Lower aldehyde adsorbent, lower aldehyde adsorbing fiber, and method for producing lower aldehyde adsorbent

Abstract

To provide an adsorbent, a fiber, and a method for producing the adsorbent, in which a functional agent having high reactivity with aldehydes does not detach from a base material and aldehyde adsorption capacity can be maintained for a long period.SOLUTION: A lower aldehyde adsorbent of the present invention comprises: a base-material resin which contains, as a main component, a copolymer of a base-material-constituting monomer having two vinyl groups and a reactive monomer having a glycidyl group, and which has numerous pores; and an adsorption site that is chemically bonded to the base-material resin, has a primary amino group at a terminal portion, and adsorbs aldehydes having 2 to 10 carbon atoms.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a lower aldehyde adsorbent that adsorbs aldehydes, which are odor-causing substances, particularly aldehydes having 2 to 10 carbon atoms, a lower aldehyde-adsorbing fiber, and a method for producing the lower aldehyde adsorbent. [Background technology]

[0002] Homes are filled with a variety of odors, including those from pets, cigarettes, toilets, building materials, and other everyday odors. These odor components are primarily classified into nitrogen-based (ammonia, trimethylamine, etc.), fatty acid-based (acetic acid, isovaleric acid, etc.), and aldehyde-based (acetaldehyde, nonenal, etc.) odor components. Among these, aldehyde components such as formaldehyde (HCHO) and acetaldehyde (CH3CHO) account for approximately 80% of indoor odor components, and acetaldehyde is particularly detected in homes where pets (dogs, cats, etc.) have been kept for extended periods. On the other hand, aldehydes are also detected in homes without pets. For example, it is known that fibers from clothing treated with fabric softener can fall into the room and cause odors. This is due to nonanal (C8H), which is contained in fabric softeners as a fragrance component for flowers and fruits. 17 CHO) is converted to nonenal (C7H 14 =CHCHO) etc.

[0003] The interior of an automobile is a small, enclosed space, so even trace or low-concentration odors can be strongly felt. The urethane used in seat cushioning generates acetaldehyde during its manufacturing process, and the trace amounts of acetaldehyde and other volatile components remaining in the urethane give off a distinctive odor. This is particularly noticeable in new cars and in midsummer. Even if you don't smoke in the car, the smell of cigarette smoke can fill the car if someone who smokes elsewhere rides with you, creating an unpleasant odor for other passengers, especially non-smokers, and making it difficult to eliminate. Furthermore, odors inside the car can cause sick car syndrome, including allergies, headaches, and dizziness.

[0004] Activated carbon is commonly known for its deodorizing and odor-eliminating properties, but physical adsorption of activated carbon alone is insufficient to adsorb aldehydes. Furthermore, among aldehydes, formaldehyde is highly hydrophilic and can be removed relatively easily by washing with water using a wet scrubber or similar device, but other aldehydes are not easily adsorbed and removed. In response to this, aldehyde adsorbents are commercially available, in which functional chemicals highly reactive with acetaldehyde and other aldehydes are impregnated onto activated carbon or porous inorganic substrates.

[0005] For example, Patent Document 1 discloses an air purification filter (claim 1) that includes activated carbon impregnated with hydrazines. Hydrazines are compounds containing a hydrazino group (-NH-NH). Because a nitrogen atom with an unshared electron pair is bonded to the α-position of the nitrogen atom at the terminal of the hydrazino group, they have extremely high nucleophilic reactivity. This unshared electron pair nucleophilically reacts with the carbonyl carbon of aldehydes, immobilizing the aldehydes as hydrazide derivatives, which is thought to achieve high aldehyde removal performance (paragraph 0011 of Patent Document 1). However, the catalytic action of activated carbon promotes the decomposition of hydrazines on the activated carbon. Therefore, while activated carbon impregnated with hydrazine initially exhibits aldehyde adsorption function, after long-term use or storage, only the physical adsorption function of the activated carbon itself is exerted, resulting in insufficient aldehyde adsorption.

[0006] Patent Document 2 discloses a deodorizing material in which hydrazine salt or metal salt hydrazine double salt is impregnated onto a porous clay or porous ceramic carrier. The porous clay is a clay mineral primarily composed of chain-like magnesium silicate, consisting of at least one of sepiolite, kallionite, smectite, imogolite, and pargoskite (claims 1 and 2). It adsorbs and removes acetaldehyde, the main component of tobacco odor (paragraph 0001). However, because the deodorizing material in Patent Document 2 uses an inorganic substrate such as sepiolite, hydrazine is simply trapped in the pores of the inorganic substrate without chemically bonding. Instead, water-soluble hydrazine is released from the inorganic substrate by water or moisture in the air. If it were released by washing with water, it would be unsuitable for use in fixing hydrazine to fibers such as clothing. While it is possible to prevent release by mixing hydrazine into a binder and adhesively bonding it to the surface of the porous inorganic substrate, this would clog many pores, reducing the specific surface area and significantly reducing the aldehyde adsorption function.

[0007] Therefore, it is desirable to develop an aldehyde adsorbent that has a large specific surface area and in which functional chemicals with high chemical adsorption capacity for aldehydes do not decompose on the substrate surface or are released into water. Furthermore, because deodorizing and eliminating aldehydes is not easy, there have been no adsorbents that can maintain their deodorizing effect for a long period of time. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2008-212448 A [Patent Document 2] Japanese Patent Application Publication No. 11-553 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, an object of the present invention is to provide an adsorbent that adsorbs lower aldehydes having 2 to 10 carbon atoms, a fiber containing the adsorbent, and a method for producing the lower aldehyde adsorbent. Another object of the present invention is to provide an adsorbent, a fiber, and a method for producing the adsorbent that can maintain aldehyde adsorption ability for a long period of time without a functional agent that is highly reactive with aldehyde being released from the substrate. [Means for solving the problem]

[0010] The lower aldehyde adsorbent 10 of the present invention is composed of a base resin 30 having numerous pores 31 and consisting primarily of a copolymer of a base material constituent monomer having two vinyl groups and a reactive monomer having a glycidyl group, and an adsorption site 20 chemically bonded to the base resin 10, having a primary amino group at an end 21, and adsorbing an aldehyde having 2 to 10 carbon atoms.

