JP2000154464A - Water repellent polymer material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water repellent polymer material not causing the degradation of feeling, excellent in durability, water repellency and abrasive resistance and capable of preventing the deterioration of the material when being treated, and also to provide a method for producing the same material. SOLUTION: This polymer material having water repellent function is obtained by the acylation reaction of a polymer material with a long-chain dibasic acid anhydride having one double bond in a molecule so as to introduce a long-chain acyl group into reaction sites of the polymer material. The above anhydride is expressed by the formula [wherein, (n) is an integer of 10-19] and is used in a dissolved state in an organic solvent. The water repellent polymer is expressed by the formula S-NHCO-CH2-CH(COOH)-CH2-CH=CH- CnH2n+1 [where in, S is a molecule of the polymer material; (n) is an integer of 10-19] or the formula S'-OCO-CH2-CH(COOH)-CH2CH=CH-CnH2n+1 [wherein, S' is a molecule of the polymer material; (n) is an integer of 10-19].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent polymer material and a method for producing the same, and more particularly, to a polymer material which is not degraded during a modification treatment, that is, during a chemical modification reaction. Further, the present invention relates to a water-repellent polymer material which does not decrease the feeling of feeling, has excellent durability and durability, and has good wear resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, silk fibers having good dyeing properties and characteristic texture have been used as clothing materials for a long time. Silk fiber has traditionally been used as a kimono material, but in recent years the lifestyle has changed and behavioral clothing materials have become increasingly preferred, and the use of silk fiber as a kimono material has been decreasing. It is in. In order to increase the demand for silk fiber materials, it is required to use and develop not only traditionally used materials in the Japanese clothing field but also materials in the Western clothing field. For example, it is important to develop technology for use as a material in the casual field such as shirts, blouse products, upper garments and hats. For this purpose, silk fibers are chemically processed without losing the excellent practical functional characteristics of natural silk fibers, and various functions such as form stability, heat resistance, water repellency, oil repellency, etc. that are not originally possessed It is necessary to obtain a silk fiber and its fiber product which have been modified by imparting the same. Attempts to impart various functions such as form stability, heat resistance, water repellency, oil repellency, etc. to silk fibers have the problem of material deterioration during chemical processing, and often impair the feel of the product. Processing without such problems is desired. This is also true for wool fibers and other protein fibers.

[0003] Protein fibers such as silk fibers and wool fibers have limited applications because their surfaces exhibit strong hydrophilicity. However, if a water-repellent function can be imparted to this surface, clothing materials and non-clothing materials are used. The possibility of being used as is expanded. Thus, if a technique for expressing the water-repellent function on the surface of the protein fiber can be established, a highly functional material that can be used as an advanced material not only in the clothing field but also in the medical field can be provided.

Further, the surface of silk fiber or a silk fiber composite material such as silk fiber / polyester fiber or silk fiber / wool fiber has a problem that dirt easily adheres and dirt during washing is difficult to remove. When using these silk fibers or silk fiber composite materials for casual applications such as shirts and blouses,
There were many restrictions in terms of easy care (things that do not take time, such as the need for ironing after washing, are called easy care).

[0005] Various techniques have been proposed for compensating for the drawbacks of the practical functionality of silk fibers and improving the performance as clothing materials.
For example, JP-A-3-213572 discloses that a silk fiber fabric is first treated with a water-soluble epoxy compound, and a water- and oil-repellent agent having a perfluoroalkyl group and a polyoxyethylene group in the same molecule. There has been proposed a method of imparting an antifouling function to silk fibers by treating with a treatment solution containing an antistatic agent and then performing heat treatment. However, in this method, a processing step performed to impart water / oil repellency to the silk fiber, that is, a processing reaction using an epoxy compound,
Furthermore, since a plurality of subsequent processes such as antifouling processing and heat treatment are repeatedly performed, the physical and chemical changes are repeatedly given to the silk fibers, and the fine structure of the fibers changes, resulting in deterioration of the material. And the risk of microstructure destruction is high. Furthermore, since the water-repellent / oil-repellent processing solution used in the method described in this publication contains a high-concentration nonionic compound of about 20 g / L as an antistatic processing agent, There is a problem that the surface of the silk fiber is slightly hydrophilic, and it is difficult to obtain the desired effect of the antifouling treatment. In addition, since the water-repellent and oil-repellent finishing agent does not penetrate into the interior of the silk fiber and cross-links three-dimensionally on the fiber surface to form a resin, the silk fiber becomes hard if the amount of the processing agent attached is large. There is also a problem that the original feeling characteristics of silk fibers are lost.

As a method for imparting water repellency to the surface of a protein fiber such as a silk fiber, a resin is processed with an emulsion type fiber treating agent comprising a highly polymerized epoxy-modified silicone and a base polymer, and the silicone is used as a fiber sample. Techniques for introducing to surfaces are known. That is, this technology
The silk fabric is immersed and padded in the emulsion type fiber treating agent solution having a concentration of 3 to 30 g / L (the fabric and the like are passed through the treating solution, squeezed by a roller, and the treating solution is sufficiently impregnated) and taken out. Squeezing and drying to complete processing. According to such a method, a soft finish can be performed on a fiber product, and a product having excellent flexibility, smoothness, texture, etc. can be obtained. , The texture, flexibility, gloss and the like become poor, and as a result, the fiber product becomes hard. Furthermore, there is also a problem that the supple and hygroscopic properties inherent to protein fibers are impaired, and the value as a clothing material is reduced by half.

