preferable to appropriately input the acid according to the amount and concentration of the composition without determining the amount or concentration thereof.

Specifically, the acid is not limited to the type as long as it is a conventional acid capable of lowering the pH, but any one or a plurality of organic acids or inorganic acids selected from sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, boric acid, formic acid, acetic acid and carbonic acid. it's good

In addition, the acid is added as a diluted solution rather than a stock solution, and the concentration of the acid in the diluted solution is preferably 20 to 50% by weight, and 10 to 20 parts by weight is preferably added based on 100 parts by weight of the water-soluble polymer.

Since the curing and foaming reaction of the composition proceeds after the acid is added, it is preferable to heat the composition at 60 to 100° C. for 10 to 20 hours to complete the solid foam. At this time, the foam may be put into a mold and foamed, but the present invention is not limited thereto, and may be molded using a punching machine after curing and foaming. The finished foam is acidic by the acid catalyst. Therefore, it is preferable to treat the foam with a neutralizing agent or to adjust the pH to 6 to 8 by washing with water. When the pH of the foam is lower than the above range, it is difficult to obtain a stable foam or filter because the polyvinyl alcohol resin is decomposed or crosslinked by acid. may occur. Neutralizing agents for neutralizing the foam include, for example, alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydrogen carbonate and potassium carbonate, alkaline earth metal compounds such as calcium hydroxide, ammonia, aqueous ammonia solution. there is. Examples of the alkylene oxides include ethylene oxide and propylene oxide; Glycidyl ethers, such as ethylene glycol diglycidyl ether, are mentioned. One or a mixture of the neutralizing agent may be used, and the concentration or treatment time of the neutralizing agent is not limited in the present invention.

In addition, it is preferable to remove the neutralizing agent, residues, and unreacted substances remaining after neutralization, and wash with water to dissolve starch, which is a water-soluble component, to form pores. In particular, when a large amount of the neutralizing agent remains, the composition is deteriorated and stable molding cannot be performed. In particular, alkali metals or alkaline earth metals contained in compounds used as neutralizers are prone to thermal decomposition, and if they remain in large amounts, severe polymer decomposition or crosslinking gelation may occur, and stable melt molding may not be possible. it is preferable

For the washing with water, there is, for example, a polar solvent such as water, methanol, or ethanol, and in particular, it is preferable to repeat the removal and washing with a mixed solution of water and methanol or ethanol.

As described above, the neutralized water-containing composition secures flexibility, which is advantageous for molding, and may be dried or processed into a filter form in a water-containing state if necessary. In addition, the composition may be coated on the surface of the support by increasing the moisture content and preparing it in a liquid state, immersing the support and curing it. In addition, the filter form may be manufactured by a molding method such as air pressure molding, vacuum molding, press molding, etc., of the molding material.

The present invention may include a composition for adsorbing harmful components prepared by the above manufacturing method. In this case, the composition may contain 10 to 30 parts by weight of iron oxide and 30 to 50 parts by weight of starch based on 100 parts by weight of the water-soluble polymer.

The composition for adsorbing harmful components may further include various additives according to the processing method, purpose, and need. The additive may include the above-described foaming agent, filler, ion exchange resin, flavorant, desiccant, etc., in addition to polymer resin, antioxidant, stabilizer, lubricant, processing aid, antistatic agent, colorant, etc. may be further blended.

In addition, the present invention may include a cigarette filter, characterized in that formed by coating or foaming the composition for adsorbing harmful components on a support.

In the present invention, it is preferable that the support has a porous structure, and for example, a nonwoven fabric, a woven fabric, or a sponge may be applied. In addition, when the support is a woven or non-woven fabric, materials such as natural fibers and inorganic fibers are not limited in addition to synthetic and semi-synthetic fibers such as polyester, polyamide, polyacrylic, polyurethane, and viscose rayon.

The composition for adsorption may be obtained by immersing the support in a composition for adsorbing harmful components to which a crosslinking agent is added to coat the support, then curing it, or spraying a coating solution on the surface of the support so that the composition is evenly coated on the surface of the support.

In the present invention, when the cigarette filter is applied to a smoking machine, two types of different filters are provided adjacent to each other, and the filter comprises: a foaming filter formed by foaming the composition for adsorbing harmful components; and a coating filter formed by coating the composition for adsorbing harmful components on any one or a plurality of supports selected from fabrics, nonwovens and foams.

When describing this in detail based on a regular cigarette, the foam filter is a part in direct contact with the lips when smoking, and when cigarette smoke is sucked (inhaled), harmful components such as tar, nicotine, and formaldehyde contained in cigarette smoke are finally removed. serves to remove In addition, the foamed filter is cured and molded of a polymer resin containing iron oxide itself, and has higher durability than a coated filter, so that the filter's filtration efficiency does not decrease even when subjected to any external force or foreign substances such as saliva are on the surface.