[0011] In the present invention, the adsorption sites 20 for aldehydes contain hydrophilic primary amino groups (-NH2), which raise concerns about their elution into water. However, the adsorption sites 20 are chemically (covalently) bonded to the base resin 30, rather than simply being physically bonded or coated. Therefore, even when the lower aldehyde adsorbent 10 of the present invention is used in continuous aeration treatment, the adsorption sites 20 do not elute into water and are firmly bonded to the base resin 30, allowing the present invention to maintain aldehyde adsorption ability for a long period of time. Furthermore, because the adsorption sites 20 have primary amino groups at the terminals 21, they are highly reactive and can effectively adsorb aldehydes with 2 to 10 carbon atoms, which have traditionally been difficult to adsorb, and effectively deodorize their odors.

[0012] The lower aldehyde adsorbent fiber of the present invention is a fiber having the above-described lower aldehyde adsorbent 10 of the present invention fixed thereto. The present invention can be applied to, for example, a nonwoven fabric filter or clothing fabric to effectively adsorb and remove aldehydes having 2 to 10 carbon atoms.

[0013] The method for producing the lower aldehyde adsorbent 10 of the present invention includes the steps of: polymerizing a base material-constituting monomer having two vinyl groups with a reactive monomer having a glycidyl group to prepare a copolymer that will be the main component of the base resin 30; and reacting the copolymer with an amine to form adsorption sites 20 that are chemically bonded to the base resin 30, have primary amino groups at terminals 21, and adsorb aldehydes having 2 to 10 carbon atoms. By using a relatively simple production method, the copolymer and amine are chemically bonded to each other, preventing the amine from being released. [Effects of the Invention]

[0014] The present invention can effectively adsorb and remove aldehydes having two or more carbon atoms, which are relatively difficult to remove and deodorize, from indoor spaces, thereby purifying the air. Furthermore, because the adsorption sites are firmly chemically bonded to the base resin and do not detach or dissolve in water, the lower aldehyde adsorbent of the present invention can be used in filters for continuous circulation treatment, and in clothing and fabric products that are washed repeatedly. [Brief explanation of the drawings]

[0015] [Figure 1] Schematic diagram showing the base resin and adsorption sites constituting the lower aldehyde adsorbent of the present invention. [Figure 2] 1 is a schematic cross-sectional view showing the inside of some pores of the lower aldehyde adsorbent of the present invention. [Figure 3] Image showing the base resin (a) and the lower aldehyde adsorbent of the present invention (b) [Figure 4] Graph showing the specific surface area remaining ratio of the present invention and the prior art [Figure 5] Graph showing aldehyde adsorption characteristics of the present invention and the prior art [Figure 6] Graph showing aldehyde adsorption characteristics of the present invention and the prior art [Figure 7] Graph showing the results of filtration tests of the present invention and the prior art DETAILED DESCRIPTION OF THE INVENTION

[0016] Embodiments of a lower aldehyde adsorbent (adsorbent material, adsorption composition, capture agent), a lower aldehyde-adsorbing fiber, and a method for producing a lower aldehyde adsorbent according to the present invention will be described with reference to Figures 1 to 3. The following embodiments are described in detail for illustrative purposes only and are not intended to limit the present invention.

[0017] 1 and 2 show a schematic diagram of a base resin 30 constituting the main body of a lower aldehyde adsorbent (hereinafter referred to as "adsorbent") 10 according to the present invention, and an adsorption site 20 bonded to the base resin 30 via a chemical bond 22, for ease of explanation. In this specification, aldehydes having 10 or fewer carbon atoms are referred to as "lower aldehydes," and the adsorption target (target substance) of the present invention is an aldehyde having 2 to 10 carbon atoms, which is relatively difficult to remove and deodorize. Aldehydes (R-CO-H) are organic compounds composed of a carbonyl group (-CO-), a hydrogen atom (H) bonded to the carbon atom, and an optional group (R), and low-molecular-weight aldehydes in particular have a pungent odor.

[0018] The aldehydes with 2 to 10 carbon atoms to be adsorbed are specifically acetaldehyde (ethanal CH3CHO), propionaldehyde (propanal C2H5CHO), butanal (C3H7CHO), pentanal (C4H9CHO), hexanal (C5H 11 CHO), heptanal (C6H 13 CHO), octanal (C7H 15 CHO), nonanal (C8H 17 CHO), nonenal (C7H 14 =CHCHO), decanal (CH 19 CHO), vinyl aldehyde (acrolein CH2=CHCHO), benzaldehyde (C6H5CHO), cinnamaldehyde (cinnamaldehyde C6H5CH=CHCHO), perillaldehyde (C9H 13 and one or more aldehydes selected from the group consisting of aldehydes of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 39, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68

