JP6351230B2 - Deodorant processing chemical for fiber and method for producing deodorant fiber - Google Patents

Description

  The present invention relates to a fiber deodorizing agent used for imparting deodorant properties to a fiber material and a method for producing a deodorant fiber that imparts the deodorant agent to a fiber material.

  Conventionally, as a fiber (deodorant fiber) for deodorizing malodorous gas, a fiber material obtained by processing a porous adsorbent such as activated carbon, alumina, or zeolite is known. Zeolite is a compound mainly composed of hydrous aluminosilicate and includes natural zeolite, synthetic zeolite, artificial zeolite and the like. All of them have ion exchange ability, and the crystal structure does not change even when dehydrated. After dehydration, molecular-sized pores are obtained, and they have a large adsorption ability. These zeolites have relatively high adsorption performance for basic gases such as ammonia and trimethylamine, and acidic malodorous gases such as isovaleric acid and acetic acid, but against aldehyde gases such as nonenal, acetaldehyde and formaldehyde. Shows little adsorption performance.

In order to improve the adsorption performance for aldehyde gases as in Patent Document 1, a compound having an NH group and / or NH ₂ groups in the molecule of the artificial zeolite, and / or copper, zinc, nickel, cobalt and manganese It is known to process a deodorant carrying metal ions into a fiber material.
However, when such a porous adsorbent such as a deodorant is used, there is a problem that the deodorizing property is lowered by washing, that is, the washing durability is low.

JP 2006-116093 A

  The present invention has been made in order to solve the problems in the conventional deodorization processing of fiber materials, and is a processing agent to be applied to fiber materials in post-processing, and has excellent deodorization properties for fiber materials. It aims at providing the manufacturing method of the deodorizing fiber for which the deodorizing processing chemical | medical agent for fibers which can provide property and washing durability, and this deodorizing processing chemical agent was provided.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have first found that a drug containing amino-modified silicone, a surfactant and water can impart a deodorizing property to a fiber material. Furthermore, it has been found that there is a clear difference in performance in deodorization and washing durability depending on the type of amino group of amino-modified silicone, specifically, primary amino group, secondary amino group, and tertiary amino group. . And if it is a specific amino modified silicone which has a primary amino group in a molecule | numerator, surfactant and the deodorizing agent for fibers which essentially contains water, it discovered that the said subject could be solved, and this invention Reached.

  That is, the present invention is a fiber deodorizing agent used for imparting deodorizing properties to a fiber material, and an amino acid represented by the following general formula (1) having a primary amino group in the molecule as an essential component. A deodorizing agent for fibers, which essentially contains a modified silicone, a surfactant and water, the amino-modified silicone has a viscosity (25 ° C.) of 200 to 100,000 mPa · s, and an amino equivalent of 500 to 7000 g / mol. It is.

X: is a group represented by —R ¹ —NH ₂ or —R ² —NH—R ³ —NH ₂ , and R ¹ , R ² and R ³ each independently represent an alkylene group.
Y: A hydroxy group, a polyether group, an alkyl group, an alkenyl group or an alkoxy group.
Z: A group represented by X or a group represented by Y.
R ⁴ : represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, a hydroxy group or an alkoxy group.
n: An integer from 1 to 400.
m: represents an integer of 0 to 400.
k: An integer of 1 to 2000 is shown.

  In General formula (1), it is preferable that Y and Z are respectively independently a hydroxy group or an alkoxy group.

The weight ratio of the amino-modified silicone and the surfactant is preferably 50/50 to 99/1.
The total weight ratio of the amino-modified silicone and the surfactant in the nonvolatile content of the drug is preferably 90% by weight or more.

  It is preferable that the deodorizing agent for fibers of the present invention is used for imparting deodorizing properties to aldehyde components.

  The method for producing a deodorant fiber of the present invention includes a step (A) of applying a treatment liquid containing the above-mentioned fiber deodorizing agent to a fiber material, and a step of heat-treating the fiber material to which the treatment liquid is applied (B ).

  The adhesion amount of the amino-modified silicone is preferably 0.01 to 30% by weight with respect to the fiber material.

The fiber deodorant agent of the present invention can impart excellent deodorant properties and washing durability to the fiber material by post-processing.
According to the method for producing a deodorant fiber of the present invention, a deodorant fiber excellent in deodorant property and washing durability can be obtained.

