JP2967470B2 - Cellulosic fiber material having oil-absorbing ability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cellulosic fiber material having an oil-absorbing ability without impairing the hydrophilic property inherent in cellulosic fibers, and is used as a raw material for spun yarns, knitted fabrics, nonwoven fabrics, papermaking and the like. The present invention provides a fiber material widely used in the fields of clothing, sanitary materials, packaging materials, industrial materials, and the like.

[0002]

2. Description of the Related Art Human skin secretes sebum by metabolism in order to protect bacteria and viruses that invade from the outside and keep the skin moist. When sebum is excessively secreted, sebum comes out and microorganisms are released. Breeding and causing odor,
It is preferable to remove excess sebum positively. In order to remove such sebum, a method of wiping with a handkerchief or towel has conventionally been used, but the material of the handkerchief or towel is mainly a cotton fiber having a water absorbing property, and is excellent in water absorption. However, the ability to absorb oil components such as sebum was poor.

[0003] Kitchens such as hotels and restaurants and kitchens at home use a lot of water and use oil components or seasoning oils derived from ingredients such as meat and fish. Therefore, it is preferable to perform cleaning immediately. Towels etc. are used in these places, but materials such as conventionally used towels, kitchen wipers, etc.
It was mainly a cotton fiber having water absorbing properties, and although it had excellent water absorbing properties, it had poor oil component absorbing ability. By controlling the fiber density of a cloth or kitchen wiper or the like, it is possible to make it easy to wipe off the oil, but it is merely a physical action. or,
It is possible to wipe off the oil by using a detergent,
After that, it takes time and effort to wipe off the water. The applicant has proposed in Japanese Patent Application No. Hei 8-94833 a fabric made of cellulosic fiber having sebum absorbing ability. Cellulose fiber or spun yarn which is a cellulosic fiber material having oil and fat absorbing ability is proposed. Had not been developed.

[0004]

SUMMARY OF THE INVENTION The present invention provides a cellulosic fiber material having an oil and fat absorbing ability while maintaining the hydrophilicity of the cellulosic fiber.

[0005] The technique proposed above is effective for ordinary cloths, but there are problems such as difficulty in workability of thick cloths and the like. If used, the fiber material can be easily used for a wide range of uses such as knitted fabrics and nonwoven fabrics.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have intensively studied the use of a nonionic surfactant to immobilize the material on a cellulosic fiber material, and have studied such a treatment. By applying the method, it has been found that the cellulose fiber has excellent absorbability of fats and oils while maintaining the original hydrophilicity of the cellulose fibers, and exhibits a fat and oil absorbency even after repeated washing and washing, and has achieved the present invention. did. That is, the present invention has a compound containing a glycidyl ether group in a molecule having nonionic surfactant activity immobilized on a cellulosic fiber or a spun yarn mainly composed of cellulosic fiber,
It is a cellulosic fiber material having an ability to absorb fats and oils.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Cellulosic fibers used in the cellulosic fiber material of the present invention include natural cellulose fibers such as cotton and hemp, viscose rayon (including polynosic), cuprammonium rayon, and cellulosic fibers obtained by solvent spinning. Such as short fibers of regenerated cellulose fibers,
Needless to say, filamentous ones and regenerated cellulose fibers in which an inorganic pigment such as titanium oxide for dulling, an antibacterial agent, an antifungal agent, a flame retardant, and the like are mixed can also be used. Further, a spun yarn mainly composed of cellulosic fibers used for a cellulosic fiber material may be a spun yarn singly or a mixture of two or more of the cellulosic fibers.
A spun yarn may be obtained by using at least 60% by weight of the cellulosic fiber and blending non-cellulosic fibers such as nylon, polyester and acrylic. The spun yarn mainly composed of the short fibers of these cellulose fibers or the cellulose fibers may be dyed before the fixing treatment.

