JP3526482B2 - New polymer compound and method for imparting water repellency - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polymer compound and a method for imparting water repellency. The polymer compound according to the present invention has a useful function by having an introduced functional group.

[0002]

2. Description of the Related Art Conventionally, various functional molecules and functional groups have been introduced into a polymer carrier to impart additional functionality to the properties of the original polymer carrier so that it can be applied to new fields or used in conventional applications. Many expansions of the scope of application have been studied and put to practical use. Particularly in the field of fibers, various studies have been conducted on fibers having additional functions such as antibacterial properties, morphological stability, water repellency, and water permeability. Among them, there are many examples of research on developing waterproof cloths that do not get damp, and many of the developed waterproof cloths have actually been commercialized. Many of the commercially available waterproof cloths are porous membranes made of a chemically synthesized polymer, and are characterized by having pores of a size that allows water molecules (water vapor) to pass through but does not allow water drops to pass through. However, the fact is that most of these chemically synthesized products do not take biodegradability into consideration. On the other hand, although waterproofing technology for cotton cloth having biodegradability has also been conventionally studied, a method of applying a waterproofing agent is mainly used, and in this case, deterioration of waterproofing property due to washing or aging cannot be avoided. By the way, cotton cloth (cellulosic fiber) is superior to synthetic products in terms of not only biodegradability but also hygroscopicity, breathability, and texture, and its utilization is extremely high. Therefore, it is important to develop a waterproof cloth that retains these characteristics of cotton cloth (touch and biodegradability) and has little performance deterioration due to aging, in order to achieve both practicality and global environmental protection. It is the theme.

As described above, waterproofness / water repellency is one of the important functions to be added to a polymer carrier such as fiber. For example, in order to impart water repellency to a cellulose fiber, there is a so-called waterproofing method in which the surface of the fiber is coated with oil, wax, rubber, cellulose ester, vinyl resin, urethane resin. It is not suitable for general-purpose clothing because it significantly impairs the sex. Therefore, for general-purpose clothing, a processing method for imparting water repellency to fibers, threads, or fabrics is mainly adopted. This is because after imparting water repellency without impairing the breathability of the fabric, the fabric is impregnated with a paraffin emulsion containing a hydrophobic compound such as aluminum acetate or zirconium compound while leaving the fabric structure porous. Although this is a processing method in which an insoluble metal compound is dried and fixed to fibers, this method has problems in discoloration of fibers, discomfort in touch, and long-term maintenance of water repellency.

Another method of adding water repellency is to chemically bond various hydrophobic reagents directly to threads or fibers. This method is frequently used because of the wide application range of hydrophobic reagents. As the hydrophobic reagent, fatty acid chloride, alkylethyleneimine compound, alkylisocyanate, N-methylolstearic acid amide, alkylepoxide, alkylchromic chloride, fatty acid-containing compound such as methylhydropolysiloxane, fatty acid amide compound, silicone resin compound Alternatively, a wide range of substances such as fluorine-containing substances are used. This method requires careful selection of the hydrophobic reagent and careful determination of the substitution rate. For example, in order to develop sufficient water repellency, it is necessary to introduce a large number of hydrophobic reagents into the polymer carrier (fiber), but conversely, placing importance on water repellency and using hydrophobic reagents with a high substitution rate. This is because when it is introduced into a polymer carrier, the inherent properties of the polymer carrier, such as hygroscopicity, air permeability and touch, are significantly impaired.

[0005]

Therefore, the object of the present invention is to achieve low substitution while maintaining the functions (hygroscopicity, breathability, dyeability, touch, biodegradability, etc.) inherent in polymer carriers. It is intended to provide a polymer compound containing a functional group that exhibits sufficient functionality (for example, water repellency and dyeability) only by introducing it at a high rate and can maintain these functions for a long period of time.