  The fiber deodorant processing agent of the present invention is used to impart deodorant properties to fiber materials, and a specific amino-modified silicone having a primary amino group in the molecule, a surfactant and water are essential. It contains. Details will be described below.

[Amino-modified silicone]
The amino-modified silicone used in the present invention essentially has a primary amino group (—NH ₂ ) in the molecule, and the amino-modified silicone represented by the above formula (1) (hereinafter simply referred to as “amino-modified silicone”). Yes). When an amino-modified silicone that does not have a primary amino group and has a secondary amino group (—NHR) and / or a tertiary amino group (—NRR ′) is used, the fiber material cannot be deodorized.

In the general formula (1), X is a group represented by —R ¹ —NH ₂ or —R ² —NH—R ³ —NH ₂ . R ¹ , R ² and R ³ each independently represent an alkylene group. Carbon number of an alkylene group becomes like this. Preferably it is 1-25, More preferably, it is 1-18, More preferably, it is 2-10. X is preferably —R ¹ —NH ₂ because the ratio of the primary amino group in the functional group is high.

In the general formula (1), Y represents a hydroxy group, a polyether group, an alkyl group, an alkenyl group or an alkoxy group.
The polyether group refers to a group represented by —O— (AO) _p —R ⁵ . AO is an oxyalkylene group having 2 to 4 carbon atoms. The number of carbon atoms of AO is preferably 2 to 3, more preferably 2. 1 type (s) or 2 or more types may be sufficient as AO, and when it is 2 or more types, you may comprise any of a block adduct, an alternating adduct, or a random adduct. p is an integer, preferably 1 to 400, and more preferably 10 to 300. It is preferable that AO contains an oxyethylene group essentially. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more. R ⁵ is a hydrogen atom or an alkyl or alkenyl group having 1 to 10 carbon atoms. The number of carbon atoms in the case R ⁵ is an alkyl or alkenyl group is preferably 1 to 8, more preferably 1-5.

  Carbon number of an alkyl group or an alkenyl group becomes like this. Preferably it is 1-25, More preferably, it is 1-21, More preferably, it is 1-18. Examples of the alkyl group include a methyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a lauryl group, a tridecyl group, and a stearyl group. Examples of the alkenyl group include vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, isobutenyl group, pentenyl group, hexenyl group, cyclohexenyl group, heptenyl group, decenyl group, dodecenyl group, tridecenyl group, An octadecenyl group, an oleyl group, an eicosenyl group, a dococenyl group, etc. are mentioned.

  Carbon number of an alkoxy group becomes like this. Preferably it is 1-12, More preferably, it is 1-10, More preferably, it is 1-8. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and a hexoxy group.

  Among these, Y is preferably a hydroxy group or an alkoxy group from the viewpoint of washing durability.

  In the general formula (1), Z is a group represented by X or a group represented by Y. Among these, from the viewpoint of washing durability, Z is preferably a hydroxy group or an alkoxy group.

  In general formula (1), n represents an integer of 1 to 400. When n is less than 1, there is no amino group in the molecule, and deodorant properties cannot be imparted. When n is more than 400, an amine odor is generated, which is not preferable. n is preferably 5 to 360, more preferably 10 to 330, and still more preferably 20 to 300.

In general formula (1), R ⁴ represents an alkyl group or alkenyl group, hydroxy group or an alkoxy group having 1 to 12 carbon atoms. Carbon number of an alkyl group or an alkenyl group becomes like this. Preferably it is 1-8, More preferably, it is 1-5. Carbon number of an alkoxy group becomes like this. Preferably it is 1-8, More preferably, it is 1-5.

  In General formula (1), m shows the integer of 0-400. When m is more than 400, Y is as follows. When Y is a hydroxy group, it reacts in the molecule and a stable product cannot be obtained. When Y is a polyether group, washing durability cannot be imparted. When Y is an alkoxy group, it is difficult to emulsify the amino-modified silicone. m is preferably 5 to 360, more preferably 10 to 330, and still more preferably 20 to 300.

  In General formula (1), k shows the integer of 1-2000. When k is less than 1, washing durability cannot be imparted. On the other hand, when k is more than 2000, the molecular weight becomes high and emulsification of amino-modified silicone becomes difficult. k is preferably 10 to 1900, more preferably 20 to 1800, and still more preferably 30 to 1700.