[0019] As illustrated in FIGS. 1 and 2, in the adsorbent 10 of the present invention, strong chemical bonds are formed between the chemical bonding portion 22 of the adsorption site 20 and the substrate surface 32a and pore surface 32b of the base resin 30. The terminal portion 21 of the adsorption site 20 is provided with a primary amino group, which adsorbs aldehydes having 2 to 10 carbon atoms present in gas. The adsorption principle of the primary amino group and aldehyde is as follows: first, the nitrogen atom of the primary amino group (primary amine) (R-NH) undergoes nucleophilic addition to the carbonyl carbon (-CO-) of the aldehyde, forming a hemiaminal (-(RHN)C(OH)-). Because the hemiaminal is chemically unstable, the hydroxyl group (-OH) and the hydrogen on the nitrogen are released as water (HO), generating an imine (Schiff base) (-(RN=)C-) in which the nitrogen and carbon are double-bonded. This imine-forming reaction allows the primary amino groups of the adsorption sites 20 to effectively capture aldehydes. Based on the above-described adsorption principle, the adsorbent 10 of the present invention effectively adsorbs aldehydes having 2 to 10 carbon atoms, preferably aldehydes having 2 to 9 carbon atoms, and more preferably aldehydes having 2 or 9 carbon atoms, which have similar chemical structures. As shown in FIGS. 1 and 2, the adsorbent 10 may contain secondary amino groups (secondary amines) and tertiary amino groups (tertiary amines), but the secondary amino groups are less reactive with aldehydes than the primary amino groups, and the tertiary amino groups hardly contribute to the reaction.

[0020] The raw material (functional agent having aldehyde adsorption ability) that forms a primary amino group at the terminal portion 21 of the adsorption site 20 is ethylenediamine (H2N(CH2)2NH2), 2,2',2''-triaminotriethylamine (N((CH2)2NH2)3), dipropylenetriamine (H2N(CH2)3NH(CH2)3NH2), triethylenetetramine (H2N(CH2)2NH(CH2)2NH(CH2)2NH2), bishexamethylenetriamine ( H2N(CH2)6NH(CH2)6NH2), 2-methyl-1,5-pentamethylenediamine (H2N(CH2)3CHCH3CH2NH2), tetraethylenepentamine (H2N(CH2)2NH(CH2)2NH(CH2)2NH(CH2)2NH(CH2)2NH2), pentaethylenehexamine (H2N(CH2)2NH(CH2)2NH(CH2)2NH(CH2)2NH(CH2)2NH(CH2)2NH2), polyallylamine (-[CH2CH(CH2NH2)] n -), polyethyleneimine (-[(CH2)2NH] n -), or one or more amines selected from any of their derivatives.

[0021] The base resin 30 constituting the adsorbent 10 of the present invention is mainly composed of a copolymer of a base monomer having two vinyl groups (-CH=CH2) and a reactive monomer having a glycidyl group (-C3H5O). The base monomer having two vinyl groups is divinylbenzene (C6H4(CH=CH2)2), divinylnaphthalene (C 10 The reactive monomer having a glycidyl group is a monomer selected from glycidyl methacrylate (glycidyl methacrylate) (CH=C(CH)COOCHO), glycidyl acrylate (glycidyl acrylate) (CH=CHCOOCHO), vinylbenzyl glycidyl ether (CH=C(CH)CHOCHO), or any derivative thereof.

[0022] A preferred combination of base resin and adsorption site is a combination of a base resin of divinylbenzene or ethylene dimethacrylate and glycidyl methacrylate with an adsorption site of ethylenediamine. This adsorbent 10 has excellent adsorption properties, particularly for acetaldehyde, which has two carbon atoms. Another preferred combination is a base resin of ethylene dimethacrylate and glycidyl methacrylate with an adsorption site of polyallylamine. This adsorbent 10 has excellent adsorption properties, particularly for acetaldehyde, which has two carbon atoms, as well as nonanal (a body odor component) and nonenal (a substance that causes aging odor), both of which have nine carbon atoms.

[0023] The present invention includes nonwoven fabrics and fabrics as lower aldehyde-adsorbent fibers in which a lower aldehyde adsorbent (adsorbent) is fixed to fibers. The lower aldehyde-adsorbent nonwoven fabrics can be immobilized by bonding the adsorbent 10 to a spunbonded nonwoven fabric made of polypropylene or the like with an acrylic binder. The lower aldehyde-adsorbent fabrics can also be immobilized by immobilizing the adsorbent 10 to polyester clothing fabrics, cotton fabrics, or the like with an acrylic or urethane binder.

[0024] In other embodiments, the adsorbent 10 can be fixed to materials other than the above-mentioned fibers, such as fabric, cloth, paper, or resin. Furthermore, in order to maintain its adsorption capacity for a long period of time, the adsorbent 10 of the present invention may be encapsulated in microcapsules. Although not shown, for example, both the adsorbent 10 itself and microcapsules encapsulating the adsorbent 10 may be fixed to filter fibers, and the adsorbent 10 itself may exhibit its adsorption capacity at the beginning of use, and as its effectiveness decreases with long-term use, the microcapsules may dissolve, allowing the adsorbent 10 inside to begin exhibiting its adsorption capacity.

[0025] Hereinafter, an embodiment of the method for producing a lower aldehyde adsorbent (adsorbent) will be described. First, a base resin 30 containing, as its main component, a copolymer obtained by polymerizing a base material-constituting monomer having two vinyl groups with a reactive monomer having a glycidyl group is prepared. In this embodiment, for example, 70 to 90 parts by weight of divinylbenzene (Chemical Formula 1) or ethylene dimethacrylate (Chemical Formula 2) as the base material-constituting monomer having two vinyl groups is polymerized with 30 to 10 parts by weight of glycidyl methacrylate (Chemical Formula 3) as the reactive monomer having a glycidyl group to produce a divinylbenzene-glycidyl methacrylate copolymer (Chemical Formula 4) or an ethylene dimethacrylate-glycidyl methacrylate copolymer (Chemical Formula 5) as the base resin 30. If the amount of divinylbenzene or ethylene dimethacrylate is more than 90 parts by weight and less than 10 parts by weight of glycidyl methacrylate, there are few glycidyl groups bonded to the adsorption sites 20, which reduces the proportion of adsorption sites 20 that can be bonded, resulting in a decrease in aldehyde adsorption ability. On the other hand, if the amount of divinylbenzene or ethylene dimethacrylate is less than 70 parts by weight and exceeds 30 parts by weight of glycidyl methacrylate, the proportion of the base material constituent monomer is low, the base material resin 30 becomes brittle, and the pores 31 are destroyed during use, making it impossible to maintain the aldehyde adsorption ability for a long period of time.