[0006]

The present invention is directed to cellulose or
Has one or more hydroxyl groups in the repeating unit
Hydrogen arsenide Dorokishiru groups in the cellulose derivative is that,
General formula (I): (Wherein, X is a hydroxyl group, a halogen atom or a lower alkoxyl group having 1 to 3 carbon atoms, and n is an integer of 8 or more), and is water-repellent.
Characterized Rukoto to have a chemically modified cellulose or of
A chemically modified cellulose derivative . In addition, the present invention is to
One or more hydroxyl groups in the roulose or repeating unit
In the cellulose derivatives having several, in the molecule
A hydrogen atom arsenide Dorokishiru group general formula (I): (Wherein, X is a hydroxyl group, a halogen atom or a lower alkoxyl group having 1 to 3 carbon atoms, and n is an integer of 8 or more), and the cellulose or The present invention relates to a method for imparting water repellency to a cellulose derivative . In the present specification, the group represented by the general formula (I) may be referred to as “functional group of the present invention”.

The present invention will be described in detail below. Of the present invention
The chemically modified cellulose or the chemically modified cellulose derivative is
Cellulose having a hydroxyl group or cellulose derivative
Hydrogen atom of at least one hydroxyl group in the body,
It is substituted with the functional group of the present invention. Long-chain alkyl moiety of a functional group of the present invention (-C _n H _{2n + 1),} which can be straight-chain or branched, from the viewpoint of biodegradability, and is preferably linear. The carbon number (n) of the long-chain alkyl moiety is 8 or more, preferably 8 to 30, more preferably 12 to 24. When the carbon number is less than 8, sufficient water repellency cannot be obtained, and when the carbon number exceeds 30, biodegradability may be deteriorated. A carbon number of 12 to 24 is particularly preferable because it has sufficient water repellency and biodegradability. The halogen atom in the functional group of the present invention can be, for example, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a bromine atom because it enhances the reactivity with an amine. The lower alkoxyl group having 1 to 3 carbon atoms is, for example, a methoxy group, an ethoxy group, an n-propoxy group or an isopropoxy group.

Cellulose into which the functional group of the present invention is introduced, or
The cellulose derivative has a hydroxyl group 1 in the repeating unit.
Number or that have a plural. The cellulose derivative may have one or more hydroxyl groups in the repeating unit, and examples thereof include esterified derivatives such as fatty acid cellulose monoester or diester, or nitrocellulose, cellulose sulfate, cellulose phosphate and the like;
Examples include etherified derivatives such as alkyl cellulose (eg, methyl cellulose), aralkyl cellulose (eg, benzyl cellulose), carboxyalkyl cellulose (eg, carboxymethyl cellulose), aminoalkyl cellulose (eg, diethylaminoethyl cellulose) and the like.

[0009] cellulose or cellulose derivatives can be in any form, if example embodiment, powder, fiber, cloth, film-like, or can be various forms of a sheet-like shape, widespread application is It is possible. In the case of this cellulose or its derivative, the functional group of the present invention is introduced.
It may be in a bulk state before forming into a desired shape or after forming.

Chemically Modified Cellulose or Chemistry According to the Invention
The modified cellulose derivative is a cellulose or a repeating unit
Cellulose having at least one hydroxyl group in the derivative
Conductor , that is, general formula (II): A (OH) _r (II) (wherein r is an integer of 1 or more and means the total number of hydroxyl groups, A is excluding all r hydroxyl groups) cell
The compound represented by the formula (II
I): (In the formula, A, r, X and n have the same meanings as described above, and s
Is the number of substitutions of the functional group of the present invention).