  In order to impart deodorant properties and durable washing properties to the fiber material, it is an amino-modified silicone represented by the above formula (1) and has a viscosity (25 ° C.) of 200 to 100,000 mPa · s. There is a need. When the viscosity is less than 200 mPa · s, washing durability cannot be imparted. On the other hand, when the viscosity is more than 100,000 mPa · s, the molecular weight becomes high and emulsification of the amino-modified silicone becomes difficult. The viscosity is preferably 400 to 90000 mPa · s, more preferably 700 to 70000 mPa · s, and still more preferably 1000 to 50000 mPa · s. In addition, the viscosity in this invention means the value measured with the Brookfield type viscometer.

  Furthermore, in order to impart deodorant properties and durable washing properties to the fiber material, it is necessary that the amino equivalent is 500 to 7000 g / mol in addition to the viscosity (25 ° C.) of the amino-modified silicone. If the amino equivalent is less than 500 g / mol, an amine odor is generated (cause of poor emulsification or yellowing). On the other hand, when the amino equivalent is more than 7000 g / mol, the deodorizing property cannot be imparted because there are few amino groups. The amino equivalent is preferably 600 to 6000 g / mol, more preferably 700 to 5000 g / mol, and still more preferably 800 to 4000 g / mol.

[Surfactant]
The fiber deodorizing agent of the present invention contains a surfactant. The surfactant is used as an emulsifier, and makes it possible to emulsify and disperse the modified silicone and the like in water. The surfactant is not particularly limited, and a known one can be appropriately selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Surfactant may use together 1 type (s) or 2 or more types.

  Examples of the nonionic surfactant include polyoxyalkylene linear alkyl ethers such as polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, and polyoxyethylene cetyl ether; Polyoxyalkylene branched primary alkyl ethers such as polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isocetyl ether, polyoxyethylene isostearyl ether; polyoxyethylene 1-hexyl hexyl ether, polyoxyethylene 1-octyl hexyl ether Polyoxyethylene 1-hexyl octyl ether, polyoxyethylene 1-pentyl heptyl ether, polyoxyethylene 1-heptylpentyl ether Polyoxyalkylene branched secondary alkyl ethers such as ter; polyoxyalkylene alkenyl ethers such as polyoxyethylene oleyl ether; polyoxys such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether Alkylene alkyl phenyl ether; polyoxyethylene tristyryl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, polyoxyethylene benzyl phenyl ether Such as polyoxyalkylene alkyl aryl phenyl ether; Laurate, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monomyristate, polyoxyethylene dilaurate, polyoxyethylene dioleate, polyoxyethylene dimyristate, polyoxyethylene distearate, etc. Polyoxyalkylene fatty acid esters; sorbitan esters such as sorbitan monopalmitate and sorbitan monooleate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; glycerin monostearate and glycerin monolaur Glycerin fatty acid ester such as rate and glycerin monopalmitate; Polyoxyalkylene sorbitol fatty acid ester; Sucrose fat Acid ester; polyoxyalkylene castor oil ether such as polyoxyethylene castor oil ether; polyoxyalkylene hardened castor oil ether such as polyoxyethylene hydrogenated castor oil ether; polyoxyalkylene alkyl such as polyoxyethylene lauryl amino ether and polyoxyethylene stearyl amino ether Amino ether; oxyethylene-oxypropylene block or random copolymer; oxyethylene-oxypropylene block or random copolymer terminal alkyl etherified product; oxyethylene-oxypropylene block or random copolymer terminal sucrose etherified product; Etc.

  Among these nonionic surfactants, polyoxyalkylene branched primary alkyl ethers, polyoxyalkylene branched secondary alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyalkylene ethers, Preferred are oxyalkylene alkyl phenyl ethers, polyoxyalkylene fatty acid esters, oxyethylene-oxypropylene block copolymers, and terminal alkyl etherified products of oxyethylene-oxypropylene block copolymers, such as oxyethylene-oxypropylene blocks or random copolymers. A terminal alkyl etherified product of an oxyethylene-oxypropylene block copolymer is more preferable.