Japanese Patent Application Laid-Open No. H10-77579 discloses a method for producing a water-repellent fiber product.
A method is described in which, after performing immersion treatment with a solution containing a sulfonated phenol formaldehyde low-condensate and a urea resin, a mixed liquid of a polyfluoroalkyl group-containing acrylic copolymer and an aminoplast resin is applied, and a heat treatment is performed. ing. Japanese Patent Application Laid-Open No. Hei 10-77580 discloses a method for producing a yellowing-resistant and water-repellent fiber product. According to this method, a textile product is subjected to a dipping treatment with a solution containing an alkyldiphenyl ether compound. Thereafter, a mixture of the polyfluoroalkyl group-containing acrylic copolymer and the aminoplast resin and / or the polyfunctional blocked isocyanate group-containing urethane resin is applied, and heat treatment is applied to impart yellowing resistance and water repellency to the textile product. it can.
These conventional methods relate to a technique of embedding a polyfluoroalkyl group-containing acrylic copolymer, a reagent for imparting water repellency to a fiber product surface, in a polymer resin and coating the fiber product surface. However, if these processing agents are used in many cases to enhance the water repellency, the fiber product becomes harder, the original material of the fiber product deteriorates, and the water repellent active ingredient is only mechanically embedded in the resin. There is a problem in durability, and there is also a problem that the texture of the textile product is lost during processing.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and provides an acylation reaction of a long-chain dibasic acid anhydride having one double bond in a molecule with a polymer material. A method for producing a water-repellent polymer material that does not deteriorate during processing, does not cause a reduction in texture, and has excellent water repellency and abrasion resistance with excellent durability and durability. It is an object of the present invention to provide a water-repellent polymer material obtained.

[0009]

Means for Solving the Problems The present inventors have intensively studied the chemical reactivity of an acylating agent chemically bonded to an insect biopolymer. At this time, as a result of a detailed study of the chemical reactivity between the dibasic acid anhydride dissolved in the organic solvent and the polymer material, a long-chain dibasic anhydride having one double bond in the molecule was converted to N , N-dimethylformamide (hereinafter referred to as D
By dissolving the polymer material in an organic solvent such as MF, which is sometimes abbreviated as MF), and chemically treating the polymer material in this solution, the polymer material does not deteriorate during the treatment, and has excellent water repellency and resistance. The present inventors have found that a water-repellent polymer material having abrasion properties and not impairing the original excellent feeling of texture can be produced, and the present invention has been completed.

In the present invention, a polymer material is subjected to an acylation reaction with a long-chain dibasic acid anhydride having one double bond in the molecule, and an alkyl group, which is a long-chain hydrocarbon, is added to the polymer material. By introducing the polymer material, a polymer material having a water-repellent function and other various functions is manufactured.

The polymer material which can be used in the present invention has the following general formula (I):

[0012]

Embedded image (Where n is an integer of 10 to 19) is a long-chain dibasic anhydride having one double bond in the molecule represented by D
A material having a reaction site where an acylation reaction occurs between the material and a long-chain dibasic acid anhydride when the material is heated in a system dissolved in an organic solvent such as MF.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, a long-chain dibasic acid anhydride which is an acylating agent that can be used in the present invention has the following general formula (I):

[0014]

Embedded image (Where n is an integer of 10 to 19),
A compound having a long-chain acyl group having one double bond in the molecule.

As the long-chain dibasic acid anhydride having one double bond in the molecule, n is preferably an integer of 10 or more in Formula (I), and the larger the value of n, the more preferably used.
Compounds having a small value of n exhibit a property of easily penetrating into a polymer material due to a short alkyl group chain, but on the other hand, have low chemical reactivity with a reaction site of the polymer material and are repelled even when reacted. Water effect is not enough. When the value of n increases to about 10, the chemical reactivity increases, and as a result, various functions such as water repellency can be effectively imparted to the polymer material. Therefore, the preferred long-chain dibasic acid anhydride in the present invention has a value of n of 1
Any dibasic acid anhydride can be used as long as it is 0 or more and the chemical reactivity with the polymer material is not reduced, and there is no particular limitation. When the value of n approaches 20, the length of the alkyl group becomes too long, so that the dibasic acid anhydride hardly penetrates into the polymer material, and the reaction efficiency decreases. Therefore, any long-chain dibasic acid anhydride can be used as long as the reaction efficiency does not decrease, and preferably, the value of n is 19
The following may be used. Preferred long-chain dibasic acid anhydrides usable in the present invention include, for example, the following acylating agents. The organic solvent that can be used in the acylation reaction may be any solvent that can dissolve the long-chain dibasic acid anhydride used in the present invention. As such, for example, D
MF, dimethyl sulfoxide (hereinafter sometimes abbreviated as DMSO), tetrahydrofuran, pyridine and the like. In the present invention, for example, DMF, DMS
The use of O or the like is particularly preferred.