The chemistry of the present invention represented by the general formula (III)
Modified cellulose or chemically modified cellulose derivative, and cellulose or cellulose derivative represented by the formula (II)
Hydrogen atom of the hydroxyl group in the body, the ratio has been replaced with a functional group of the present invention can be represented by substitution ratio (s / r). Chemically modified cellulose or chemically modified cell of the present invention
The substitution rate (s / r) of the sucrose derivative is 0.0
01 to 0.1, and more preferably 0.002 to 0.
02. If the substitution rate is less than 0.001, the water repellency is insufficient, and if the substitution rate exceeds 0.1, the properties of the raw materials (particularly hygroscopicity, biodegradability, chemical resistance, etc.) are impaired. . When the substitution rate is in the range of 0.002 to 0.02, water repellency can be introduced without impairing the characteristics of the raw materials, which is particularly preferable.

Chemically Modified Cellulose or Chemical Modification of the Invention
The cellulose derivative can be prepared, for example, by the following method. That is, it is prepared by allylating the cellulose or cellulose derivative represented by the general formula (II), converting the obtained allylated derivative into a corresponding halogenated derivative, and then coupling with a long-chain alkylamine. You can A known method (for example, see JP-A-4-76001) can be used to convert a cellulose or a cellulose derivative having a hydroxyl group into an allylated derivative and further to a corresponding halogenated derivative. According to this method, first, a double bond is introduced into the hydroxyl group of cellulose or a cellulose derivative to obtain an allylated derivative. As the allylating agent, an allyl halide (eg, allyl chloride,
Or allyl bromide) can be used. For example, when a cell Le <br/> loin is a mercerized alkali cellulose obtained by (treated cellulose in cold concentrated alkaline), an appropriate solvent (e.g., a polar organic solvent, such as dimethyl sulfoxide or By reacting with an allylating agent (eg, allyl chloride) under reflux in 2-propanol) to give a compound of general formula (IV): (In the formula, A and r have the same meanings as described above, and t is the number of introduced substituents).

Next, the allylated derivative represented by the general formula (IV) is treated with an alcohol solution (eg, ethanol) containing a halogen molecule (eg, bromine molecule) or a halogen molecule (eg, bromine molecule). The 2,3-dihalogenated propyl derivative can be easily obtained by treatment in an alkali hydroxide aqueous solution (for example, sodium hydroxide aqueous solution) at room temperature for about 1 minute. in this case,
For example, a 3-bromo-2-hydroxypropyl (bromohydrin) derivative can be obtained by using a mixed solution in which the mixing ratio of bromine molecules and sodium hydroxide is set to the condition that sodium hypobromite is produced. Instead of the bromine molecule or sodium hypobromite, when reacted with a chlorine molecule, an iodine molecule, hypochlorous acid, or hypoiodic acid, the corresponding dichloropropyl, diiodopropyl, chlorohydrin, or iodohydrin derivative is obtained. And so on. Among them, the dibromopropyl derivative and the bromohydrin derivative are relatively stable and can be stored for a long period of time.

The halogenated derivative obtained by the above operation is immersed in a neutral to slightly alkaline aqueous solution of a primary amine having a long-chain alkyl group or an organic solvent in which the primary amine having a long-chain alkyl group is dissolved. If left for several hours (1 to 5 hours, preferably 1 to 2 hours) or heated, the dehydrohalogenation reaction proceeds between the amine compound and the halogenated derivative, and the amine having a long-chain alkyl group becomes cellulose or SE
A chemically modified cell of the present invention coupled to a lulose derivative.
Lulose or a chemically modified cellulose derivative is obtained. The conditions of this coupling reaction do not require high temperature or high-concentration alkaline conditions. For example, the reaction temperature is around room temperature (1
5 to 35 ° C. approximately, if necessary by the length of the alkyl group be a 35 to 80 range ° C.), the cell an amine having all kinds of long chain alkyl groups such mild conditions
It can be covalently bonded onto the sucrose or cellulose derivative , and can be chemically modified cellulose or chemically modified cellulose of the present invention.
The saccharide derivative can be obtained very easily and safely.

Specific examples of the primary amine containing a long chain alkyl group include octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, Heptadecylamine, octadecylamine, nonadecylamine, icosylamine, henicosylamine, docosylamine, tricosylamine, or the like can be used.