  Examples of the anionic surfactant include fatty acids (salts) such as oleic acid, palmitic acid, sodium oleate, potassium palmitate, triethanolamine oleate; hydroxyacetic acid, potassium potassium hydroxyacetate, lactic acid, lactic acid Hydroxyl group-containing carboxylic acid (salt) such as potassium salt; polyoxyalkylene alkyl ether acetic acid (salt) such as polyoxyethylene tridecyl ether acetic acid (sodium salt); and many carboxyl groups such as potassium trimellitic acid and potassium pyromellitic acid Substituted aromatic compound salts; alkylbenzene sulfonic acid (salt) such as dodecylbenzene sulfonic acid (sodium salt); polyoxyalkylene alkyl ether sulfonic acid (salt) such as polyoxyethylene 2-ethylhexyl ether sulfonic acid (potassium salt); Higher fatty acid amide sulfonic acid (salt) such as theauroylmethyl taurine (sodium), lauroyl methyl taurine (sodium), myristoyl methyl taurine (sodium), palmitoyl methyl taurine (sodium); N-acyl such as lauroyl sarcosine acid (sodium) Sarcosine acid (salt); alkyl phosphonic acid (salt) such as octyl phosphonate (potassium salt); aromatic phosphonic acid (salt) such as phenyl phosphonate (potassium salt); 2-ethylhexyl phosphonate mono 2-ethylhexyl ester (potassium salt) Alkylphosphonic acid esters (salts) such as alkylphosphonic acid; nitrogen-containing alkylphosphonic acid (salt) such as aminoethylphosphonic acid (diethanolamine salt); alkylsulfuric acid such as 2-ethylhexyl sulfate (sodium salt) Esters (salts); polyoxyalkylene sulfate esters (salts) such as polyoxyethylene 2-ethylhexyl ether sulfate (sodium salt); long-chain sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate and sodium dioctyl sulfosuccinate; N -Long-chain N-acyl glutamates such as sodium lauroyl glutamate and disodium N-stearoyl-L-glutamate;

  Examples of the cationic surfactant include lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oleyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, coconut oil alkyl trimethyl. Ammonium chloride, tallow alkyltrimethylammonium chloride, stearyltrimethylammonium bromide, coconut oil alkyltrimethylammonium bromide, cetyltrimethylammonium methosulfate, oleyldimethylethylammonium ethosulphate, dioctyldimethylammonium chloride, dill Alkyl quaternary ammonium salts such as ril dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, octadecyl diethyl methyl ammonium sulfate; (polyoxyethylene) lauryl amino ether lactate, stearyl amino ether lactate, di (polyoxyethylene) lauryl Methylaminoether dimethyl phosphate, di (polyoxyethylene) laurylethylammonium ethosulphate, di (polyoxyethylene) -cured tallow alkylethylamine ethosulphate, di (polyoxyethylene) laurylmethylammonium dimethylphosphate, di (polyoxyethylene) stearyl (Polyoxyalkylene) alkylamino ether salts such as amine lactate; N- (2-hydroxyethyl)- , N-dimethyl-N-stearoylamidopropylammonium nitrate, lanolin fatty acid amidopropylethyldimethylammonium ethosulphate, acylamidoalkyl quaternary ammonium salts such as lauroylamidoethylmethyldiethylammonium methosulfate; dipalmityl polyethenoxyethyl Alkylethenoxy quaternary ammonium salts such as ammonium chloride and distearyl polyethenoxymethylammonium chloride; alkylisoquinolinium salts such as laurylisoquinolinium chloride; lauryldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride and the like Benzalkonium salt; benzyldimethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenol) Oxy) ethoxy] ethyl} ammonium chloride and other benzethonium salts; cetylpyridinium chloride and other pyridinium salts; Acyl basic amino acid alkyl ester salts such as ester pyrrolidone carboxylate and N-lauroyllysine ethyl ethyl ester chloride; Primary amine salts such as laurylamine chloride, stearylamine bromide, hardened beef tallow alkylamine chloride, rosinamine acetate; cetyl Methylamine sulfate, laurylmethylamine chloride, dilaurylamine acetate, stearylethylamine bromide, lauric Secondary amine salts such as rupropylamine acetate, dioctylamine chloride, octadecylethylamine hydroxide; dilaurylmethylamine sulfate, lauryldiethylamine chloride, laurylethylmethylamine bromide, diethanol stearylamide ethylamine trihydroxyethyl phosphate salt, stearylamide Tertiary amine salts such as ethyl ethanolamine urea polycondensate acetate; fatty acid amidoguanidinium salts; alkyltrialkylene glycol ammonium salts such as lauryltriethylene glycol ammonium hydroxide, and the like.

  Examples of amphoteric surfactants include 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, and the like. Imidazoline-based amphoteric surfactants; 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaines, amide betaines, sulfobetaine, and other betaine-based amphoteric surfactants; N- Amino acid type amphoteric surfactants such as lauryl glycine, N-lauryl β-alanine, N-stearyl β-alanine and the like can be mentioned.