[0026] [ka] [ka] [ka] [ka] [ka]

[0027] Figure 3(a) shows an image of a particle of divinylbenzene-glycidyl methacrylate copolymer (Chemical Formula 4) taken with an electron microscope. That is, it is an image of the base resin 30 before the functional drug is added and bonded. Although it is difficult to see in the image of Figure 3(a), the particle has many pores 31 on its surface.

[0028] Next, the copolymer is reacted with an amine as a functional agent. For example, divinylbenzene-glycidyl methacrylate copolymer (Chemical Formula 4) is reacted with ethylenediamine (Chemical Formula 6), an aldehyde-adsorbing component, under heating and stirring. This results in an adsorbent (Chemical Formula 8) 10 of the present invention, in which adsorption sites 20 having primary amines at their terminals 21 are chemically bonded to the base resin 30. Alternatively, for example, ethylenediamine dimethacrylate-glycidyl methacrylate copolymer (Chemical Formula 5) is reacted with ethylenediamine (Chemical Formula 6) or polyallylamine (Chemical Formula 7), an aldehyde-adsorbing component, under heating and stirring. This results in an adsorbent (Chemical Formula 9 or 10) 10 of the present invention, in which adsorption sites 20 having primary amines at their terminals 21 are chemically bonded to the base resin 30. Chemical formulas 8 and 9 show examples of chemical structures in which only one ethylenediamine is bonded, but as shown in Figures 1 and 2, two or more ethylenediamines can be bonded in series and / or in a branched manner.

[0029] [ka] [ka] [ka] [ka] [ka]

[0030] FIG. 3(b) is an electron microscope image of the resulting adsorbent 10 (specifically, the adsorbent shown in Chemical Formula 8). Compared to FIG. 3(a), which shows the base resin 30 itself, the adsorbent 10 of the present invention shown in FIG. 3(b) has cracks and pores 31 on the base surface 32a, resulting in a larger surface area and a different surface morphology. This is thought to be due to the aldehyde-adsorbing component being chemically bonded to the base surface 32a of the base resin 30, as well as physical influences such as stirring during the reaction process. As shown in FIGS. 1 and 2 and Chemical Formulas 8 to 10, the present adsorbent 10 has primary amino groups at the terminals 21 of the adsorption sites 20, and exhibits particularly high adsorption performance for aldehydes having 2 to 10 carbon atoms. [Example]

[0031] Examples of adsorbents according to the present invention will be described in detail below in comparison with comparative examples of the prior art.

[0032] [1] Preparation of the adsorbent of the present invention (Examples 1 to 3) [1-1] Manufacturing of copolymer (base resin) [1-1-1] Divinylbenzene-glycidyl methacrylate copolymer (base resin) <Weighing and preparation> 320 g (84 wt % of the total amount of monomers) of divinylbenzene (DVB) (chemical formula 1) as the base material constituent monomer and 60 g (16 wt % of the total amount of monomers) of glycidyl methacrylate (GMA) (chemical formula 3) as the reactive monomer were placed in a container and stirred, then 420 g of toluene was added and stirred, and 2,2'-azobis[isobutyronitrile] as a radical polymerization initiator was added and stirred to obtain a mixed liquid.

[0033] <Polymerization reaction> The mixture was heated at 68 to 72°C for 7 hours (polymerization reaction) to produce polymer particles.

[0034] <Washing> The polymer particles were transferred to another container, methanol was added, and the mixture was stirred for about an hour and filtered. This procedure was repeated. The mixture was then washed with water, dehydrated, and pulverized to obtain divinylbenzene-glycidyl methacrylate copolymer (IPA) (Figure 3(a), Chemical Formula 4) as the base resin (Example 1a). [1-1-2] Ethylene dimethacrylate-glycidyl methacrylate copolymer (base resin) <Weighing and preparation> 280 g (70 wt% of the total monomer amount) of ethylene dimethacrylate (EGDM) (chemical 2) as the base material constituent monomer and 120 g (30 wt% of the total monomer amount) of glycidyl methacrylate (GMA) (chemical 3) as the reactive monomer were placed in a container and stirred, 400 g of lauryl alcohol was added and stirred, and then 2,2'-azobis[isobutyronitrile] was added and stirred to obtain mixed solution 1. In a separate container, 820 mL of ion-exchanged water, 1.0 g of methylcellulose, and 50 mL of 1% sodium dodecylbenzenesulfonate solution were placed and stirred to obtain mixed solution 2.

[0035] <Dispersion of oil droplets> Mixture 1 was gradually transferred to the container of mixture 2 while stirring, and the contents were pre-dispersed to form mixture 3. Mixture 3 was stirred at a specified rotation speed for 10 minutes, and after stirring was stopped, the contents were sampled and the particle size was confirmed using an optical microscope. Further stirring was continued while adjusting the rotation speed and dispersion time to achieve the specified particle size.

[0036] <Polymerization reaction> After adjusting the particle size to a predetermined value, the mixed solution 3 was stirred at 75 to 85° C. for 20 hours to cause a reaction (polymerization reaction) to produce polymer particles.

[0037] <Washing> The polymer particles were transferred to another container, water was added, stirred for about an hour, and filtered. This procedure was repeated. After further washing with water and dehydration, an ethylene dimethacrylate-glycidyl methacrylate copolymer (Chemical Formula 5) was obtained as the base resin (Example 2a).

