JPH0670304B2 - Sustained release fiber material and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a sustained-release fiber material such as various fibers, spinning or various paper materials, etc., which can provide long-lasting aromaticity, and a method for producing the same.

(Prior Art) In recent years, various fibers, spun fibers, or various paper materials have been impregnated with a perfume (aromatic substance) and dried to make the fiber materials aromatic. For example, the fiber material is immersed in a treatment liquid obtained by dissolving the fiber material in a binder, and then the fiber material is taken out into the air to cure the fiber binder, thereby adhering the fiber material to the fiber material.

However, although the fragrance is temporarily attached to the fiber material in this way, the fragrance is easily volatilized, but the fragrance is not maintained for a long time.

On the other hand, a method of microencapsulating a fragrance has been attempted. For example, by the coacervation method,
By coating perfume molecules with a film of gelatin, polyvinyl alcohol (PVA), etc., microencapsulated perfume with a particle size of 10 to 100 μm can be obtained. Such microencapsulated fragrance has already been commercialized. However, since the perfume in this microcapsule is sealed with the above-mentioned gelatin or PVA film, it does not give off a scent in the as-manufactured state. When the capsule film is destroyed by physical force, it emits a scent for the first time. When the capsule is destroyed, the fragrance is released all at once, and the released fragrance evaporates in a short time. Therefore, after the microcapsule is destroyed, the fragrance is not maintained for a long time.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and an object thereof is a sustained-release fiber material capable of obtaining a fiber material having sustained-release characteristics such as aromaticity over a long period of time. Another object of the present invention is to provide a method for producing a sustained-release fiber material which is relatively easy to produce.

(Means and Actions for Solving the Problems) The inventor has found that if a perfume molecule and / or drug particles can be encapsulated or included in a porous polymer matrix, the sustained release fiber material having excellent sustained release properties can be obtained. Therefore, the present invention was completed by studying the preparation of a sustained-release fiber material using such a polymer.

That is, in the sustained-release fiber material of the present invention, the fiber material is impregnated with a sol-state sustained-release composition containing a fragrance and / or a drug, ethyl silicate, a solvent and a catalyst, and the sustained-release composition is a gel. The above-mentioned purpose is achieved by this.

In addition, the method for producing a sustained-release fiber material of the present invention comprises a fragrance and
Or a step of impregnating a fibrous material with a sol-state sustained-release composition containing a drug, ethyl silicate, a solvent and a catalyst,
And a step of gelling the sustained-release composition, whereby the above object is achieved.

Hereinafter, the present invention will be described in detail.

The fragrance used in the sustained-release composition of the present invention may be any of animal natural fragrance, plant natural fragrance and synthetic fragrance. In addition, the medicines are good in terms of organization and health,
Examples include pesticides, insecticides, pesticides and the like. At least one or more of these flavors and agents are included. They are,
It is used in an amount of 1 to 300 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of ethyl silicate. If it is less than 1 part by weight, a sustained-release fiber material having desired aroma cannot be obtained. It is difficult to microencapsulate perfume in amounts above 300 parts by weight.

The catalyst used in the sustained-release composition of the present invention is a so-called sol-gel method catalyst (used for hydrolyzing / polycondensing ethyl silicate and silane coupling agent).
Can be used and can include an acid or its anhydride and an organic base. As the above-mentioned acid, a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid is usually used. A similar effect can be obtained with an anhydride of mineral acid, such as hydrogen chloride gas. Besides, organic acids and their anhydrides can also be used. This includes, for example, tartaric acid, phthalic acid, maleic acid, dodecylsuccinic acid, hexahydrophthalic acid, methylnadic acid, pyromellitic acid, benzophenonetetracarboxylic acid, dichlorosuccinic acid, chlorendic acid, phthalic anhydride, maleic anhydride. , Dodecyl succinic anhydride, hexahydrophthalic anhydride, methyl nadic acid anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, dichlorosuccinic anhydride, and chlorendic anhydride.
These acids are used in an amount of 0.01 mol or more, preferably 0.01 to 0.5 mol, per 1 mol of ethyl silicate. If it is too small, hydrolysis hardly progresses.

Also, the organic base is substantially insoluble in water, and
A tertiary amine soluble in an organic solvent is preferably used. Tertiary amines include N, N-dimethylbenzylamine, tributylamine, tri-n-propylamine, tripentylamine, tripropargylamine, N, N, N-trimethylethylenediamine, tri-n-hexylamine, etc. To be The tertiary amine is in an equimolar amount or more than the above acid, preferably 0.001 mol per 1 mol of ethyl silicate.
It is used in a proportion of 1 to 0.10 mol. The amount of the tertiary amine used is appropriately determined within the above range depending on the degree of dissociation. When the amount of the tertiary amine is too small, the polycondensation reaction after hydrolysis of the ethyl silicate and the silane coupling agent becomes extremely slow. Further, it is preferable to adjust the pH of the sustained release composition to about 5 to 6 so that the sol state is maintained for a predetermined time.