The chemically modified cellulose of the present invention thus obtained
The cellulose or chemically modified cellulose derivative can exhibit water repellency derived from the hydrophobicity of the long-chain alkyl moiety, and also has excellent dyeability due to the presence of an amino group in the functional group of the present invention. It also has an effect. In general, it is expected from the knowledge of ordinary organic chemistry that, in order to impart water repellency to cellulose or a cellulose derivative (eg, cellulose), a large number of hydrophobic groups should be introduced. Also, cellulose or cellulose
It is common knowledge that the smaller the number of substituents to be introduced, the better in order to maintain the biodegradability of the derivative . The present invention is to provide challenges this discrepancy, by introducing a functional group of the present invention at a low substitution ratio, while express sufficient water repellency, also realized excellent durability against laundering, etc., further cellulose or
Made it possible to sufficiently retain various excellent functions (hygroscopicity, breathability, dyeability, biodegradability, etc.) inherent in cellulose derivatives .

The novel chemically modified cellulos obtained in this way
Since the cellulose or chemically modified cellulose derivative has excellent water repellency while maintaining its hygroscopicity and air permeability, it can be applied to all directions. General clothing materials (general clothing,
Not only for exercise clothing), but also as a special application, it can be applied to gauze, eye patch, test garment, bandage, bandage, mask, diaper, bed sheet, etc. in the medical field.
In this case, the entire chemically modified cellulose of the present invention or
It is composed of a chemically modified cellulose derivative , or partly (for example, the outside that comes into contact with the outside air / water, the outside of the multilayer formation,
Or a specific one site) of the chemically modified cellulose of the present invention or
It can also be composed of a chemically modified cellulose derivative .

[0018]

The present invention will be described in detail below with reference to examples, but these do not limit the scope of the present invention. Example 1: Alkylamino of powdered cellulose and absorbent cotton
And its physical properties Cellulose powder (filter paper powder, manufactured by Toyo Advantech)
Was treated with 18% sodium hydroxide to form mercer, and then 20% by weight of allyl chloride and 2-propanol (10%
It was suspended in a mixed solution of 80% by weight (containing sodium hydroxide) and reacted under a reflux condenser to obtain allyl cellulose having a substitution rate of 20%. The cold water washing of the obtained allyl cellulose was repeated until the washing liquid became neutral to remove excess alkali and reaction reagents. Next, bromine was dissolved in a sodium hydroxide aqueous solution to prepare a bromine solution (8% BrOH). The above allyl cellulose was immersed in this solution for several minutes at room temperature to quantitatively replace the allyl group with a dibromopropyl group, and O- (2,3-dibromopropyl cellulose)
Got This dibromo-substituted cellulose is a solution containing various long-chain alkylamines (propylamine, hexylamine, dodecylamine, or octadecylamine) (octadecylamine is 2-propanol solution at 70 ° C., dodecylamine or shorter-chain alkyl). The amine was alkylamine-ized in an aqueous solution at 37 ° C. for 1 hour, washed thoroughly with water, and then vacuum dried to obtain (3-alkylamino-2-bromopropyl) cellulose. The substitution ratio of the alkylamino group of each of the obtained chemically modified cellulose or chemically modified cellulose derivative is about 15% for the propylamino group, about 10% for the hexylamino group, and about 6% for the dodecylamino group. The content of octadecylamino group was about 3%.

When these long-chain alkylamino group-introduced cellulose powders were floated on the water surface, propylaminated cellulose immediately submerged in water and hexylaminated cellulose submerged in water in about 4 hours. It was confirmed that the derivatized cellulose and the octadecyl aminated cellulose floated on the water surface for 24 hours or longer and had water repellency. In addition, these chemically modified cellulosic derivatives are commercially available from Trichodoma
The crude enzyme preparation of cellulase produced by the bacterium (erma viride) showed biodegradability comparable to that of untreated cellulose powder. Use absorbent cotton instead of cellulose powder,
Allylation, halogenation, and alkylamination were carried out in the same procedure as above, and the physical properties were examined. The same results as in the case of cellulose powder were obtained.