The coating filter is located between the foam filter and tobacco (tobacco leaf), and the composition for adsorbing harmful ingredients is coated on a filter-type support, and since the coating layer may be lost by external force, it is in direct contact with the smoker's lips. It is provided so that it is relatively adjacent to the tobacco rather than a part, so that harmful components in the intake air can be adsorbed and the filtration efficiency can be increased.

The cigarette filter limits the positions of the foam filter and the coated filter in the smoking machine as described above, but the location and number of the tobacco filter may be different depending on the type, length, diameter, type, amount of tobacco, etc. of the smoking machine. . In addition to the foam filter and the coating filter, a general filter capable of adsorbing harmful substances may be further provided, but the present invention is not limited thereto.

The present invention includes a filter for adsorbing harmful components, characterized in that formed by coating or foaming the composition for adsorption of harmful components on a support. The filter for adsorption of harmful substances effectively adsorbs various harmful substances contained in water or air, particularly substances such as formaldehyde, 1,3-butadiene, and benzopyrene, which are first-class carcinogens, as well as acetaldehyde, catechol, styrene, and isoprene. , it is possible to effectively remove the harmful components in an environment where harmful components such as indoor and industrial environments and packaging exist.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are only examples for explaining the present invention in more detail, and the present invention is not limited by the following examples.

The physical properties of the specimens prepared in the following Examples and Comparative Examples were measured as follows.

(The ability to remove harmful substances)

The removal efficiency of harmful substances was measured in accordance with KS I 2218 (detector tube type gas meter). First, a sample having a size of 100 × 200 × 10 mm prepared in Examples and Comparative Examples was placed in a 5L reactor and sealed. Then, a test gas having an initial concentration of 50 μmol/mol was injected, and the concentration was measured for 2 hours in 30-minute increments from the initial (before injection) using a gas detection tube (SPS-KCL I2218-6218). The temperature during the test was 23.0±5.0° C., and the RH humidity was 50±10%. In addition, in order to calculate the concentration reduction rate, the concentration was measured after injection of the test gas in the absence of a sample. Measurement items are methyl mercaptan (CH ₃ SH), formaldehyde (CH ₂ O), pyridine (C ₅ H ₅ N), ammonia (NH ₃ ), toluene (C ₆ H ₅ CH ₃ ), hydrogen sulfide (H ₂ S) ), trimethylamine ((CH ₃ ) ₃ N).

[Equation 1]

(In Equation 1, A is the concentration of the test gas in the absence of a sample, and B is the concentration of the test gas after inputting the sample.

In addition, the tobacco filter tow manufactured in Examples and Comparative Examples is tar and nicotine in accordance with KS H ISO 6565 (Tobacco and tobacco products - Inhalation resistance of tobacco (cigarette) and pressure drop of filter rod - Standard conditions and measurement method) The resistance to suction was measured.

(whether or not cells are formed)

The manufactured filter was cut in a direction perpendicular to the long axis so that the cross-section was circular, and then visually checked and evaluated according to the following criteria.

◎: Very good

○: good

△: bad

×: cannot be formed

(Example 1)

First, an aqueous solution of polyvinyl alcohol having a weight average molecular weight of 100,000 was prepared, and the polyvinyl alcohol concentration in the entire aqueous solution was adjusted to 15% by weight.

Next, goethite (α-FeOOH) and carboxymethyl cellulose having an average particle diameter of 5 μm and a specific surface area of 100 m 2 /g were added to the polyvinyl alcohol aqueous solution prepared as described above and uniformly mixed. At this time, the amount of the components added was 20 parts by weight of goethite and 40 parts by weight of carboxymethyl cellulose based on 100 parts by weight of polyvinyl alcohol. In order to further enhance the foaming effect, 1 part by weight of sodium carbonate (NaCO ₃ ) was further added.

The uniformly mixed solution was heated at a temperature of 70°C for 1 hour, then 50 parts by weight of formaldehyde and 15 parts by weight of sulfuric acid having a concentration of 30% by weight were further added, followed by curing at 80°C for 15 hours to form a foam. completed. The finished foam was neutralized with an aqueous sodium hydroxide solution (concentration: 15% by weight) until the pH reached 7.

(Example 2)

In Example 1, the composition before curing was supported on a support (cellulose acetate, 100 × 200 × 10 mm) for 30 minutes, and then a temperature of 80° C. was applied for 15 hours to form a coating layer of the composition on the surface of the support. The cured support was neutralized with an aqueous sodium hydroxide solution (concentration: 15 wt%) until the pH reached 7.

(Comparative Example 1)

A sample was prepared in the same manner as in Example 1, except that goethite was not added during the preparation of the composition.

(Comparative Example 2)

A sample was prepared in the same manner as in Example 1, except that the amount of goethite was added to 40 parts by weight during the preparation of the composition.