[Deodorizing agent for textiles]
The fiber deodorizing agent (hereinafter sometimes simply referred to as a drug) of the present invention is used for imparting deodorizing properties to a fiber material. The fiber material and the provision of deodorant properties will be described in the method for producing deodorant fibers. The chemical | medical agent of this invention contains the above-mentioned amino modified silicone, surfactant, and water essential, The amino modified silicone is in the state emulsified in water.

  The average particle diameter of the amino-modified silicone is preferably 0.001 to 50 μm, more preferably 0.002 to 10 μm, still more preferably 0.005 to 5 μm, particularly preferably 0.007 to 2 μm, and most preferably 0.01. ˜1 μm. When the average particle diameter is less than 0.001 μm, it may cause secondary aggregation. On the other hand, when the average particle diameter is more than 50 μm, the product stability is poor and the product may be separated. The average particle size used in the present invention is a value obtained by measuring a median particle size based on volume using a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.).

  The weight ratio of the amino-modified silicone and the surfactant is preferably 50/50 to 99/1, more preferably 60/40 to 95/5, still more preferably 70/30 to 90/10. When the weight ratio is less than 50/50, washing durability may not be imparted. On the other hand, when the weight ratio exceeds 99/1, product stability may be deteriorated.

  The total weight ratio of amino-modified silicone and surfactant in the nonvolatile content of the drug is preferably 90% by weight or more, more preferably 92% by weight or more, and further preferably 95% by weight or more. If the weight ratio is less than 90% by weight, deodorizing properties may not be imparted. The non-volatile content in the present invention refers to an absolutely dry component when a sample is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.

  The weight ratio of the amino-modified silicone in the nonvolatile content of the drug is preferably 10 to 99% by weight, more preferably 20 to 97% by weight, and still more preferably 30 to 95% by weight. When the said weight ratio is less than 10 weight%, wash durability may not be provided. On the other hand, when the weight ratio exceeds 99% by weight, product stability may be deteriorated.

  The weight ratio of the surfactant to the nonvolatile content of the drug is preferably 1 to 90% by weight, more preferably 3 to 80% by weight, and still more preferably 5 to 70% by weight. When the said weight ratio is less than 1 weight%, product stability may worsen. On the other hand, when the weight ratio is more than 90% by weight, washing durability may not be imparted.

  The chemical | medical agent of this invention contains water essential. The water used in the present invention may be any of pure water, distilled water, purified water, soft water, ion exchange water, tap water and the like.

  The chemical | medical agent of this invention may also contain other components other than the said component in the range which does not impair the effect of this invention. Other components include anti-discoloring agents, antibacterial agents, antifungal agents, insecticides, acaricides, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, antifouling agents, and deep colors. Examples include post-processing agents for fibers such as agents, smoothing agents, softening agents or water-absorbing agents, oil agents, surfactants, inorganic substances, preservatives, pH adjusters, antifoaming agents, solvents, fatty acids (salts), and the like.

The drug of the present invention preferably contains substantially no polyhydroxyamine compound or a salt thereof from the viewpoint of more exerting the effects of the present invention. Specifically, the amount is preferably less than 1 part by weight, more preferably less than 0.1 part by weight, and further preferably 0 part by weight with respect to 100 parts by weight of the amino-modified silicone.
Examples of the polyhydroxyamine compound or a salt thereof include 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3- Propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, 4-amino-4-hydroxypropyl-1,7-heptanediol 2- (N-ethyl) amino-1,3-propanediol, 2- (N-ethyl) amino-2-hydroxymethyl-1,3-propanediol, 2- (N-decyl) amino-1,3 -Neutralized with propanediol, 2- (N-decyl) amino-2-hydroxymethyl-1,3-propanediol, and the like, and inorganic acid or organic acid Salt and the like. Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, a fatty acid having 1 to 12 carbon atoms, and an alkyl sulfuric acid having 1 to 3 carbon atoms.

Moreover, it is preferable that the chemical | medical agent of this invention does not contain a hydrazide compound substantially from the point which exhibits the effect of this invention more. Specifically, the amount is preferably less than 1 part by weight, more preferably less than 0.1 part by weight, and further preferably 0 part by weight with respect to 100 parts by weight of the amino-modified silicone.
Examples of the hydrazide compound include a monohydrazide compound having one hydrazide group in the molecule, and 2 in the molecule.
Examples thereof include a dihydrazide compound having one hydrazide group and a polyhydrazide compound having three or more hydrazide groups in the molecule.