The chemical modification of the polymer material is usually performed under heating at 60 to 90 ° C. The preferred reaction temperature is 70
８５85 ° C. If the reaction temperature is lower than 60 ° C., the reaction efficiency is not good. If the reaction temperature is higher than 90 ° C., there is a problem that the long chain dibasic acid anhydride or the structural stability of the polymer material is lowered. The concentration of the long-chain dibasic anhydride in the organic solvent may be 5 to 30%. If the concentration is less than 5%, there is a problem that the reaction efficiency is reduced. If the concentration is more than 30%, the amount of the long-chain dibasic acid anhydride dissolved in the organic solvent is gradually reduced, and the reaction temperature is increased to extend the reaction time. However, the reaction efficiency does not increase and there is a problem in efficiency. When performing chemical modification processing at a high temperature, for example, at a temperature of 75 ° C. or higher, the solvent gradually evaporates, and the concentration of the dibasic acid anhydride of the processing agent changes accordingly. There is concern that it will change. Therefore, it is desirable to perform the chemical modification processing in an apparatus such as an eggplant-shaped flask or an Erlenmeyer flask equipped with a backflow cooler.

After completion of the acylation reaction, the modified polymer material is taken out of the organic solvent solution, drained, washed with an organic solvent, and then dissolved in a long-chain dibasic acid anhydride with a water-soluble organic solvent acting as a good solvent. Wash, finally rinse with water and dry. In this case, as the organic solvent used immediately after the removal of liquid, preferably, various organic solvents at the time of the above-mentioned acylation reaction are mentioned, and as the water-soluble organic solvent, preferably, a lower solvent such as methanol, ethanol, and propanol is used. Examples thereof include ketones such as alcohol, acetone, and methyl ethyl ketone.

In the present invention, examples of the polymer material that can impart a water repellent function include silk protein, wool keratin, collagen, polyvinyl alcohol, and cellulose. As the form of these materials, any form that the material can take, such as fibrous, film-like, powder-like, and lump-like forms, can be used.

Among these materials, silk protein fibers include, for example, silkworm silk, mulberry silk, tussah silk, Eri silkworm, and helmet silk as wild silk. In order to prepare a silk protein membrane, the silk fiber is first immersed in a concentrated neutral salt solution, heated and dissolved in a cellulose dialysis membrane, and replaced with pure water. Subsequently, the aqueous solution of silk fibroin thus prepared is spread on a polyethylene membrane and blown dry at room temperature to obtain a water-soluble silk fibroin membrane. In the case of a silk protein film sample, it is desirable to perform a water insolubilization treatment on the film sample prior to chemical modification for water repellency processing. The silk protein membrane is immersed in a 50 v / v% methanol aqueous solution for 1-2 hours, taken out, and dried at room temperature to increase the aggregation density between protein molecules, form hydrogen bonds between the molecules, and insolubilize water. Is done. This silk protein membrane can be prepared by adding (1) a silk fibroin aqueous solution obtained by dissolving liquid silk fibroin in a silk gland taken out from the silkworm body of a mature silkworm into water, or (2) a silk fibroin solution into a neutral salt aqueous solution such as lithium bromide. Soak the fiber, 5
After heating and dissolving at 0 ° C. or higher, silk fibroin aqueous solution obtained by placing in a cellulose dialysis tube and replacing with pure water is spread on a polyethylene membrane and evaporated to dryness. According to the present invention, the long-chain dibasic acid anhydride can impart water repellency to fibers, films, and the like of such silk proteins.

The present invention is also applicable to animal hair fibers such as wool and mohair. Furthermore, it is possible to chemically modify collagen that is distributed in many tissues such as skin, blood vessels, bones, teeth, and tendons with proteins that form connective tissues in a living body.
Collagen is a biological macromolecule that has immunological activity, induces a platelet aggregation reaction, and participates in thrombus formation originating therefrom, and is conventionally known by treatment with the long-chain dibasic acid anhydride. In addition to the above-mentioned functional properties of collagen, it is possible to newly impart excellent water-repellent properties, and it is possible to further enhance the functional properties of collagen.

Since polyvinyl alcohol (hereinafter abbreviated as PVA) has a hydroxyl group in a molecular side chain, this site becomes a base of the acylation reaction. Water repellent treatment of natural cellulose cotton fiber or the like is also possible. This is because a hydroxyl group serving as a base of the acylation reaction is contained in the cellulose molecule.

The long-chain dibasic acid anhydride used in the present invention reacts with a basic amino acid side chain such as lysine, arginine or histidine residue of a polymer material to form S-NHCO-C
_{H 2 -CH (COOH) -CH 2} -CH = CH-C n H 2n + 1
(S is a molecule of a polymer material, and n is as defined above), and an acyl group can be introduced into the material. In addition, long-chain dibasic acid anhydride, tyrosine of polymer material, phenolic hydroxyl group such as threonine residue, hydroxyl group of serine residue,
Alternatively, it reacts with a hydroxyl group of polyvinyl alcohol or the like, and further with a hydroxyl group of a cellulose molecule to form S'-OCO-C
_{H 2 -CH (COOH) -CH 2} CH = CH-C n H
_An acyl group can be introduced into the material as in _{2n + 1} (S 'is a molecule of a polymer material, and n is as defined above). The long-chain dibasic acid anhydride undergoes an acylation reaction with a basic amino acid side chain, has higher stability than the case of an acylation reaction with a hydroxyl group, and has a higher bonding force with the polymer material.