Examples of the solvent used in the present invention include water used for hydrolysis and organic solvents. As an organic solvent,
A solvent that can be mixed with water or a solvent that can be partially dissolved in water is used. These include, for example, methanol, ethanol, butanol, propanol, pentanol, hexanol, acetone, methyl ethyl ketone, formamide.

You may mix | blend a silane coupling agent with the sustained-release composition of this invention. A known silane coupling agent can be used as the silane coupling agent. For example, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropylmethyldiethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane ・ hydrochloride, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyl Trimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, hexamethyldisilazane, -Anilinopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, There are aminosilane formulations.

The silane coupling agent is used in an amount of 300 parts by weight or less, preferably 1 to 300 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of ethyl silicate. Even if an amount of the silane coupling agent exceeding 300 parts by weight is added, the physical properties of the obtained polymer (gelled product) are almost unchanged and expensive.

An organic monomer can be added to the sustained-release composition of the present invention. Examples of the organic monomer include acrylic acid, methacrylic acid, dimethylformamide, acrylonitrile, styrene, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
However, the present invention is not limited to this, and other vinyl monomers can be used. The amount of the organic monomer is 300 parts by weight or less, preferably 100 parts by weight or less, preferably 100 parts by weight of the ethyl silicate.
It is used in the range of 10 to 300 parts by weight, more preferably 30 to 100 parts by weight. It is also preferable to blend a resin such as nylon or butyral.

The sustained-release fiber material of the present invention is mainly produced by the following three methods.

The first method is to prepare a sustained-release composition mainly using a fragrance and / or a drug, ethyl silicate, a solvent and a catalyst, and to impregnate the fiber material with the sustained-release composition in the sol state.
Then, the sustained-release composition impregnated in the fiber material is gelled. The second method is a sustained-release composition mainly using a fragrance and / or a drug, ethyl silicate, a solvent, a catalyst and a silane coupling agent. A composition is prepared, a fiber material is impregnated with the sustained-release composition in the sol state, and then the sustained-release composition impregnated in the fiber material is gelled.
In the method of (1), a sustained-release composition is prepared mainly using a fragrance and / or a drug, ethyl silicate, a solvent, a catalyst, a silane coupling agent and an organic monomer, and the sustained-release composition in the sol state is used as a fiber material. This is for impregnating and then gelling the sustained-release composition impregnated in the fiber material.

According to the first method, for example, first, the ethyl silicate is dissolved in the organic solvent, for example, alcohol. The concentration of ethyl silicate is not particularly limited, but usually 5
It is from 00 to 600 g / l. Then water is added. The amount of water is 1 to 30 mol per mol of ethyl silicate. Water may be previously mixed with the alcohol. In this ethyl silicate solution (including water),
The fragrance and / or drug is dissolved or dispersed. The fragrance and / or drug is dissolved in, for example, an organic solvent or used as an aqueous solution. An acid (or an anhydride thereof) and a tertiary amine of the sol-gel method catalyst are added thereto, and the mixture is stirred at room temperature. This reaction is preferably performed at room temperature to prevent volatilization of the fragrance.
Here, the pH of the sustained-release composition is set low, and gelation does not proceed rapidly. This gelation time depends on the amount of water used and the amount of sol-gel process catalyst.

Next, the fiber material is impregnated with the sustained-release composition by passing the fiber material through the tank containing the sustained-release composition in the sol state. The sustained release composition is gelled. As the fiber material, various natural fibers, synthetic fibers, spun yarns, various paper materials and the like are used.

The gel is formed because an inorganic polymer compound is produced by hydrolysis and polycondensation of the ethyl silicate. Perfume particles and / or drug particles (here, perfume molecules and / or drug molecules and, if necessary, solid or liquid fine particles containing an organic solvent in which the perfume is dissolved) are contained in the matrix of the polymer compound. Pointed) is captured. More specifically, it is considered that the perfume particles and / or the drug particles are encapsulated and / or included in the following forms. In the above reaction, the hydrolyzed ethyl silicates are polycondensed with each other and crosslinked to form a particulate three-dimensional structure. When this particulate three-dimensional structure is formed, the perfume particles and / or the drug particles are trapped in the three-dimensional space. That is, the perfume particles and / or the drug particles are in the form of being encapsulated in the polymer particles. When a plurality of these particles are collected and the polycondensation / cross-linking reaction proceeds, a continuous three-dimensional matrix is formed. The fragrance particles and / or the drug particles are incorporated into the internal space and are in an encapsulated or clathrate form. Such encapsulated or clathrate perfume and / or drug particles have a porous matrix skeleton when the solvent and alcohol (generated by the reaction) are volatilized and removed from the skeleton of the three-dimensional matrix, as described later. The fragrance and / or the drug is trapped inside.
Moreover, it is known that the pore size of the small pores of the porous matrix is extremely small. Therefore, gradually fragrance and /
Or, it has an effect that the drug is volatilized and sustained release is sustained for a long time.