The compound having a glycidyl ether group in a molecule having a nonionic surfactant activity referred to in the present invention is a compound obtained by reacting a nonionic surfactant described below with a crosslinking agent having a glycidyl ether group, And a glycidyl ether compound having a nonionic surfactant activity in the molecule.

The nonionic surfactant used in the present invention includes a polyethylene glycol condensation type surfactant,
Fatty acid monoglycerin ester, fatty acid polyethylene glycol ester, fatty acid sorbitan ester, fatty acid sucrose ester, fatty acid alkanolamide, etc., molecules having a hydrophilic group and a hydrophobic group exhibiting surface activity in a molecule and not ionizing in an aqueous solution. It is not particularly limited, and it is preferable to use lauryl polyethylene glycol, palmitoyl polyethylene glycol, stearoyl polyethylene glycol, or fatty acid sucrose ester, and these may be used alone or in combination of two or more.

The crosslinking agent having a glycidyl ether group used in the present invention includes ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Glycidyl ether and the like,
High hydrophobicity increases the water repellency, so it is better to use a highly hydrophilic one having a glycidyl ether group.
Preferably, ethylene glycol diglycidyl ether is good.

The glycidyl ether compound having a nonionic surfactant in the molecule used in the present invention is a compound in which a glycidyl ether group is coordinated to the above-mentioned nonionic surfactant, and in particular, lauryl. Preferred are polyethylene glycol monoglycidyl ether, palmitoyl polyethylene glycol monoglycidyl ether, stearoyl polyethylene glycol monoglycidyl ether, and phenyl polyethylene glycol monoglycidyl ether. These may be used alone or in combination of two or more.

One of the methods for producing a cellulosic fiber material having an oil-absorbing ability is to use a mixed aqueous solution of a nonionic surfactant and a crosslinking agent having a glycidyl ether group to form a nonionic surfactant and cellulose. The hydroxyl group of the fiber constituting the base fiber material is immobilized by a covalent bond. If the amount of the immobilizing agent of the nonionic surfactant is small, the desired oil-absorbing ability is not exhibited if the amount is small, and if the amount is too large, the strength of the cellulosic fiber material having the oil-absorbing ability is reduced. The concentrations of the surfactant and the cross-linking agent having a glycidyl ether group are respectively 2 to 24% by weight, preferably 4 to 16% by weight of the same aqueous solution, and the cellulose fiber material is immersed for 1 to 40 seconds, The diaphragm is squeezed at a squeezing ratio of 30 to 150%. Then at 110-180 ° C
Heat treatment is performed for 0 seconds to 5 minutes to obtain a cellulosic fiber material having an oil and fat absorbing ability. At this time, a water washing treatment may be performed to completely remove unreacted chemicals. Although it is possible to treat the nonionic surfactant and the crosslinking agent having a glycidyl ether group in two stages, if the nonionic surfactant is first treated with the nonionic surfactant, the fiber constituting the cellulosic fiber material can be treated. Crosslinking between nonionic surfactants progresses before covalent bonding with hydroxyl groups, and if the crosslinker having a glycidyl ether group is first treated with a crosslinking agent having a glycidyl ether group, the crosslinking between the hydroxyl groups of the fibers constituting the cellulosic fiber material can be achieved. Is likely to progress, which is not preferable.

In another production method, a glycidyl ether having a nonionic surfactant in a molecule is immobilized by covalent bonding to a fiber constituting a cellulosic fiber material. If the concentration of the aqueous solution of glycidyl ether having a nonionic surfactant in the molecule is low, the desired oil-absorbing ability is not exhibited, and if it is too high, the strength is reduced. Therefore, the concentration of the aqueous solution is preferably 2 to 24% by weight, preferably Is an aqueous solution of 4 to 16% by weight, immersed for 1 to 40 seconds, and a squeezing ratio of 30 to 150%
After drying at about 100 ° C.,
A heat treatment is performed at 0 ° C. for 30 seconds to 5 minutes to obtain a cellulosic fiber material having an ability to absorb fats and oils. At this time, a water washing treatment may be performed to completely remove unreacted chemicals.