  Moreover, it is preferable that the chemical | medical agent of this invention does not contain an alkyl polyamine derivative substantially from the point which exhibits the effect of this invention more. Specifically, the amount is preferably less than 1 part by weight, more preferably less than 0.1 part by weight, and further preferably 0 part by weight with respect to 100 parts by weight of the amino-modified silicone.

  The concentration of the nonvolatile content of the drug of the present invention is preferably 1 to 80% by weight, more preferably 2 to 70% by weight, and still more preferably 5 to 60% by weight.

  There is no limitation in particular as a preparation method of the chemical | medical agent of this invention, A well-known method is employable. For example, it can be obtained by mixing amino-modified silicone, surfactant and water and emulsifying using a general stirring device and an emulsifier such as a homomixer, homogenizer, colloid mill, or line mixer.

[Method for producing deodorant fiber]
The manufacturing method of the deodorant fiber of this invention is the process (A) which provides the fiber material with the process liquid containing the deodorizing agent for fibers of this invention, and the process (B) which heat-processes the fiber material which provided the process liquid. ). Therefore, the manufacturing method of the deodorant fiber of this invention provides the fiber material with the deodorizing agent for fibers by post-processing. Post-processing means processing after the fiber material is manufactured. According to this production method, it is possible to obtain a deodorant fiber that is excellent in deodorizing properties and excellent in washing durability.

  The fiber material may be either natural fiber or chemical fiber. Examples of natural fibers include plant fibers such as cotton, cannabis, flax, palm, and rush; animal fibers such as wool, goat wool, mohair, cashmere, camel, and silk; and mineral fibers such as asbestos. Examples of the chemical fiber include inorganic fibers such as rock fiber, metal fiber, graphite, silica, and titanate; regenerated cellulosic fibers such as rayon, cupra, viscose, polynosic, and purified cellulose fiber; melt-spun cellulose fiber; Protein fibers such as milk protein and soybean protein; Regenerated and semi-synthetic fibers such as regenerated silk and alginate fiber; Polyamide fiber, Polyester fiber, Cationic dyeable polyester fiber, Polyvinyl fiber, Polyacrylic alcohol fiber, Polyurethane fiber, Acrylic fiber, Examples thereof include synthetic fibers such as polyethylene fibers, polyvinylidene fibers, and polystyrene fibers. Two or more of these fibers may be combined (mixed spinning, mixed fiber, union, union, etc.).

  Examples of the form of the fiber material include forms such as a woven fabric, a knitted fabric, a fabric, a thread shape, and a non-woven fabric. Examples of the use of the fiber material include objects that impart antibacterial properties, water absorption, and washing resistance, such as underwear, sports clothing, bedding, and covers.

  In the present invention, examples of the component to be deodorized include aldehyde components such as nonenal, acetaldehyde, and formaldehyde.

The treatment liquid in the step (A) is obtained by diluting the chemical of the present invention with water or the like. The weight ratio of the amino-modified silicone in the treatment liquid is preferably 0.0001 to 10% by weight, more preferably 0.0005 to 7% by weight, and still more preferably 0.001 to 5% by weight.
The treatment liquid may contain other components other than the above components as long as the effects of the present invention are not impaired. Examples of other components include the same components as those exemplified for the drug.

  There is no limitation in particular as a method of giving the processing liquid of a process (A) to textile material, and a publicly known method is employable. Among these, at least one method selected from the exhaust method, the pad dry method, the spray method, and the coating method is preferable, and the pad dry method is more preferable from the viewpoint that the drug can be reliably fixed to the fiber material.

  Known methods can be employed as the exhaust method, pad dry method, spray method, and coating method. The exhaust method is a method in which a diluted solution of a drug is used, conditions such as temperature, immersion time, number of times of liquid circulation, etc. are set, and the drug is selectively adsorbed on a fiber to be exhausted and adhered. Thereafter, washing is usually carried out, followed by centrifugal dehydration and drying. The pad dry method is a method in which fibers are immersed in a drug solution for a short time and immediately attached by squeezing with a dehydrated mangle or the like. Then, drying is performed and curing is performed as necessary. The spray method is a method in which fibers are placed on a conveyor at a constant speed and adhered by spraying a predetermined amount of a solution of the drug from the fiber. Then, drying is performed and curing is performed as necessary. The coating method is a method in which a drug solution is usually applied by applying from one side with a mangle. Then, the excess drug is scraped off with a doctor, dried, and cured if necessary.