In order to impart a strong water repellent function to a polymer material, a long-chain dibasic acid anhydride is used, the concentration of the reagent is increased, and the reaction temperature and the reaction time are controlled so as to increase the processing efficiency. Good to do. The water repellency can be appropriately changed depending on the intended use by controlling the processing efficiency in this way.

The acylating agent used in the present invention undergoes an acylation reaction with a basic amino acid side chain or a hydroxyl group of a polymer material. As an acylating agent, n-octadecylsuccinic anhydride (hereinafter sometimes abbreviated as Cn = 15) will be described as an example, and the amount of the acylating agent will be described below. Since the total amount of reaction sites where the acylation reaction occurs is specific to the polymer material, the reaction amount based on Cn = 15 is limited by the total number of the reaction sites of the polymer material, and the acylation reaction does not proceed indefinitely. Absent. Description will be made by taking wool fiber containing more reaction sites as an example than silk fiber as an example. The total amount of basic amino acid residues such as lysine, arginine and histidine constituting wool fiber is 1.468 × 10 ⁻³ mol / g, and the total amount of amino acid residues including hydroxyl groups such as serine, tyrosine and threonine is 8.4.
Since it is 6 × 10 ⁻⁴ mol / g, the total amount of the reaction sites is 2.314 × 10 ⁻³ mol / g. Assuming that all possible reaction sites react when the water repellent treatment is performed using Cn = 15, the weight increase rate is 76.4%.
Is estimated. Here, tryptophan having a very small content was not considered. As is clear from Table 2 shown in the following examples, the reaction temperature was 75 ° C. and the reaction time was 7 hours.
The 73.2% weight gain over time was obtained
This indicates that all reaction sites are involved in the acylation reaction. The weight increase rate can be freely controlled by the reagent concentration, the reaction temperature, the reaction time or the type of the processing solvent.

[0025]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited by these examples. The function evaluation of the polymer material to which water repellency was imparted by the acylation treatment was performed by the following method.

Since the degree of water repellency is easily affected by a trace amount of oils and fats remaining in the silk fabric, it is necessary to eliminate this influence in the evaluation, and acetone extraction of the oils and fats is performed by the following method. Was. That is, in order to remove oil and fat components on the surface of the silk fabric after the water-repellent treatment, a water-repellent sample was put into a Soxhlet extractor using acetone as a solvent, and a cooler was attached. Extracted for minutes. After acetone extraction, wash with pure water,
Next, what was dried at 105 ° C. for 2 hours was used as a water-repellent test sample. For these samples,
The contact angle, the softness and the flexural wear strength were measured, an oil repellency test was performed, and the mechanical properties before and after the water repellent treatment were measured.

Contact angle: Using a contact angle measuring device (FACE model CAS, manufactured by Kyowa Interface Science Co., Ltd.), a single fiber constituting a warp yarn of a silk fabric is taken out, and fine water droplets are applied to the yarn while applying a force to the yarn. Was sprayed, and the area where the polka dots were attached to the fiber surface in a bead shape was photographed with an optical microscope with a magnification of 36 times, and the area where the polka dots were attached was enlarged and baked on photographic paper, and the contact angle was evaluated by drawing. For comparison, using a single fiber sprayed with a commercially available water-repellent agent (manufactured by Sumitomo 3M Limited, fluororesin fiber protective agent Scotchguard (trade name), hereinafter simply referred to as Scotchguard), The contact angle was evaluated by the same method. The larger the contact angle, the higher the water repellency.

Bending resistance: 2 cm × 15 c by the cantilever method specified in JISL1079 (1966).
A sample piece having a size of m was fed horizontally, and the feeding length until reaching a 45 ° slope was measured. The measurement was performed by cutting out five sample pieces from the woven fabric of the sample in the weft direction, measuring from the front side and the back side, and showing the average value in mm. Numerical values indicate that the larger the hardness, the harder the smaller the value.

Flexural wear strength: JIS L1096 (199
According to the A-2 method (bending method) defined in 0), the silk fabric is 2.5 × 20 from the warp direction and the weft direction.
5 cm test pieces were cut out, each of which was folded in two and attached to a test apparatus so as to sandwich a bar.
The test was performed under the condition of reciprocating 125 times per minute at a distance of 2.5 cm, and the number of times of friction when the test piece was cut was measured. The flexural wear strength of five test pieces cut out in the warp and weft directions of the silk fabric was measured, and the average of the measured values was defined as flexural wear strength.

Oil repellency: AATCCTM118 (197
The oil repellency function of the sample fabric was evaluated based on 2). That is, an arbitrary standard solution selected from the following standard solutions is gently placed at three places on the sample fabric by dropping one drop with a dropper, and after three minutes, it is determined whether or not the droplet is kept without collapsing. When the liquid is sucked into the sample or the shape of the liquid droplet is lost, the same operation is sequentially performed with the standard liquids having the smaller numbers described in the oil repellency column of the following criteria. The number of the largest standard solution that maintains a clean droplet form is used as the evaluation value of the oil repellency. AA
The standard liquid for oil repellency evaluation, the surface tension (dyn / cm) and the number of the evaluation standard for oil repellency in TCCTM118 (1972) are shown below.