The fixation by the above two methods can be easily carried out in an aqueous system, so that a strong bond is formed and the washing resistance is increased without damaging the cellulosic fiber material and causing deterioration in physical properties. A catalyst may be used in combination to promote the covalent bond reaction of the immobilization.When the catalyst is used, the obtained cellulose-based fiber material having an oil-absorbing ability is sufficiently washed with water to remove the remaining catalyst. It is necessary to wash. In addition, in order to produce the cellulosic fiber material having an oil-absorbing ability of the present invention, it is also possible to carry out the treatment by spraying or the like in addition to immersing the cellulose fiber material in a treatment aqueous solution.

The cellulosic fiber material having an oil-absorbing ability according to the present invention is characterized in that the adhesion rate of a compound containing a glycidyl ether group in a molecule having a nonionic surfactant activity to the cellulosic fiber material is physical, hydrophilic, 4-20 than lipophilic
It is preferably in the range of% by weight, and if the adhesion ratio is less than 4%, the lipophilicity decreases, and if it exceeds 20%, the hydrophilicity may decrease.

The cellulosic fiber material having an oil-absorbing ability of the present invention has a nonionic surfactant compound having a glycidyl ether group in a molecule immobilized on the fiber material. Is immersed in a sufficient amount of water and acetone to soak the cellulosic fibrous material having the ability to absorb fats and oils, and extracted at 60 ° C. for 5 hours.
This can be confirmed by the fact that a compound containing a glycidyl ether group in a molecule having a nonionic surfactant activity does not elute.

The cellulosic fiber material of the present invention having an oil-absorbing ability has a high degree of immobilization of a compound containing a glycidyl ether group in a molecule having a nonionic surface-active ability. In addition to the above, the oil and fat absorbing ability is further provided, and the performance is maintained even after washing and washing. When the obtained cellulosic fiber material having the ability to absorb fats and oils is not dyed before the immobilization treatment, it goes without saying that ordinary dyeing treatment can be performed.

[0018]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these ranges. In addition, each measurement value described in the example was measured by the following method.

1) Fineness, dry strength, wet strength and knot strength of short fibers Polynosic fibers are JIS L 1015 (1981)
Cotton fiber is measured according to the "Chemical fiber staple test method", and JIS L 1019 (1977) "Cotton fiber test method"
Was measured by However, regarding the fineness of the cotton fiber, the micro nail value was converted to a denier value and displayed.

2) Number, twist number and strength of spun yarn Measured according to JIS L 1008 (1976) "Cotton yarn test method".

3) Evaluation of lipophilicity 3-1) Evaluation of lipophilicity of short fibers A short fiber is formed into a card web shape, and a nonwoven fabric sample having a basis weight of 70 g / m ^{2 and} a width of 5 mm and a length of 15 cm is prepared by a hydroentanglement method. Then, the lower end 5 mm in the longitudinal direction was immersed in a solution in a petri dish mixed with a ratio of oleic acid to triolein at a volume ratio of 1: 3, and the time required to suck up to a height of 10 mm from the liquid surface was set to seconds. It was measured in units. It was determined that the shorter the time, the better the lipophilicity. 3-2) Evaluation of lipophilicity of spun yarn 5 mm of the lower end of the spun yarn sample cut to a length of 15 cm was immersed in a solution in a petri dish in which oleic acid to triolein was mixed at a volume ratio of 1: 3, and the liquid was immersed. The time required to suck up to a height of 10 mm from the surface was measured in seconds. It was determined that the shorter the time, the better the lipophilicity.

[0022] 4) Preparation 5mm wide having a basis weight of 70 g / m ^2, the nonwoven fabric specimen length 15cm by hydrophilic Evaluation 4-1) molded hydroentangling hydrophilic Evaluation short fibers of the short fibers in the card web form Then, the lower end 5 mm in the longitudinal direction was immersed in pure water in a petri dish, and the time required to suck up to a height of 20 mm from the liquid level was measured in seconds. It was determined that the shorter the time, the better the hydrophilicity. 4-2) Evaluation of hydrophilicity of spun yarn The time required for immersing 5 mm of the lower end of a spun yarn sample cut into a length of 15 cm in pure water in a petri dish and sucking it up to a height of 20 mm from the liquid surface is expressed in seconds. Was measured. It was determined that the shorter the absorption time, the better the hydrophilicity.