According to the second method, a silane coupling agent is used in addition to the sustained release composition of the first method. For example, first, a fragrance, a silane coupling agent and, if necessary, a photosensitizer are added to a solution containing ethyl silicate, alcohol and water to prepare a sustained release composition. Diacetyl or the like is used as the photosensitizer, which accelerates the photopolymerization reaction by ultraviolet irradiation. Further, other monomers and polymers may be added if necessary. Examples of such a monomer include vinyl monomers, and examples of the polymer include polymers or copolymers obtained by polymerizing vinyl chloride, vinyl acetate, butadiene, and the like. These monomers and polymers are added for the purpose of promoting the polymerization reaction and copolymerization reaction described later and forming a homogeneous and reinforced polymer. A sol-gel method catalyst is added to this mixed solution in the same manner as in the first method to prepare a sustained release composition, and a sustained release fiber material is produced in the same manner as in the first method. .

After the fiber material is impregnated with the sustained release composition, the fiber material impregnated with the sustained release composition may be exposed to ultraviolet rays and / or
Alternatively, an electron beam may be irradiated. UV wavelength is 250n
Less than or equal to m. Above 250 nm, the radical polymerization, crosslinking reaction, and polycondensation reaction, which are described later, do not proceed sufficiently. The electron beam dose is in the range of 0.1 to 50 megarads. The amount of energy is preferably 150 to 200 KV. Below 0.1 megarad, the radical polymerization, cross-linking reaction and polycondensation reaction described below are difficult to proceed sufficiently. It does not require an electron beam in excess of 50 megarads. As the electron beam irradiation device, for example, an area beam type electron beam irradiation device (Curetron, manufactured by Nissin Electric Co., Ltd.) is used.

The ethyl silicate and the silane coupling agent of the above-mentioned sustained release composition are hydrolyzed, and then the polycondensation reaction proceeds rapidly. Furthermore, if the silane coupling agent has, for example, an epoxy moiety, the above catalyst causes acid cleavage reaction or base cleavage reaction (ring opening reaction) of the epoxy ring. On the other hand, by irradiation with ultraviolet rays and / or electron beams, for example, a radical is generated from a vinyl group, and this radical is
Initiate a crosslinking reaction or radical polymerization (photopolymerization or electron beam polymerization) of the organic portion of the silane coupling agent. Radicals are generated from photosensitizers in the case of UV irradiation. In addition to electron beams and ultraviolet rays, a method of utilizing radiation can be adopted.

In this way, the hydrolysis reaction and polycondensation reaction of ethyl silicate and the silane coupling agent (inorganic part) rapidly proceed. Radical polymerization (including crosslinking reaction) of the organic portion of the silane coupling agent also proceeds simultaneously with the polycondensation reaction. The above reactions occur both between homologous and heterologous molecules. The inorganic part (silica part) of the silane coupling agent is incorporated into the skeleton of the inorganic polymer or polymerized alone to form the inorganic polymer. The organic portion forms a crosslinked portion while being bonded to the silicon atom.

The polymer compound thus formed is formed by polymerizing the inorganic polymer portion formed by hydrolysis and polycondensation of ethyl silicate and the silane coupling agent and the functional group (organic portion) of the silane coupling agent. And an organic polymer portion. In other words, a polymer compound in which ethyl silicate and a silane coupling agent react to bond at the molecular level (this is considered to be a composite polymer compound having an organic part and an inorganic part) is formed. The reaction system in which such a polymer compound is formed is in the form of gel as in the first method. The complex polymer compound forms a three-dimensional matrix almost similar to that obtained by the first method, and the perfume particles and / or drug particles present in the reaction system are encapsulated in the matrix in a similar form. And / or is included.

According to the third method, in addition to the sustained-release composition of the second method, an organic monomer is further used to prepare a sustained-release composition, and the sustained-release composition is prepared in substantially the same manner as the first method. A loose fiber material is manufactured.