Example 2: Alkyl amination of cotton cloth and
Physical Properties Cotton Plain Woven Fabric (Kanakin No.3; Warp = # 36/1; Weft =
# 40/1; weave density = 27 / cm × 30 / cm; refining =
Various alkylaminated cotton fabrics were produced through allylation treatment and dibromination treatment in the same manner as in Example 1 using 0.5% NaOH) for 10 minutes, and the functionality thereof was investigated. In this case, the substitution ratio of the alkylamino group is about 10% for the propylamino group and about 6% for the hexylamino group.
It was about 4% for dodecylamino groups and about 2% for octadecylamino groups. In addition, these cotton fabrics introduced with long-chain alkylamino groups also showed water repellency and biodegradability comparable to those of alkylaminated cellulose powder. The test methods and results for each physical property are shown below.

Test 1: Water Drop Contact Angle and Water Repellency First, in order to investigate the water repellency of an alkylaminated cotton cloth, a water repellency test by a drop method and a spray test were carried out. The drop method is for measuring the contact angle (θ) of a water drop 2 dropped on a test cloth 1, as shown in FIG.
Specifically, water droplets (10μ
l) is photographed from the side, and the height h of the water droplet 2 shown in FIG.
And the diameter d of the contact surface are measured, and tan (θ / 2) = 2h
The contact angle θ was determined from the relationship of / d. The treated fabrics of the present invention all exhibited high contact angles. That is, the water droplets on the cloth surface did not spread wet. Also, the spray test is JIS
It carried out based on L1092-1992. Water repellency 7
A point of 0 indicates wetting on half of the surface, and a small individual wetting penetrates the cloth, and a water repellency of 80 points indicates
Refers to those exhibiting small individual water droplet-like wetting on the surface. Propyl amination (alkyl length · n = 3), hexyl amination (alkyl length · n = 6), dodecyl amination (alkyl length · n = 12), or octadecyl amination (alkyl length · n = 18) The results for the fabrics are shown in Table 1.

[0022]

[Table 1] Alkyl length Contact angle (θ degree) Water repellency (point) n = 3 118 0 n = 6 118 0 0 n = 12 118 70 70 n = 18 118 80

Test 2: Water absorption, hygroscopicity, moisture permeability, and permeability
Moisture Next, a water absorption test by a sedimentation method (JIS L 1096), a hygroscopicity test by a weighing bottle method (JIS L 1004), and an evaporation cup method (JIS L 1099-199).
The moisture permeability test was performed according to 3), and the breathability test was performed using a gas permeability measuring device (KATO TECH KES-F8-API: manufactured by KATO TECH). As the functional cotton cloth according to the present invention, an octadecyl aminated (alkyl length · n = 18) cotton cloth was used, and as a control, an untreated cotton cloth was used. The results are shown in Figure 2. In FIG. 2, the solid line shows the result of the treated cloth according to the present invention, and the broken line shows the result of the untreated cloth. Regarding hygroscopicity and moisture permeability, no significant difference was observed between the treated cloth of the present invention shown by the solid line and the untreated cloth shown by the broken line. Regarding the water absorption, the value of the treated cloth of the present invention was considerably lower than that of the untreated cloth. Regarding the air permeability, the treated cloth of the present invention showed a considerably large air resistance value as compared with the untreated cloth, and the air permeability was considerably lowered. However, this increase in the ventilation resistance value is due to the increase in the weave density due to the tensionless mercerization. Almost no reduction in breathability was observed with the other treated fabrics of the present invention prepared by the tension mercerization treatment.