5) Confirmation of immobilization (presence or absence of eluted material) 10 g of a sample was immersed in 200 ml of water and acetone, and treated at 60 ° C. for 5 hours with stirring.
The ml was collected in a beaker, evaporated to dryness on a hot plate, and the presence or absence of the immobilized substance was confirmed with an infrared spectrophotometer, and the presence or absence of an elute was determined.

6) Adhesion rate of immobilized component The amount of increase in weight relative to the unprocessed sample was measured and calculated as the adhesion rate according to the following equation, which was defined as the immobilized adhesion rate.

[0025]

(Equation 1)

Example 1 1 kg of cotton fibers which had been subjected to ordinary scouring and bleaching were placed in a stainless steel wire mesh container, and they were respectively 1%, 2%, 4% of phenyl polyethylene glycol monoglycidyl ether.
%, 8%, 16%, 24%, and 30% (wt%) of each aqueous solution were immersed in 5 L, stirred for 30 seconds, immersed, and squeezed with a mangle at a squeezing rate of 70%. Then about 100 ° C
And then heat-treated at 135 ° C. for 2 minutes to obtain cotton fibers (samples 1 to 7) on which phenyl polyethylene glycol monoglycidyl ether was immobilized. As a comparative example, 8% of phenyl polyethylene glycol was used instead of phenyl polyethylene glycol monoglycidyl ether.
A cotton fiber scoured and bleached in 5 L of an aqueous solution (% by weight) was treated in the same manner to obtain Sample 8. In addition, a cotton fiber subjected to ordinary scouring and bleaching was used as a raw sample. Various tests were performed on Samples 1 to 8 and unprocessed samples, and the results are shown in Table 1.

[0027]

[Table 1]

According to Table 1, Sample 1 was inferior in lipophilicity and Sample 7
Is inferior in hydrophilicity and drops off because phenyl polyethylene glycol is not immobilized in sample 8,
Not preferred. That is, the adhesion rate (%) of phenyl polyethylene glycol monoglycidyl ether is 4 to 20%.
It is clear that the cotton fiber having the ability to absorb fats and oils (weight%) is excellent in physical properties, hydrophilicity, lipophilicity and the like.

[Example 2] Polynosic fiber (1.25 denier, fiber length 38 m) subjected to scouring treatment in the manufacturing process
m) is placed in a stainless steel wire mesh container by 1 kg, and 1%, 2%, 4%, 8%, 16%, 24%, 3% of lauryl polyethylene glycol monoglycidyl ether is placed in each container.
After stirring and immersing in 5 L of each aqueous solution having a concentration of 0% (% by weight) for 30 seconds, the same treatment as in Example 1 was carried out, and lauryl polyethylene glycol monoglycidyl ether was immobilized. I got
As a comparative example, the same treatment was carried out on polynosic fiber in 5 L of an aqueous solution of 8% (weight%) of lauryl polyethylene glycol instead of lauryl polyethylene glycol monoglycidyl ether to obtain sample 16. The raw material polynosic fiber was used as a raw sample. Sample 9-1
Various tests were performed on Sample No. 6 and the unprocessed sample, and the results are shown in Table 2.

[0030]

[Table 2]

According to Table 2, Sample 9 was inferior in lipophilicity and Sample 1
Sample No. 5 is inferior in lipophilicity and hydrophilicity. In Sample 16, lauryl polyethylene glycol is not immobilized and thus drops off, which is not preferable. That is, the adhesion rate (%) of lauryl polyethylene glycol monoglycidyl ether was 4%.
It is clear that polynosic fibers having an oil-absorbing ability of up to 17% (% by weight) are excellent in physical properties, lipophilicity, hydrophilicity and the like.