[0031] Mechanical properties: The mechanical properties were evaluated in order to examine how the mechanical properties of the fibrous sample changed before and after the water-repellent treatment. Using an Instron manufactured by Shimadzu Corporation with a sample length of 100 mm, a tensile speed of 10 mm / min, and a chart full scale of 250 g, the strength (gf) at break of fiber, elongation (%), and energy required for cutting ( gf-m
m) was measured. The number of measurement repetitions was set to 10 times.

Example 1: Processing into Bombyx mori silk fabric 1 of JIS dye fastness test (based on JIS L0803)
A water-repellent function was imparted to the silkworm silk, double-layered silkworm (hereinafter abbreviated as silk fabric), with the following method. 100m as immersion bath
20 g of n-octadecyl succinic anhydride (Lot No. FIG. 0, manufactured by Tokyo Chemical Industry Co., Ltd.) in DMF of L.
1, sometimes abbreviated as Cn = 15), and used was a 20% n-octadecylsuccinic anhydride solution.
DMF 20 times the weight of the silk fabric (bath ratio 1:20) was placed in a 100 mL eggplant-shaped flask with a backflow cooler, and the silk fabric was completely immersed in the DMF using a water bath. A water-repellent silk fabric was produced by reacting at 80 ° C. for 7 hours. After the reaction was completed, the sample was taken out, washed with DMF, and then washed with acetone at 55 ° C. to remove unreacted reagent. Finally, it was washed with water, dried and weighed. 14. Weight gain 15.
A 4% sample was obtained.

Comparative Example 1 Processing into Silk Fabric n-octadecylsuccinic anhydride of Example 1 (Cn = 1
Dodecenyl succinic anhydride (040-16251, Lot No. LE, manufactured by Wako Pure Chemical Industries, Ltd.) instead of 5)
E7584 (hereinafter sometimes abbreviated as Cn = 9), and processed into a silk fabric under the same conditions as in Example 1 to obtain a sample having a weight increase rate of 13.2%.

Comparative Example 2: Scotch guard processing A commercially available water-repellent agent ("Scotch guard") was sprayed on the silk fabric used in Comparative Example 1 until the silk fabric was moistened, completely air-dried, and repelled. An aqueous silk fabric was obtained.

Water droplets weighing 12 mg were attached to the surfaces of the acylated silk fabrics obtained in Example 1 and Comparative Example 1 and the water-repellent silk fabric of Comparative Example 2, respectively.
At regular intervals, the adsorption and penetration of water droplets on the surface of each silk fabric were visually observed. Table 1 shows the obtained results.

[0036]

[Table 1] In Table 1, ++: the state of water droplets is maintained and there is no permeation; +: that it is in the form of water droplets but partially permeates;
-: It is no longer water-drop-like, indicating that all of the water has penetrated.

As apparent from Table 1, the modified silk fabric of the present invention, which has been acylated using a long-chain dibasic acid anhydride (Cn = 15), has good and durable stable water repellency. As shown, a water repellent effect superior to the silk fabric treated with Cn = 9 and the silk fabric treated with water repellency by a commercially available Scotchguard was obtained.

Example 2: Processing into wool fiber and silkworm silk fiber Wool fiber and silkworm silk fiber (hereinafter simply referred to as silk) in the same manner as in Example 1 using n-octadecylsuccinic anhydride (Cn = 15). Acylation treatment).
Samples with 35.4% and 12.8% weight gain were obtained.

Example 3 A silk fabric was subjected to a water-repellent treatment under the same conditions as in Example 1 except that Cn = 10 was used instead of Cn = 15 used in Example 1. The weight increase rate of the obtained silk fabric was 16.5%.

Example 4 Silk fibers and wool fibers were subjected to water repellency at 75 ° C. using DMSO instead of DMF used in Example 1 and using Cn = 15 as an acylating agent. The relationship between the weight increase rate of the obtained sample and the reaction time was examined, and the results are shown below.

[0041]

[Table 2] As is clear from Table 2, when DMSO is used instead of DMF, the weight gain obtained at the same reaction temperature and reaction time shows a larger value in DMSO. To obtain a sample having a weight gain of 10% or less, it is more advantageous to use DMF.

Example 5 Processing into a Protein Membrane A water-repellent treatment was applied to a silkworm silk fibroin membrane and a tussah silk fibroin membrane (hereinafter sometimes simply referred to as a silk fibroin membrane in this example) by the following method. went. First, in order to make each silk fibroin film insoluble in water, the silk fibroin film was immersed in a 50 v / v% methanol aqueous solution for 1 hour, taken out from the methanol aqueous solution, and then lightly dried at room temperature. After drying at 105 ° C. for 2 hours, the sample weight was weighed. Next, in order to break the structure of the surface of the silk fibroin film having poor chemical reactivity and facilitate the reaction, the solvent was replaced as follows. That is, 55 ° C,
A silkworm silk fibroin membrane and a tussah silk fibroin membrane were separately placed in a 1 M aqueous solution of LiSCN (lithium thiocyanate).
Dipped for 0 minutes. Take out the silk fibroin membrane and add 100
% Methanol was used to remove LiSCN attached to the membrane surface, and then the silk fibroin membrane was subjected to 50 v /
v% methanol aqueous solution for 25 minutes, then 100%
After washing lightly with% DMF, the membrane was immersed in DMF for 25 minutes, and then reacted in DMF containing 20% Cn = 15 at 80 ° C. for 7 hours to impart a water repellent function to the silk fibroin membrane. After completion of the reaction, the silk fibroin membrane was placed in DMF at 55 ° C.
Acetone and then with water, and lightly dried at room temperature. Next, by drying at 105 ° C. for 2 hours, Cn =
Fifteen introduced water-repellent silk fibroin membranes were obtained. The weight increase rates of the thus-obtained silkworm silk fibroin membrane and tussah silk fibroin membrane were 29.9% and 25.8%, respectively.
Met.