[0038] [1-2] Adsorbent production [1-2-1] Addition of ethylenediamine (chemical modification) Water was added to the obtained base resin IPA (Example 1a) and heated, and ethylenediamine (EDA) was added as a functional agent that forms adsorption sites, and the mixture was stirred and reacted for 20 hours at a liquid temperature of 48 to 52°C. The reaction product was filtered and dehydrated, and water was added and dehydrated again to produce a particulate adsorbent of the present invention (Figure 3(b), Chemical Formula 8) in which ethylenediamine was chemically bonded to the base resin (Example 1).

[0039] [1-2-2] Addition of polyallylamine (chemical modification) Water was added to the obtained base resin (Example 2a) and heated, and ethylenediamine (EDA) was added as a functional agent for forming adsorption sites, followed by stirring and reaction for 20 hours at a liquid temperature of 48 to 52°C. The product after the reaction was filtered and dehydrated, and water was added and dehydrated again to produce a particulate adsorbent (Chemical Formula 9) of the present invention in which ethylenediamine was chemically bonded to the base resin (Example 2).

[0040] 2-propanol and water were added to the obtained base resin (Example 2a) in a weight ratio of 1:1, and the mixture was heated. Polyallylamine (PAA) was added as a functional agent for forming adsorption sites, and the mixture was stirred and reacted for 20 hours at a liquid temperature of 55 to 65°C. The reaction product was filtered and dehydrated, and water was added and dehydrated again to produce a particulate adsorbent (Chemical Formula 10) of the present invention in which polyallylamine was chemically bonded to the base resin (Example 3).

[0041] [2] Preparation of conventional adsorbents (Comparative Examples 1 to 10) Commercially available silica gel (Comparative Example 1a), activated alumina (Comparative Example 2a), activated clay (Comparative Example 3a), sepiolite (Comparative Example 4a), and activated carbon (Comparative Example 5a) were each obtained as a base material before ethylenediamine addition. Furthermore, for Comparative Examples 1a to 5a, ethylenediamine was added to the base material in the same manner as in [1-2-1] above to produce silica gel (Comparative Example 1), activated alumina (Comparative Example 2), activated clay (Comparative Example 3), sepiolite (Comparative Example 4), and activated carbon (Comparative Example 5) each impregnated with ethylenediamine.

[0042] Furthermore, a commercially available particulate alumina-based adsorbent (Comparative Example 6) pre-impregnated with tetraethylenepentamine (TEPA) as a functional agent for adsorbing acetaldehyde was prepared. The alumina-based adsorbent of Comparative Example 6 was dispersed in pure water, ultrasonicated for 3 minutes, filtered under suction with 5B filter paper, dried at 100°C for 2 hours, and allowed to cool to prepare a particulate water-washed alumina-based adsorbent (Comparative Example 7).

[0043] To reduce the specific surface area, the adsorbent of the present invention (Example 1) was immersed in a 0.2 M aqueous solution of tetraethylenepentamine and dried to intentionally block the pores, producing a particulate pore-blocked adsorbent (Comparative Example 8). Comparative Example 8 is an adsorbent in which the pores (reference numeral 31 in Figure 2) are filled. Furthermore, to replace the terminal primary amino groups, which are highly reactive with aldehydes, with carboxy groups (-COOH), the adsorbent of the present invention (Example 1) was mixed with chloroacetic acid (CH2ClCOOH), reacted at 60°C for 4 hours, and then dried to produce a particulate carboxy-substituted adsorbent (Comparative Example 9) that is substantially free of primary amino groups at the terminals (containing only secondary and tertiary amino groups) (Chemical Formula 11). [ka]

[0044] A divinylbenzene-glycidyl methacrylate copolymer (IPA) was obtained in the same manner as in [1-1-1] above, except that 368 g (92 wt % of the total amount of monomers) of divinylbenzene (DVB) (Chemical Formula 1) was used as the base monomer and 32 g (8 wt % of the total amount of monomers) of glycidyl methacrylate (GMA) (Chemical Formula 3) was used as the reactive monomer (Comparative Example 10a). Ethylenediamine was added to the resulting base resin (Comparative Example 10a) in the same manner as in [1-2-1] above, producing a particulate adsorbent in which ethylenediamine was chemically bonded to the base resin (Comparative Example 10).

[0045] [3] Preparation of the present invention and conventional nonwoven fabrics (Example 4 and Comparative Example 11) An acrylic binder (NW-7060 manufactured by Toa Gosei Co., Ltd.) in which the adsorbent of the present invention (Example 1) was dispersed was sprayed onto a sheet-shaped polypropylene nonwoven fabric with a spray gun, and the resulting mixture was applied to a 100 cm 2 The adsorbent was immobilized to a weight of 1 g per 1000 g of nonwoven fabric. This was then dried in a thermostatic oven at 120°C for 1 hour to produce a nonwoven fabric on which the adsorbent of the present invention was immobilized (Example 4). Furthermore, a water-washed alumina-based adsorbent (Comparative Example 7) was immobilized on a polypropylene nonwoven fabric and dried in the same manner as above to produce a nonwoven fabric on which a conventional adsorbent was immobilized (Comparative Example 11).

[0046] [4] Preparation of milled dough (Examples 5 and 6) An acrylic binder containing the adsorbent of the present invention (Example 3) dispersed therein was sprayed onto a 10 cm x 10 cm area of ​​100% polyester milling fabric to prepare a milling fabric with approximately 0.3 g of adsorbent immobilized thereon (Example 5).Also, an acrylic binder alone was sprayed onto a 10 cm x 10 cm area of ​​100% polyester milling fabric to prepare a milling fabric with the adsorbent immobilized thereon (Blank 5).

[0047] A urethane binder containing the adsorbent of the present invention (Example 3) dispersed therein was sprayed onto a 10 cm x 10 cm area of ​​100% cotton milling fabric to prepare a milling fabric with approximately 0.3 g of adsorbent immobilized thereon (Example 6).Also, a 10 cm x 10 cm area of ​​100% cotton milling fabric was sprayed with only the urethane binder to prepare a milling fabric with the immobilized adsorbent (Blank 6).