Example 3 A spun yarn (cotton count 80 ' ^s ) consisting only of cotton fibers was subjected to scouring treatment, and 100 g each was formed into seven skeins. 1%, 2% of lauryl polyethylene glycol monoglycidyl ether,
After being stirred and immersed in 500 ml of each of 4%, 8%, 16%, 24%, and 30% (wt%) aqueous solutions for 30 seconds, centrifugal dehydration was performed at a squeezing ratio of 70%. Then about 100 ° C
And then heat-treated at 135 ° C. for 3 minutes to obtain cotton spun yarns of samples 17 to 23 in which lauryl polyethylene glycol monoglycidyl ether was immobilized. As a comparative example, lauryl polyethylene glycol monoglycidyl ether was replaced with lauryl polyethylene glycol 8
The cotton spun yarn was treated in the same manner in 500 ml of an aqueous solution (% by weight) to obtain a sample 24. The scoured cotton spun yarn was used as a raw sample. Various tests were performed on Samples 17 to 24 and the unprocessed sample, and the results are shown in Table 3.

[0033]

[Table 3]

From Table 3, it can be seen that Sample 17 is inferior in lipophilicity, Sample 23 is inferior in hydrophilicity, and Sample 24 is not preferred because lauryl polyethylene glycol is not fixed and drops off. That is, the adhesion rate (%) of lauryl polyethylene glycol monoglycidyl ether is 4 to 17
% (% By weight) of the spun cotton yarn is clearly excellent in physical properties, lipophilicity, hydrophilicity and the like.

[Example 4] Cotton fiber and polynosic fiber (1.25 denier, fiber length 38 mm) were obtained by mixing cotton fiber and polynosic fiber 45:55.
It was combined filament at a ratio (by weight), to obtain a spun yarn of cotton count 40 ^'S, which normal scoured, was 100g increments to respectively its seven racemes. 1%, 2%, 4% of phenyl polyethylene glycol monoglycidyl ether
%, 8%, 16%, 24%, and 30% (wt%) were immersed in 500 ml of each aqueous solution for 30 seconds.
For centrifugal dehydration. Thereafter, the mixture was dried at about 100 ° C., and then heat-treated at 135 ° C. for 3 minutes to obtain a blend yarn of cotton fibers and polynosic fibers of Samples 25 to 31 in which phenyl polyethylene glycol monoglycidyl ether was immobilized. Incidentally, in an aqueous solution 500ml 8% phenyl polyethylene <br/> glycol instead of phenyl polyethylene glycol monoglycidyl ether as a comparative example (wt%), similarly to process blended yarn of cotton fiber and polynosic fiber sample 32 I got A blended yarn of scoured cotton fiber and polynosic fiber was used as a raw sample. Various tests were performed on the samples 25 to 32 and the unprocessed sample, and the results are shown in Table 4.

[0036]

[Table 4]

From Table 4, it can be seen that Sample 25 is inferior in lipophilicity, Sample 31 is inferior in hydrophilicity, and Sample 32 is not preferable because phenyl polyethylene glycol is not fixed and drops off. That is, the adhesion rate (%) of phenyl polyethylene glycol monoglycidyl ether is 4 to 19
% (% By weight) of a blended yarn having an oil-absorbing ability is clearly excellent in physical properties, lipophilicity, hydrophilicity and the like.