Water was applied to the surfaces of the water-repellent film and the untreated film thus obtained with a micropipette by 50 μL (0.05 μL).
mL), and the state of the water drop was visually observed every predetermined time. In the untreated silk fibroin membrane, water droplets dissolved on the membrane surface and were absorbed into the membrane, and the membrane was partially dissolved, but the processed membrane was absorbed with water droplets attached even after 3 hours. There was no.

Example 6 Processing into Silk Fabric The silk fabric was immersed in DMF containing 20% of Cn = 15, and an acylation reaction to the silk fabric was performed at 75 ° C. DM
By reacting at 75 ° C. for 30, 45, 60 minutes in F,
Chemically modified silk fabrics having weight increase rates of 1.5, 4.0 and 5.2%, respectively, were obtained. Also, in DMF containing Cn = 9 as a control instead of Cn = 15, 60, 90, at 75 ° C.
By reacting for 120 minutes, the rate of weight increase is 3.
1, 4.5, 5.6% of chemically modified silk fabric was obtained. 50 μm of these treated silk fabrics was obtained in the same manner as in Example 5.
L of water was added dropwise, and the state of the water droplets and how water soaked were visually observed. Table 3 shows the obtained results.

[0045]

[Table 3] In Table 3, ++: the state of water droplets is maintained and there is no permeation. +: It is in the form of water droplets but partially permeates.
-: It is no longer water-drop-like, indicating that all of the water has penetrated.

As is evident from Table 3, when processing was carried out using Cn = 9 having a short chain length of the dibasic anhydride of the acylating agent, it took about one minute after the water droplet was placed on the surface of the silk fabric. It can be seen that only a moderate water repellent effect is observed, but the water repellent effect is lost after 2 minutes. However, when processing is performed using Cn = 15 having a sufficiently long chain length, the water-repellent effect lasts for a long time even after a water droplet is placed.

Example 7 Processing into Silk Fabric, Silk Fiber, Wool Fiber, and Cotton Fiber DMF containing 20% dodecenylsuccinic anhydride (Cn = 9) was placed in four 200 mL eggplant-shaped flasks, and then Silk fabric, silk fiber, wool fiber, and cotton fiber were put into each eggplant-shaped flask and reacted at 75 ° C. for various times (however, in the case of cotton fiber which is a cellulose fiber product, 80 ° C., 7 hours). Reacted). After the reaction, it was washed first with DMF and then with acetone at 55 ° C. to remove unreacted Cn = 9. Finally, after washing with water, dry
The dry weight of the sample was measured to determine the rate of weight increase of the sample.
Table 4 shows the obtained results.

[0048]

[Table 4] As is clear from Table 4, natural materials that can be water-repellent by using Cn = 15 include silk fabrics, silk fibers, wool fibers,
It is cotton fiber. When processing was performed using Cn = 15 instead of Cn = 9, when the weight increase rate at the same temperature and the same processing time was compared, the weight increase rate using Cn = 15 was all higher. This suggests that the chemical reactivity of the long-chain dibasic acid anhydride is increased. Therefore, the silk fabric, silk fiber, wool fiber and cotton fiber which have been subjected to the water repellent treatment as described above have excellent water repellency as compared with Cn = 9 even when the weight increase rate is low when Cn = 15 is used. Indicated.

Example 8 Processing into Various Polymer Material Films A film sample of collagen, chitosan, or PVA was subjected to a water-repellent treatment as follows.

The collagen membrane was prepared by spreading a collagen aqueous solution (pH 3.0, concentration 0.3) for tissue culture of Koken Co., Ltd. on a polyethylene membrane and drying and solidifying it at room temperature. The chitosan film was made of chitosan (Nacalai Tesque, Ltd., Lot No. MOT3327) at a concentration of 1.5.
%, Dissolved in a formic acid solution, spread on a polyethylene membrane, and dried and solidified at room temperature. The PVA film is made of PVA (manufactured by Wako Pure Chemical Industries, Ltd .;
0, Lot No. TSJ0964) was dissolved in water to prepare a 1.0% PVA aqueous solution, and the aqueous solution was spread on a polyethylene membrane, and evaporated to dryness at 25 ° C. to prepare a solution. These three types of sample films were subjected to the following water-repellent treatment without any insolubilization treatment.

Each of the collagen membrane, the PVA membrane and the chitosan membrane was placed in DMF containing 20% of n-octadecylsuccinic anhydride (Cn = 15) and treated at 80 ° C. for 7 hours. Water-repellent treatment. After the reaction, it was washed with DMF and then with acetone at 55 ° C. to remove unreacted Cn = 15. After drying, 1
The sample was dried at 05 ° C for 2 hours, and the rate of weight increase of the sample was determined. Table 5 shows the obtained results. In addition, the following three-level evaluation was performed about the water repellency by visual observation. ++: Good water repellency. +: Some water repellency is observed. -: No water repellency was observed.