[0048] The components, processing methods, and forms of Examples 1 to 6 and Comparative Examples 1 to 11 are summarized in Table 1. In the table, DVB stands for divinylbenzene, EGDM stands for ethylene dimethacrylate, GMA stands for glycidyl methacrylate, EDA stands for ethylenediamine, PAA stands for polyallylamine, TEPA stands for tetraethylenepentamine, and PP stands for polyethylene.

[0049] [Table 1]

[0050] [5] Test method [5-1] Specific surface area test The specific surface area of ​​each adsorbent (Examples 1a and 1, Comparative Examples 1a-5a and 1-5) before and after the addition of ethylenediamine was measured by the BET method using a gas adsorption measurement device (Microtrackbell's BELSORP MINI X). A test was conducted to determine whether the surface area of ​​the adsorbent was maintained without reduction by the addition of a functional agent. The percentage obtained by dividing the specific surface area of ​​the adsorbent (Example 1, Comparative Examples 1-5) after the addition of ethylenediamine by the specific surface area of ​​the adsorbent (substrate) before the addition (Example 1a, Comparative Examples 1a-5a) was taken as the specific surface area residual rate [%]. A higher specific surface area residual rate indicates a smaller decrease in surface area due to the addition of a functional agent.

[0051] [5-2] Acetaldehyde adsorption characteristics test A predetermined amount of acetaldehyde gas adjusted to a concentration of 25±2 ppm was injected into a 3-L collection bag containing 0.1 g of the adsorbent of Example 1 and sealed. The acetaldehyde gas concentration was measured using a detector tube (Gastec, No. 92 for acetaldehyde, No. 92L). After the acetaldehyde gas was completely discharged, leaving the adsorbent in the 3-L collection bag, 25±2 ppm acetaldehyde gas was again injected into the bag, sealed, and the concentration was measured after two hours had passed. The above series of discharge, injection, and measurement was repeated multiple times every two hours, and the adsorption amount [μL] and adsorption rate [%] were determined as the adsorption characteristics for each measurement. In Example 2 and Comparative Examples 6 to 10, the acetaldehyde gas concentration was measured and the adsorption characteristics were determined in the same manner as in Example 1.

[0052] [5-3] Nonwoven fabric circulation filtration test A 10 L gas collection bag containing acetaldehyde gas at a concentration of 25 ± 2 ppm was fluidly connected to an air pump (CM-15-24, manufactured by Enomoto Micro Pump Mfg. Co., Ltd.), a 3 L measurement container, and a filter paper holder (Type B, manufactured by SHIBATA) loaded with the nonwoven fabric of Example 4 or Comparative Example 11. A circulation flow (not shown) was prepared, returning the gas from the filter paper holder to the 10 L gas collection bag. The flow rate of the circulation flow was controlled to 0.5–1 L / min using a flow meter (RK1600R-10-B-Air-1, manufactured by Kofloc) and the air pump. The total volatile organic compounds (TVOCs) of the gas passing through the 3 L measurement container were measured using an air meter (manufactured by Restars). This circulation flow contained only acetaldehyde gas, and the TVOC concentration was substantially proportional to the acetaldehyde concentration, so this measurement corresponds to the measurement of acetaldehyde concentration. One filter paper holder loaded with one piece of nonwoven fabric from Example 4 (Example 4-1), two in series (Example 4-2), and three in series (Example 4-3) were arranged, and one filter paper holder loaded with one piece of nonwoven fabric from Comparative Example 11 (Comparative Example 11) was arranged, and aldehyde gas was passed through each to test its filtration (removal) performance.

[0053] [5-4] Washing durability test An initial concentration of 14 ppm of acetaldehyde was filled into a 3 L sampling bag containing unwashed rib fabric (Example 5 and Blank 5), and the acetaldehyde concentration was measured using a gas detector tube after 2 hours (n = 3). On the other hand, the rib fabric (Example 5 and Blank 5) after washing was washed 20 times according to the SEK Mark textile product washing method "2.6 Washing Method" and then dried, and the acetaldehyde concentration was measured in the same manner as above.

[0054] 5 μL of 2-nonenal was dropped into a 500 mL Erlenmeyer flask containing unwashed rib fabric (Example 6 and Blank 6), and the 2-nonenal concentration was measured by gas chromatography after 2 hours (n=3). Separately, the rib fabric (Example 6 and Blank 6) was washed 10 times according to the SEK Mark textile product washing method "2.6 Washing Method" and then dried, and the 2-nonenal concentration was measured in the same manner as above.

[0055] 5 μL of nonanal was dropped into a 500 mL Erlenmeyer flask containing unwashed rib fabric (Example 6 and Blank 6), and the nonanal concentration was measured by gas chromatography after 2 hours (n=3). Separately, the nonanal concentration of washed rib fabric (Example 6 and Blank 6) that had been washed 10 times according to the SEK Mark textile product washing method "2.6 Washing Method" and then dried was measured in the same manner as above.

[0056] [6] Results and Discussion [6-1] Results and considerations of specific surface area test [Table 2]

[0057] The results of the specific surface area test are shown in Table 2 and Figure 4. The residual specific surface area of ​​the adsorbent of the present invention (Example 1) was 98%, meaning that the specific surface area remained almost unchanged before and after the addition of ethylenediamine (EDA). On the other hand, the residual specific surface area of ​​activated carbon (Comparative Example 5) was 74%, which was relatively high. However, the residual specific surface areas of silica gel (Comparative Example 1), activated alumina (Comparative Example 2), activated clay (Comparative Example 3), and sepiolite (Comparative Example 4) were 31%, 15%, 8%, and 17%, respectively, indicating that the addition of ethylenediamine (EDA) significantly reduced the specific surface area. That is, in Example 1 of the present invention, the addition of the functional agent prevents the pores 31 (Figure 2) from being blocked, preventing a decrease in specific surface area and maintaining high adsorption capacity. In contrast, in the comparative examples, particularly Comparative Examples 1 to 4, many pores were blocked, reducing the specific surface area and adsorption capacity.