  5-40 degreeC is suitable for the temperature at the time of providing the processing liquid of a process (A) to a fiber material. When the application temperature is lower than 5 ° C., it may be difficult to maintain the constant temperature, and thus it may not be possible to perform constant application to the fiber material. On the other hand, when the application temperature is higher than 40 ° C., the elution of dyes and the like contained in the fiber material may increase.

  A process (B) is a process of heat-processing the fiber material which provided the process liquid. About the temperature to heat-process, Preferably it is 100 degreeC or more, More preferably, it is 105-200 degreeC, More preferably, it is 110-150 degreeC. If the temperature is lower than 100 ° C., washing durability may not be imparted.

The step (B) may be performed simultaneously with the drying step of drying the fiber material, or may be provided separately after drying. The fiber material to which the treatment liquid is applied is dried by a method such as tensionless or applying tension. Examples of the tensionless drying method include a non-touch dryer, a short loop dryer, a tensionless roller type, and a cylinder dryer. Examples of the method of applying a tension and drying include a pin tenter and a clip tenter.
Thus, the deodorant fiber of this invention can be obtained through a process (A) and a process (B).

  The production method of the present invention may include a process that can be processed simultaneously with the deodorizing process as long as the effects of the present invention are not impaired. Processes that can be processed at the same time include discoloration inhibitors, discoloration inhibitors, insecticides, antifungal agents, acaricides, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, and antifouling agents. , A step of imparting a color deepening agent, a smoothing agent, a softening agent or a water absorbing agent. A plurality of these steps can be performed simultaneously. About each chemical | medical agent, a well-known thing is employable.

  The amount of amino-modified silicone applied is preferably 0.01 to 30% by weight, more preferably 0.05 to 25% by weight, and still more preferably 0.1 to 20% by weight with respect to the fiber material. If the application amount is less than 0.01% by weight, deodorizing properties may not be provided. When the application amount is more than 30% by weight, the slip resistance of the fiber material may be reduced. The adhesion amount of amino-modified silicone can be calculated by quantifying Si element by fluorescent X-ray, ICP or the like.

The amino group adhesion amount of the amino-modified silicone is preferably 10 ⁻⁷ to 10 ⁻³ mol / kg, more preferably 5 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol / kg, and still more preferably with respect to the fiber material. 10 ⁻⁶ to 10 ⁻⁴ mol / kg. When the adhesion amount is less than 10 ⁻⁷ mol / kg, deodorizing properties may not be imparted. When the adhesion amount is more than 10 ⁻³ mol / kg, an amine odor may be generated (cause of emulsification failure or yellowing). The amino group adhesion amount of amino-modified silicone can be calculated from the adhesion amount of Si element and the amine value of the amino-modified silicone.

EXAMPLES Hereinafter, examples of the present invention will be shown and the present invention will be described in more detail. However, the present invention is not limited to these examples . “Part” and “%” in the examples represent “part by weight” and “% by weight”, respectively. Examples 1 to 8 and 10 to 15 are used as reference examples.

Example 1
In a reactor having a capacity of 3 liters equipped with a thermometer reflux condenser and a stirrer, 300 g of amino-modified silicone 1 shown in Table 1 and surfactant 1 (polyoxyethylene alkyl ether having 12 to 14 carbon atoms, ethylene oxide addition mole) (Several 7 moles) was added to 100 g, and after sufficient stirring, 600 g of water was added to obtain a deodorizing agent for fibers having an active ingredient (nonvolatile content) of 40% by weight.
Using the obtained fiber deodorizing agent, it was processed into a test cloth under the following processing conditions to obtain a test sample. About the test sample, deodorant property, washing durability, and evaluation of texture were performed by the following method. The results are shown in Table 2.

<Processing conditions>
Test cloth: Cotton knit spadding: Twice twice, two times squeezing, squeezing rate 100% by weight
Treatment liquid: deodorant processing agent 2.5 wt% soln. (Water dispersion)
Non-volatile content: 1% by weight
Heat treatment (drying) conditions: 100 ° C. × 3 minutes

<Deodorant>
About the obtained test sample, the deodorization performance is measured by the deodorization performance measurement method in the Fiber Analysis Technology Council Deodorization processed fiber product certification standard equipment analysis implementation manual (detection tube method, gas chromatography method). did. The deodorizing property was targeted at Nonenal, and 75% or more were acceptable levels according to the SEK standard.