[0052]

[Table 5] Since the treatment for imparting the water-repellent function to PVA, which is a water-soluble vinyl polymer, is performed not in an aqueous system but in an organic solvent such as DMF, it is not necessary to perform a water insolubilization treatment of PVA prior to the treatment. As is clear from Table 5, PVA and C
The chemical reactivity with n = 15 is extremely high, and the water repellency of the obtained film is remarkable. In addition, the chemical reactivity with collagen is almost the same as that of silk protein, and the water repellency of the film is good. The collagen membrane and PV in Table 5 were used.
Regarding the weight increase rate of the A film, the weight increase rate is higher than the weight increase rate of the silk fabric in Example 1. This difference is due to the fact that the C and C membranes on the collagen and PVA membranes do not have a fibrous structure than silk fabrics, which have a uniform molecular structure and a fibrous structure.
This is probably because the permeation amount of n = 15 was large and many acylation reactions with the sample molecules occurred. Water repellent treatment could not be applied to the chitosan film.

Example 9: Mechanical properties of processed silk fiber and wool fiber Water-repellent treatment with dodecenylsuccinic anhydride (Cn = 9) and n-octadecylsuccinic anhydride (Cn = 15), respectively. The mechanical properties (strength, elongation, energy) of silk fiber and wool fiber were examined. Table 6 shows the obtained results.
Shown in

[0054]

[Table 6] As is evident from Table 6, no significant difference in strength and elongation characteristics appears in the silk fibers, regardless of which anhydride is chemically modified. The strength of the silk fiber treated with Scotchguard decreased compared to the control. The strength of the wool fibers subjected to the water-repellent treatment is slightly increased in any of the anhydrides, but the elongation is considerably increased in any of the anhydrides. The degree increased by more than 80% as compared to before processing.

Example 10 In the same manner as in Example 1, a silk fabric was subjected to water repellency treatment using Cn = 9 and Cn = 15, respectively. That is,
Put silk fabric in DMF containing 20% Cn = 9,
By immersion treatment for 1 hour and 3 hours, respectively, to prepare silk fabrics with a weight increase rate of 3.1 and 10.7%, respectively. Also, the silk fabric having a weight gain of 1.5 and 10.8% was added by placing the silk fabric in DMF containing 20% of Cn = 15 and immersing at 80 ° C. for 30 minutes and 1 hour, respectively. Prepared. About the obtained water-repellent finished silk fabric,
The water repellency, oil repellency, hand properties, and flex wear strength were measured, and the results are shown in Table 7.

[0056]

[Table 7] In Table 7, ++: the state of water droplets is maintained and there is no permeation. +: It is in the form of water droplets but partially permeates.
-: It is no longer water-drop-like, indicating that all of the water has penetrated.

As is clear from Table 7, the water-repellent silk fabric of the present invention exhibits the same excellent water repellency as the silk fabric treated with Scotchguard, but lacks oil repellency. This is because Scotchguard contains a processing agent containing a fluoroalkyl group, and this fluorine compound exhibits a strong oil-repellent effect, and the long-chain dibasic anhydride in the present invention has an excellent water-repellent function. This is because it is not a reagent for the purpose of imparting an oil-repellent function. In addition, the bristles of the silk fabrics subjected to the water-repellent treatment of the present invention are lower than those of the control section and the Scotch guard even after the processing, and the feeling of feeling in the processing process is not reduced. It was confirmed that the bending wear strength of the silk fabric subjected to the water repellent treatment was increased by the processing. Thus, the problem of silk fabric material deterioration during chemical processing can be prevented.

[0058]

According to the present invention, a long-chain dibasic acid anhydride having one double bond in the molecule is used as an acylating agent and is reacted with a polymer material. The material can be prevented from deteriorating at the time of processing without giving any adverse effect to the polymer material, and excellent water repellency and wear resistance can be imparted to the polymer material. Unlike conventional resin processing, the processing chemical is not a type of processing that covers the surface of the polymer material, but because it exhibits the above-mentioned functions such as excellent water repellency by chemically bonding with the polymer material, There is no problem such as deterioration of the polymer material during the processing, and the feeling of texture is not reduced. Moreover, the long-chain acyl group introduced into the fiber according to the present invention is not easily removed since it is chemically bonded to the amino group or hydroxyl group of the polymer material. Therefore, polymer materials with long-chain acyl groups introduced,
The water repellency and the abrasion resistance can be stably maintained even after a long time has passed since the production, resulting in excellent durability.

Since the interfacial energy on the surface of the polymer material can be modified by the water-repellent treatment, it can be applied to various fields such as composite materials, electronic materials, biotechnology and marine sports. For example, a silk thread that applies this technology has excellent water repellency and hardly adheres to a suspension of pathogenic bacteria, which can reduce the chance of infection by various bacteria during surgery, so it is used as a surgical suture. it can.

Further, when applied to clothing materials, it is possible to utilize it taking advantage of the antifouling function, and it is possible to use it as a material not only in the Japanese clothing field but also in the Western clothing field.