[0058] [6-2] Results and considerations of acetaldehyde adsorption characteristics test The results of an acetaldehyde adsorption characteristic test (13 measurements, 26 hours) for each adsorbent of the present invention (Example 1), alumina-based (Comparative Example 6), and water-washed alumina-based (Comparative Example 7) to which ethylenediamine (EDA) had been added are shown in Figure 5(a) for the adsorption amount and Figure 5(b) for the adsorption rate. For Example 1, the cumulative adsorption amount for 13 measurements exceeded 600 μL (Figure 5(a)). As shown in Figure 5(b), the adsorption rate gradually decreased, but maintained a high adsorption rate of 50% or more up to 9 measurements, and remained above 10% up to 13 measurements. For Comparative Example 6, the cumulative adsorption amount for 13 measurements was 1000 μL (Figure 5(a)). As shown in Figure 5(b), the adsorption rate remained nearly 100% up to 13 measurements. For Comparative Example 7, in which the adsorbent of Comparative Example 6 was washed with water, the cumulative adsorption amount for 13 measurements was just under 400 μL (Figure 5(a)). As shown in Figure 5(b), the adsorption rate was 0% after 9 measurements. That is, it was found that tetraethylenepentamine attached to an alumina-based substrate does not desorb under dry conditions (dry air) (Comparative Example 6), but is easily desorbed by rinsing with water (Comparative Example 7). Therefore, alumina-based adsorbents are unsuitable for use in the presence of water and in high-humidity environments. This is thought to be because the functional agent is merely incorporated into the pores of the inorganic substrate and does not form a strong chemical bond. On the other hand, in Example 1 of the present invention, the functional agent is chemically bonded to the base resin in the presence of water during production, and therefore it was confirmed that the functional agent can be used in the presence of water and in high-humidity environments without being affected by moisture.

[0059] The results of acetaldehyde adsorption tests for the following adsorbents are shown in Figure 6(a) for the adsorption amount and Figure 6(b) for the adsorption rate. Figure 6(a) shows the cumulative adsorption amount over a maximum of five measurements. Figure 6(a) shows the cumulative adsorption amount over a maximum of five measurements.

[0060] In Examples 1 and 2, the cumulative adsorption volume after five measurements was 338 μL and 473 μL, respectively, as shown in FIG. 6(a). As shown in FIG. 6(b), a high adsorption rate of 50% or more was maintained for up to 9 and 6 measurements. In Comparative Example 8, the cumulative adsorption volume after five measurements was approximately 271 μL, as shown in FIG. 6(a). As shown in FIG. 6(b), the adsorption rate fell below 50% after four measurements. In Comparative Example 9, the cumulative adsorption volume was only 45 μL, and the adsorption rate fell to 0% after three measurements. In Comparative Example 10, the cumulative adsorption volume was only 84 μL, and the adsorption rate fell to 0% after five measurements. Therefore, it was found that the acetaldehyde adsorption performance of Comparative Example 8 was reduced due to pore blockage, while that of Comparative Example 9 was significantly reduced due to substitution with carboxyl groups. It was also found that the adsorption capacity of Comparative Example 10, which contained 8 wt% GMA, significantly decreased. In Comparative Example 10, the amount of glycyl methacrylate (GMA) bonded to ethylenediamine (EDA), which exerts acetaldehyde adsorption ability, was small, which is thought to be why the amount of EDA and primary amino groups was small, resulting in reduced adsorption ability. In contrast, in Examples 1 and 2 of the present invention, there was no clogging of pores and the presence of an appropriate amount of primary amino groups resulted in excellent adsorption characteristics for acetaldehyde. Furthermore, the adsorption results for Comparative Example 10 (8 wt% GMA), Example 1 (16 wt% GMA), and Example 2 (30 wt% GMA) revealed that the GMA content relative to the total amount of monomers (total amount of [DVB or EGDM] + GMA) was found to be preferably 16 to 30 wt% or 10 to 30 wt%.

[0061] [6-3] Results and considerations of nonwoven fabric circulation filtration test Figure 7 shows the results of filtration tests for Examples 4-1, 4-2, and 4-3, in which one to three filter paper holders loaded with the nonwoven fabric of Example 4 according to the present invention were arranged in series; Comparative Example 11, in which one filter paper holder loaded with a conventional nonwoven fabric was arranged; and Blank 4, in which no nonwoven fabric was loaded. As shown in Figure 7, after 30 minutes of measurement, the TVOC concentration was 9.9 mg / L, 2.5 mg / L, and 2.0 mg / L for Examples 4-1, 4-2, and 4-3, respectively, compared to 23 mg / L for Blank 4, and 16 mg / L for Comparative Example 11. That is, at this point, the TVOC concentration in Example 4-1 was reduced to less than half, while in Examples 4-2 and 4-3, almost all TVOC components were removed. After 60 minutes of measurement, the TVOC concentration was 6.7 mg / L, nearly 0 mg / L, and nearly 0 mg / L for Examples 4-1, 4-2, and 4-3, respectively, compared to 23 mg / L for Blank 4, and 13 mg / L for Comparative Example 11. That is, at this point, TVOC components were almost completely removed in Examples 4-2 and 4-3. After 120 minutes of measurement, the blank was 21 mg / L, while Examples 4-1, 4-2, and 4-3 were 3.1 mg / L, nearly 0 mg / L, and nearly 0 mg / L, respectively, and Comparative Example 11 was 12 mg / L. That is, at this point, the TVOC components were almost completely removed in Example 4-1, but more than half of the TVOC remained in Comparative Example 11. Therefore, the nonwoven fabric (Example 4) immobilized with the adsorbent of the present invention (Example 1) was confirmed to have an effective aldehyde adsorption effect in recycled use. In contrast, the conventional nonwoven fabric (Comparative Example 11) immobilized the adsorbent of Comparative Example 7, from which the functional agent had already been released by washing with water, and therefore the aldehyde adsorption effect was insufficient.