<Washing durability>
About what wash | cleaned the obtained test sample on the following conditions, deodorizing property was measured by the same method as said deodorizing property test method, and washing durability was evaluated.
In accordance with JIS L 0217 103, using a JAFET standard detergent at a rate of 3 g / L, washing with water at 40 ° C. for 5 minutes at a bath ratio of 1:30, then rinsing twice at 40 ° C. for 2 minutes, and centrifugal dehydration After that, the work of drying in the shade was defined as one cycle, and this was performed for 10 cycles.

<Texture>
The texture of the obtained test sample was evaluated by touch. In addition, the evaluation of the texture was determined by classifying into the following four stages based on the following criteria.
A: Flexible.
○: Slightly flexible (equivalent to raw cotton knit)
Δ: Slightly coarse and hard
×: Rough

(Examples 2-15, Comparative Examples 1-7)
Evaluation was made in the same manner as in Example 1 except that the deodorizing agent for fibers of Example 1 was changed to the amino-modified silicone, surfactant, and blending amounts shown in Table 2. The results are shown in Table 2. The types of amino-modified silicones are shown in Table 1, and the types of surfactants are shown below.
Surfactant 2: Polyoxyethylene-polyoxypropylene alkyl ether (carbon number 12-14, ethylene oxide addition mole number 8 mole, propylene oxide addition mole number 2 mole)
Surfactant 3: Lauryltrimethylammonium chloride

(Comparative Example 8)
Adipic acid dihydrazide 3 (5.0 g) and zinc chloride (7.0 g) were dissolved in 2 L of water, and 100 g of fluorine phlogopite was added, followed by stirring for 15 hours. After the reaction, it was filtered, washed with water, and dried at 110 ° C. to obtain a natural zeolite carrying adipic acid dihydrazide. 300 g of the obtained natural zeolite carrying adipic acid dihydrazide, 100 g of surfactant 1 (polyoxyethylene alkyl ether carbon number 12-14, ethylene oxide addition mole number 7 mol), and 600 g of soft water were added to a stirrer and stirred sufficiently. And dispersed to prepare a slurry liquid. Next, this slurry was micronized for 4 hours using Starmill ZRS (manufactured by Ashizawa Finetech Co., Ltd.) to obtain a deodorizing agent for fibers having an active ingredient (nonvolatile content) of 40% by weight.
Evaluation was performed in the same manner as in Example 1 except that the fiber deodorizing agent for Example 1 was changed to the agent obtained above. The results are shown in Table 2.

(Comparative Example 9)
As a blank, an unprocessed test cloth was evaluated in the same manner as in Example 1. The results are shown in Table 2.

From Table 2, it can be seen that the fiber band deodorizing agent of the present invention can impart superior deodorizing properties and washing durability to the fiber material as compared with the comparative example.

Claims (4)

A deodorizing agent for fibers used to impart deodorizing properties of aldehyde components to fiber materials,
Containing an amino-modified silicone represented by the following general formula (1) having a primary amino group in the molecule as essential, a surfactant and water;
A deodorizing agent for fibers, wherein the amino-modified silicone has a viscosity (25 ° C.) of 200 to 100,000 mPa · s and an amino equivalent of 500 to 7000 g / mol.

X: is a group represented by —R ¹ —NH ₂ or —R ² —NH—R ³ —NH ₂ , and R ¹ , R ² and R ³ each independently represent an alkylene group.
Y: A hydroxy group, a polyether group, an alkyl group, an alkenyl group or an alkoxy group.
Z: represents an alkoxy group .
R ⁴ : represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, a hydroxy group or an alkoxy group.
n: An integer from 1 to 400.
m: represents an integer of 0 to 400.
k: An integer of 1 to 2000 is shown. The weight ratio of the amino-modified silicone and the surfactant is 50/50 to 99/1,
The deodorizing agent for fibers according to claim 1 , wherein the total weight ratio of the amino-modified silicone and the surfactant in the nonvolatile content of the agent is 90% by weight or more. A process comprising a step (A) of applying a treatment liquid containing the fiber deodorizing agent according to claim 1 or 2 to a fiber material, and a step (B) of heat-treating the fiber material to which the treatment liquid has been applied. Manufacturing method of odorous fiber. The manufacturing method of the deodorizing fiber of Claim 3 whose adhesion amount of the said amino modification silicone is 0.01-30 weight% with respect to fiber material.