Since the water-repellent polymer material of the present invention has a property of repelling water for a long time even when it comes in contact with water, it is used in marine materials such as marine ropes, buoy mooring ropes, fish nets, and water-repellent materials in the field of civil engineering. It can be used as a soft ground improvement material.

[Procedure amendment]

[Submission date] December 22, 1999 (1999.12.
22)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image (Where, n in the formula is an integer of 10-19) was modified by reacting acylating a polymer material having a long-chain dibasic acid anhydride and a basic amino acid side chain represented by,
The following general _{formula: S-NHCO-CH 2 -CH} (COOH) -CH 2 CH = C
H—C _n H _{2n + 1} (where S is a molecule of the polymer material, and n is 10 to 1)
Water-repellent polymer material having an integer of 9) .

Embedded image (Where n is an integer of 10 to 19)
Consists of long-chain dibasic acid anhydride and polyvinyl alcohol
Modified by an acylation reaction with a polymer material
And the following general _{formula: S'-OCO-CH 2 -CH} (COOH) -CH 2 CH = C
_{H-C n H 2n + 1} ( where, S 'is the molecule of the polymer material, n represents 10 to
A water-repellent polymer material having an integer of 19) .

Embedded image (Where n is an integer of 10 to 19)
High molecular weight with long-chain dibasic acid anhydride and basic amino acid side chains
Acylation reaction between the parent material and organic solvent at 60-90 ° C
The following general formula: S—NHCO—CH ₂ —CH (COOH) —CH ₂ CH ＝ C
H—C _n H _{2n + 1} (where S is a molecule of the polymer material, and n is 10 to 1)
To obtain a water-repellent polymer material having an integer of 9)
A method for producing a water-repellent polymer material, comprising:

Embedded image (Where n is an integer of 10 to 19) and a long-chain dibasic acid anhydride and polyvinyl alcohol or a cell
A polymer material consisting of loin is mixed with an organic solvent for 60 to 9
An acylation reaction is performed at 0 ° C. to obtain the following general formula: S′-OCO—CH ₂ —CH (COOH) —CH ₂ CHＣＨC
_{H-C n H 2n + 1} ( where, S 'is the molecule of the polymer material, n represents 10 to
A water-repellent polymer material having an integer of 19) .

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

[0012]

[Of 5] (Where n is an integer of 10 to 19) is a long-chain dibasic anhydride having one double bond in the molecule represented by D
A material having a reaction site where an acylation reaction occurs between the material and a long-chain dibasic acid anhydride when the material is heated in a system dissolved in an organic solvent such as MF.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

[0014]

[Omitted] (Where n is an integer of 10 to 19),
A compound having a long-chain acyl group having one double bond in the molecule.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // D06M 101: 10 101: 12 F term (reference) 4H020 BA07 4J031 CD09 4J100 AD02P CA01 CA31 HA11 HA57 HC30 4L033 AA02 AA03 AA05 AC03 BA18 CA02

Claims (7)

[Claims] 1. A compound having one double bond in a molecule and having the following general formula (I): (Where n is an integer of 10 to 19), a water-repellent polymer material modified by subjecting a long-chain dibasic anhydride to an acylation reaction with the polymer material. 2. The modified water-repellent polymer material after the acylation reaction does not deteriorate during the acylation reaction between the long-chain dibasic acid anhydride and the polymer material, and
2. The water-repellent polymer material according to claim 1, wherein the material does not decrease the feeling of feeling and has excellent water repellency and abrasion resistance. 3. The method according to claim 1, wherein the polymer material is silk protein, wool keratin, collagen, polyvinyl alcohol, or cellulose, and the shape is a film, a fiber, a powder, or a lump. Item 3. The water-repellent polymer material according to Item 1 or 2. 4. The polymer material having a basic amino acid side chain, wherein the water-repellent polymer material has the following general formula: S-NHCO—CH ₂ —CH (COOH) —CH ₂ — CH =
_{CH-C n H 2n + 1} ( where, S is a molecule of the polymer material, n represents 10 to 1
9 which is an integer of 9).
4. The water-repellent polymer material according to any one of 3. 5. The polymer material having a hydroxyl group, wherein the water-repellent polymer material has the following general formula: S′-OCO—CH ₂ —CH (COOH) —CH ₂ CH ＝ C
_{H-C n H 2n + 1} ( where, S 'is the molecule of the polymer material, n represents 10 to
2. The method of claim 1, wherein
4. The water-repellent polymer material according to any one of items 1 to 3. 6. A compound having one double bond in the molecule and having the following general formula (I): (Where n is an integer of 10 to 19), and a long-chain dibasic acid anhydride is subjected to an acylation reaction with a polymer material to obtain a water-repellent polymer material. Manufacturing method of polymer material. 7. When the polymer material has a basic amino acid side chain, the water-repellent polymer material has the following general formula: S-NHCO—CH ₂ —CH (COOH) —CH ₂ —CH =
_{CH-C n H 2n + 1} ( where, S is a molecule of the polymer material, n represents 10 to 1
And an integer of 9), and when the polymer material has a hydroxyl group, the water-repellent polymer material has
The following general _{formula: S'-OCO-CH 2 -CH} (COOH) -CH 2 CH = C
_{H-C n H 2n + 1} ( where, S 'is the molecule of the polymer material, n represents 10 to
7. An integer of 19).
A method for producing the water-repellent polymer material according to the above.