[0062] [6-4] Results and considerations of washing durability test Table 3 shows the results of the wash durability test for polyester fabric (Example 5) and cotton fabric (Example 6) on which the adsorbent of Example 3 with polyallylamine (PAA) added thereto was immobilized. [Table 3] As shown in Table 3, when the adsorption target was acetaldehyde, in Example 5, the concentration was below the detection limit before and after washing, confirming good adsorption effects even after 20 washes. When the adsorption targets were nonenal and nonanal, in Example 6, the concentrations were 0.1 ppm before and after washing, confirming good adsorption effects even after 10 washes. Therefore, it was confirmed that the fabric with the adsorbent of the present invention immobilized thereon retains its adsorption properties for acetaldehyde, nonenal, and nonanal even after washing, i.e., the adsorbent does not detach from the fibers even after washing, and the adsorption properties can be maintained. Furthermore, not only ethylenediamine (Chemical Formula 6) but also polyallylamine (Chemical Formula 7) were used as adsorption site-forming substances, and high adsorption ability for the aldehydes was confirmed. [Industrial Applicability]

[0063] The lower aldehyde adsorbent, fibers using the adsorbent, and method for producing a lower aldehyde adsorbent according to the present invention can be used for a variety of purposes, whether for home or business use, such as purifying indoor air in homes, offices, schools, hospitals, nursing homes, automobiles, railway vehicles, aircraft, etc.; purifying gases released from factories, restaurants, etc.; and immobilizing the adsorbent on fibers, cloth, paper, resin, etc. [Explanation of symbols]

[0064] 10··Lower aldehyde adsorbent (adsorbent), 20··Adsorption site, 21··Terminal portion, 22··Chemical bond portion, 30··Base resin, 31··Pore, 32a··Base surface, 32b··Pore surface,

Claims

1. a base resin having many pores, the base resin being mainly composed of a copolymer of a base material constituent monomer having two vinyl groups and a reactive monomer having a glycidyl group; an adsorption site that is chemically bonded to the base resin, has a primary amino group at its terminal, and adsorbs an aldehyde having 2 to 10 carbon atoms; A lower aldehyde adsorbent characterized by comprising:

2. 2. The lower aldehyde adsorbent according to claim 1, wherein the aldehyde having 2 to 10 carbon atoms is one or more aldehydes selected from the group consisting of acetaldehyde (ethanal), propionaldehyde (propanal), butanal, pentanal, hexanal, heptanal, octanal, nonanal, nonenal, decanal, vinyl aldehyde (acrolein), benzaldehyde, cinnamaldehyde, perillaldehyde, vanillin, dialdehyde (glyoxal), malondialdehyde, and glyceraldehyde.

3. 2. The lower aldehyde adsorbent according to claim 1, wherein the raw material that forms a primary amino group at the end of the adsorption site is one or more amines selected from ethylenediamine, 2,2',2''-triaminotriethylamine, dipropylenetriamine, triethylenetetramine, bishexamethylenetriamine, 2-methyl-1,5-pentamethylenediamine, tetraethylenepentamine, pentaethylenehexamine, polyallylamine, and polyethyleneimine.

4. the base material-constituting monomer having two vinyl groups is a monomer selected from divinylbenzene, divinylnaphthalene, ethylene dimethacrylate, or a derivative thereof; The reactive monomer having a glycidyl group is a monomer selected from glycidyl methacrylate (glycidyl methacrylate), glycidyl acrylate (glycidyl acrylate), vinylbenzyl glycidyl ether, or a derivative thereof; The lower aldehyde adsorbent according to claim 1.

5. a base resin mainly composed of a copolymer of divinylbenzene or ethylene dimethacrylate as a base constituent monomer and glycidyl methacrylate as a reactive monomer; It consists of an adsorption site made from ethylenediamine, 2. The lower aldehyde adsorbent according to claim 1, which adsorbs acetaldehyde as the aldehyde having 2 to 10 carbon atoms.

6. a base resin mainly composed of a copolymer of ethylene dimethacrylate as a base constituent monomer and glycidyl methacrylate as a reactive monomer; It consists of an adsorption site made from polyallylamine, 2. The lower aldehyde adsorbent according to claim 1, which adsorbs acetaldehyde, nonanal, and nonenal as aldehydes having 2 to 10 carbon atoms.

7. A lower aldehyde-adsorbing fiber, characterized in that the lower aldehyde adsorbent according to claim 1 is immobilized on the fiber.

8. a step of polymerizing a base material constituent monomer having two vinyl groups with a reactive monomer having a glycidyl group to prepare a copolymer that will be a main component of the base material resin; a step of reacting the copolymer with an amine to form an adsorption site that is chemically bonded to the base resin, has a primary amino group at the terminal, and is capable of adsorbing an aldehyde having 2 to 10 carbon atoms; A method for producing an adsorbent for lower aldehydes, comprising the steps of:

9. 9. The method for producing a lower aldehyde adsorbent according to claim 8, wherein the step of preparing a copolymer as a main component of the base resin comprises polymerizing 70 to 90 parts by weight of divinylbenzene or ethylene dimethacrylate as a base constituent monomer having two vinyl groups with 30 to 10 parts by weight of glycidyl methacrylate as a reactive monomer having a glycidyl group.

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