Test 3: Dyeability Next, Solar Orange [CI Acid Orange
e 7, C.I. I. (Color index number) 15
510] and Direct Orange (CI Direct
Orange 26, C.I. I. 29150) was used. The sample to be dyed is immersed in each dyeing solution having a dye concentration of 40 mg / l so that the bath ratio becomes 1:30,
After dyeing at 90 ° C. for 30 minutes, the absorbance of the dyeing solution before and after dyeing was measured to determine the dyeing amount. As a functional cotton cloth according to the present invention, octadecyl amination (alkyl length /
(n = 18) was used, and an untreated cotton cloth was used as a control. The results are shown in Table 2. The treated cloth of the present invention is
The dyeability was greatly improved compared to the untreated cloth.

[0025]

Table 2 Control Treated cotton cloth of the present invention Untreated cotton cloth (n = 18) Direct orange Dyeability (%) 5.0 71.9 (mg / g) 1.17 14.37 Solar orange Dyeability ( %) 3.1 88.9 (mg / g) 0.72 19.24

Test 4: Washing test Further, in order to examine the durability of the water-repellent function against washing and the like, a washing test based on JIS L 0844 was conducted. As the functional cotton cloth according to the present invention, an octadecyl aminated (alkyl length · n = 18) cotton cloth is used, and the control cloth is an untreated cotton cloth, which is a commercially available waterproof spray (fluorine resin, nonflammable solvent). And LPG mixture: trade name = Scotch Guard; manufactured by Sumitomo 3M Co., Ltd.) were applied and used according to the instruction manual. The results are shown in Table 3. In the commercially available waterproof spray, the water repellent effect disappeared after 6 washes, whereas in the treated cloth of the present invention, the water repellent effect did not change even after 100 washes.

[0027]

Table 3 Treated cotton cloth of the invention Control (n = 18) Untreated cotton cloth Number of washings Contact angle spray test Contact angle spray test 0 118 80 80 135 90 3 118 80 131 131 80 6 118 118 80 0 0 20 20 116 80 50 116 80 80 114 114 80 100 114 80

[0028]

EFFECT OF THE INVENTION Chemically modified cellulose or chemical modification of the present invention
The decorative cellulose derivative has only introduced a functional group that adds functionality (for example, water repellency and dyeability) at a low substitution rate, so that the function originally possessed by the cellulose or cellulose derivative (for example, hygroscopicity, breathability) , Dyeability, touch, biodegradability, etc.) can be sufficiently retained. Furthermore, the functionality introduced by the functional group is also low, despite the low substitution rate.
Sufficient water repellency and dyeability are exhibited, and it is also excellent in durability against washing and deterioration with time, which causes functional deterioration.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a drop shape method in Test 1.

FIG. 2 is a graph showing water absorption, moisture absorption, moisture permeability and breathability of functionalized cotton cloth and untreated cotton cloth according to the present invention.

Front page continuation (56) Reference JP-A-4-76001 (JP, A) Sawatari et al., Proceedings of the Textile Society of Japan, July 1994, G275 (58) Fields investigated (Int.Cl. ⁷ , DB name) C08B 1/00-37/18 JISST file (JOIS)

Claims (2)

(57) [Claims] 1. Cellulose or hydroxy within the repeating unit
The hydrogen atom of the hydroxyl group in the cellulose derivative having one or more silyl groups has the general formula (I): (Wherein, X is a hydroxyl group, a halogen atom or a lower alkoxyl group having 1 to 3 carbon atoms, and n is an integer of 8 or more), and is water-repellent.
And having a chemically modified cellulose or of
Scientifically modified cellulose derivatives . 2. Cellulose or hydroxy within the repeating unit
One Sill group or Te cellulose derivative odor <br/> having a plurality, a hydrogen atom arsenide Dorokishiru groups in the molecule the general formula (I): (Wherein, X is a hydroxyl group, a halogen atom or a lower alkoxyl group having 1 to 3 carbon atoms, and n is an integer of 8 or more), and the cellulose or A method of imparting water repellency to a cellulose derivative .