In addition, when performing photopolymerization which irradiates an organic monomer and ultraviolet rays, it is preferable to add a photosensitizer, such as diacetyl. Further, if necessary, as in the second method, other monomers and polymers are preferably added. The reaction caused by the addition of a sol-gel method base catalyst and irradiation with ultraviolet rays and / or electron beams is similar to that of the second method, but in this method, the organic monomer is further polymerized by radical reaction. .
This polymerization reaction occurs between organic monomer molecules,
Furthermore, the organic part of the silane coupling agent (epoxy group,
Between vinyl groups) and the organic monomer molecule.
As described above, in the third method, a complex crosslinked complex polymer compound containing more organic moieties than the polymer compound contained in the composition obtained in the second method is produced.
The fragrance particles and / or drug particles are encapsulated and / or included in the composite polymer matrix as in the first and second methods.

By the way, although a mineral acid is generally known as a sol-gel method catalyst, when this catalyst is adopted, in the third method, compared with the polymerization reaction of an organic monomer, ethyl silicate or a silane coupling agent is used. Hydrolysis / polycondensation reaction is extremely slow. As a result, a homogeneous composite polymer compound is not formed. On the other hand, in the method of the present invention,
Since the sol-gel method catalyst (acid and tertiary amine) developed by the inventor is used, the polycondensation reaction of the ethyl silicate and the silane coupling agent proceeds very rapidly, and a homogeneous composite polymer compound is obtained. It is formed.

When radical polymerization using electron beams and / or ultraviolet rays is carried out by the above second and third methods, the reaction proceeds even at a low temperature of 20 to 30 ° C., so that the fragrance and / or the drug is volatilized.
It never disappears. Also in the compositions obtained by these second and third methods, when the solvent and alcohol are removed from the reaction system (including the inside of the matrix skeleton), a porous polymer matrix containing perfume particles and / or drug particles is obtained. can get. Therefore, this composition is also excellent in the sustained release effect of the fragrance. Since the polymer compound in the composition obtained by these methods contains an organic component, it has an excellent film forming rate and excellent adhesion to the fiber material. Therefore, it is possible to obtain various yarns, spun yarns, and papers having excellent durability and aromatic properties with excellent sustained release effect.

In various fiber materials using the composition of the present invention, aromaticity, insecticidal effect, disinfectant effect, etc. are maintained for a long period of time.

(Example) Hereinafter, the present invention will be described with reference to Examples.

Example 1 The above components were mixed to obtain a sustained-release composition adjusted to pH 5-6.

Then, wool spinning was dipped in the sustained-release composition for scanning, and the spinning was directly wound on a wood tube by a winding machine and dried and cured at room temperature for 3 hours to obtain an aromatic spinning.
The scanning speed of the spinning was 70 m / min.

When a woven fabric was made from the obtained aromatic spinning, a certain aromaticity was maintained for 8 months.

Example 2 The above components were mixed to obtain a sustained-release composition adjusted to pH 5-6. Next, this sustained-release composition was impregnated with acrylic yarn and scanned, and then this spun yarn was directly wound on a wood tube by a winding machine and dried and cured at room temperature for 3 hours to obtain an aromatic yarn. The scanning speed of the above spinning was 18.2 m / min.

When a woven fabric was made from the obtained aromatic spinning, a certain aromaticity was maintained for 8 months.

Example 3 The above components were mixed to obtain a sustained-release composition adjusted to pH 5-6.

Next, a cloth (broad cloth made of 100% cotton) was dipped in the sustained-release composition, pulled up and dried. The amount of solid matter deposited on the fabric was 13.8 g / m ² . The scanning speed of the above spinning was 18.2 m / min.

This aromatic fabric retained its scent for 6 months.

(Effects of the Invention) According to the present invention, as described above, a sustained-release fiber material which is excellent in the sustained-release property of a fragrance component or a drug component and can maintain the sustained-release property for a long period of time, and a method for producing the same are provided. . Using this sustained-release fiber material, it is possible to obtain various fibers, spinning, woven fabrics, net cloths, non-woven fabrics, clothes, bedding, and paper that have excellent sustained-release properties over a long period of time.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location D21H 19/32 D06M 15/647

Claims (4)

[Claims] 1. A fragrance and / or a drug, ethyl silicate,
A sustained-release fiber material obtained by impregnating a fiber material with a sol-state sustained-release composition containing a solvent and a catalyst, and gelling the sustained-release composition. 2. A catalyst according to claim 1, wherein the catalyst contains a tertiary amine which is substantially insoluble in water and soluble in an organic solvent.
The sustained-release fiber material according to the item. 3. A perfume and / or drug, ethyl silicate,
A method for producing a sustained-release fiber material, which comprises a step of impregnating a fiber material with a sol-state sustained-release composition containing a solvent and a catalyst, and a step of gelling the sustained-release composition. 4. A catalyst according to claim 3, wherein the catalyst contains a tertiary amine which is substantially insoluble in water and soluble in an organic solvent.
The method for producing a sustained-release fiber material according to item.