(Comparative Example 3)

Samples were prepared in the same manner as in Example 1, except that the amount of formaldehyde added was 30 parts by weight when preparing the composition.

(Comparative Example 4)

A sample was prepared in the same manner as in Example 1, except that the amount of formaldehyde added was 70 parts by weight when preparing the composition.

(Comparative Example 5)

A sample was prepared in the same manner as in Example 1, except that carboxymethyl cellulose was not added during the preparation of the composition.

(Comparative Example 6)

A sample was prepared in the same manner as in Example 1, except that the heating temperature was set to 40° C. after adding starch instead of carboxymethyl cellulose when preparing the composition.

(Comparative Example 7)

Samples were prepared in the same manner as in Example 1, except that the composition was not neutralized with caustic soda when preparing the composition.

[Table 1]

As shown in Table 1 above, it was confirmed that the cigarette filter manufactured through the present invention had excellent suction resistance with nicotine suction resistance of 50% or more and tar suction resistance of 60% or more.

On the other hand, Comparative Example 1, in which goethite was not added during the manufacture of the filter, had significantly lowered resistance to nicotine and tar, and Comparative Examples 2 to 4 and carboxymethylcellulose were added in the amounts of goethite and formaldehyde, respectively, out of the scope of the present invention. In Comparative Example 5, in which foaming or cell formation did not proceed, there was no filter effect, and in Comparative Example 7, which was not neutralized with caustic soda, goethite did not remain in the filter and was lost, and it was confirmed that the adsorption effect was reduced.

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

As shown in Tables 2 to 8, it was confirmed that the filters manufactured according to the present invention effectively adsorb harmful substances in the air, such as methyl mercaptan, formaldehyde, pyridine, ammonia, toluene, trimethylamine, and hydrogen sulfide. Separately, as in Comparative Examples 2 to 5, when foaming did not proceed properly, the filter could not maintain the shape of the filter and thus the adsorption effect could not be measured. It was confirmed that the adsorption effect of harmful components decreased rapidly.

The above description is merely illustrative of the technical spirit of the present invention, and various modifications and variations will be possible without departing from the essential characteristics of the present invention by those skilled in the art to which the present invention pertains. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain, and the scope of the technical spirit of the present invention is not limited by these embodiments. The protection scope of the present invention should be construed by the claims below, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (12)

a) dissolving a water-soluble polymer in a solvent to prepare a water-soluble polymer solution;
b) adding 10 to 30 parts by weight of goethite (α-FeOOH) and 30 to 50 parts by weight of carboxymethylcellulose to 100 parts by weight of the water-soluble polymer solution;
c) heating the solution of step b);
d) adding 40 to 60 parts by weight of an aldehyde and 10 to 20 parts by weight of an acid to the solution in step c);
e) heating and curing the solution of step c) to prepare a soft cured body; and
f) neutralizing the cured product with a basic solution;
A method for preparing a composition for adsorbing harmful components, comprising:
The method of claim 1,
The water-soluble polymer is polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polyethyleneimine, polyacrylic acid, and a method for producing a composition for adsorption of harmful components, characterized in that a plurality of one or more selected from the group consisting of polyethylene glycol.
The method of claim 1,
The method for producing a composition for adsorption of harmful components, characterized in that the average particle diameter of the goethite is 1 to 100㎛.
delete The method of claim 1,
Step c) is a method for preparing a composition for adsorbing harmful components, characterized in that it is performed at 50 to 180° C. for 30 to 240 minutes.
The method of claim 1,
The aldehyde is a method for manufacturing a composition for adsorption of harmful components, characterized in that any one or a plurality selected from monoaldehyde and dialdehyde.
The method of claim 1,
In step d), any one or a plurality of acids selected from sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid, boric acid, formic acid, acetic acid and carbonic acid is added.
The method of claim 1,
The basic solution is one or more selected from calcium hydroxide, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, sodium phosphate and ammonium hydroxide.
10 to 30 parts by weight of goethite, 30 to 50 parts by weight of carboxymethylcellulose, 40 to 60 parts by weight of aldehyde, and 10 to 20 parts by weight of acid, based on 100 parts by weight of water-soluble polymer.
Tobacco filter, characterized in that formed by coating or foaming the composition for adsorbing harmful components according to claim 9 on a support.
11. The method of claim 10,
The cigarette filter is provided with two types of different filters adjacent to each other, the filter,
a foaming filter formed by foaming the composition for adsorbing harmful components; and
a coating filter in which the composition for adsorbing harmful components is coated on any one or a plurality of supports selected from fabrics, nonwovens and foams;
Cigarette filter comprising a.
A filter for adsorption of harmful components, characterized in that it is formed by coating or foaming the composition for adsorption of harmful components according to claim 9 on a support.