Example 5 Polynosic fiber (1.25)
Denier, fiber length 38mm) and polyester fiber (1.5
(Denier, fiber length: 38 mm) was mixed with polynosic fiber: polyester fiber at a ratio of 7: 3 (weight ratio) to obtain a spun yarn (cotton count 20 ′ ^s ) in the form of seven skeins each of 100 g. 1%, 2%, 4%, 8%, 16% of phenyl polyethylene glycol monoglycidyl ether
3% each in 500 ml of 24% and 30% (wt%) aqueous solution
After immersion for 0 seconds, centrifugal dehydration was performed at a squeezing ratio of 70%. Thereafter, the mixture was dried at about 100 ° C. and then heat-treated at 135 ° C. for 3 minutes to obtain a mixed spun yarn of polynosic fiber and polyester fiber of Samples 33 to 39 in which phenyl polyethylene glycol monoglycidyl ether was immobilized.
As a comparative example, a mixed fiber of polynosic fiber and polyester fiber was similarly treated in 500 ml of an aqueous solution containing 8% (weight%) of phenyl polyethylene glycol instead of phenyl polyethylene glycol monoglycidyl ether to obtain a sample 40. A blended yarn of polynosic fiber and polyester fiber was used as a raw sample. Various tests were performed on the samples 33 to 40 and the unprocessed sample, and the results are shown in Table 5.

[0039]

[Table 5]

From Table 5, it can be seen that Sample 33 is inferior in lipophilicity, Sample 39 is inferior in hydrophilicity, and Sample 40 is not preferable because phenyl polyethylene glycol is not fixed and drops off. That is, the adhesion rate (%) of phenyl polyethylene glycol monoglycidyl ether is 4 to 17
% (% By weight) is clearly superior in physical properties, lipophilicity, hydrophilicity and the like.

[Application Example] A cotton spun yarn (cotton count 80 ' ^s ) was scoured, and 8% of lauryl polyethylene glycol monoglycidyl ether was used in the same manner as in Sample No. 20 of Example 3.
(Weight%) using a cotton spun yarn having an oil-absorbing property obtained by immobilization treatment with an aqueous solution of
m ² , a process density of 98 lines × 80 lines / in) (sample 4
1) was obtained. In addition, raw cotton spun yarn (cotton count 8
0 ' ^s ) using cotton lawn fabric (unprocessed product, basis weight 60 g)
/ M ² and a weft density of 98 lines / 80 lines / in). Sample 4
1 and 1 wash before washing raw cotton lawn fabric and 10
The lipophilicity and hydrophilicity after the rotation were measured by the following methods, and the results are shown in Table 6. In addition, the washing method at the time of measurement,
JIS L 0217-1995, "Indication Symbols and Handling Methods for Handling of Textile Products" 2.1. (1) Performed according to washing method number 103.

<Evaluation of Lipophilicity> A solution obtained by mixing oleic acid and triolein at a ratio of 1: 3 (volume ratio) to a sample was mixed with 1
The drop (0.03 ml) was dropped and the time to complete absorption by the sample was measured in seconds. It was determined that the shorter the absorption time, the better the lipophilicity.

<Evaluation of hydrophilicity> One drop of water (0.0
3 ml) and the time to complete absorption by the sample was measured in seconds. It was determined that the shorter the absorption time, the better the lipophilicity.

[0044]

[Table 6]

As can be seen from Table 6, the spun cotton yarn was preliminarily subjected to the treatment of the present invention, and the spun yarn was used as a woven fabric without deteriorating the inherent hydrophilicity of the spun cotton yarn. It is also evident that a textile is obtained that retains lipophilicity.

[0046]

The cellulosic fiber material having an oil-absorbing ability according to the present invention has a compound containing a glycidyl ether group attached to a molecule having a nonionic surfactant activity in an amount of 4 to 20% by weight. Demonstrates the ability to absorb fats and oils without impairing the inherent hydrophilicity of cellulosic fibers, and is used as a raw material for yarns, knitted fabrics, non-woven fabrics, papermaking, etc. There is an effect that can be used.

Claims (2)

(57) [Claims] 1. A cellulosic fiber material having an oil-absorbing ability, wherein a compound having a glycidyl ether group in a molecule having a nonionic surfactant property is immobilized on the cellulosic fiber. 2. A cellulose having an oil-absorbing ability, wherein a compound containing a glycidyl ether group in a molecule having a nonionic surfactant is immobilized on a spun yarn mainly composed of a cellulose-based fiber. Based fiber material.