JPH02216269A - Method for finishing resin of natural fiber product - Google Patents

Abstract

PURPOSE:To enable resin finish without exerting a bad influence upon handle and strength by dipping a natural fiber product into an aprotic polar solvent containing a reactive resin finishing agent and reaction accelerating catalyst and heat-treating the dipped fiber product under specific conditions to react the natural fiber product with the resin finishing agent. CONSTITUTION:A natural fiber product is dipped into an aprotic polar solvent (e.g. dimethylsulfoxide) containing a resin finishing agent (e.g. amino resin or epoxy resin) reactive with the above-mentioned fiber, catalyst capable of promoting solid-liquid surface reaction and surfactant, preferably of an amphipatic compound and then heat-treated under conditions suppressing evaporation of the above mentioned solvent to rapidly react the natural fiber with the resin finishing agent. The shrink-resistance, yellowing resistance, chemical resistance, etc., of the natural fiber product is improved without exerting a bad influence upon the strength, etc., by the above-mentioned method.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for processing natural fiber products with resin.

Prior Art A number of resin processing agents that react with natural fibers have been developed for the purpose of permanently modifying natural fibers. Examples of processing agents that have been put into practical use include amino resins, epoxy resins,
Known examples include ethyleneimine resins, urethane resins, and esterification resins.

In order to modify the physical properties of natural fibers by applying this type of reactive resin finishing agent to natural fibers, the following method is used for -a.

a) The fibers are impregnated with a treatment liquid (aqueous solution, emulsion or organic solvent solution) containing a resin finishing agent, pre-dried and heat treated.

b) The fibers are reacted while immersed in the treatment solution.

C) A fiber containing an appropriate amount of moisture is thermally reacted with a solution of a resin finishing agent in a poorly water-soluble organic solvent.

In the case of a) above, the heat treatment step in which a covalent bond is formed between the fiber and the resin finishing agent is a solid phase for both the fiber and the resin finishing agent.
Alternatively, the reaction is a two-phase system in which the fiber is in the solid phase and the resin processing agent is in the liquid phase. In such a method, the resin migrates as the solvent evaporates during the pre-drying and heat treatment steps, resulting in uneven concentration distribution of the resin finishing agent, which tends to cause unevenness in the modification effect. reaction is due to limited contact between the two,
Generally reaction rate is slow.

In the case of b), since water competes with the functional groups on the fibers in the reaction with the resin finishing agent, when water is present, some of the finishing agents react with water and transform into reagents that do not react with the fibers.

In order to avoid this, there are examples in which the reaction is carried out in an organic solvent (Journal of the Japan Institute of Textile Science and Technology, 42-1 T152 (1986)), but in these cases as well, the main purpose is to use the resin finishing agent as a solution, and improvements in the reaction rate, etc. It is not allowed.

Furthermore, as an example of C), an example of a two-phase system of water and a poorly water-soluble organic solvent is found in Japanese Patent Publication No. 52-38131, but this case has the disadvantage that the reaction requires a long time.

Problems to be Solved by the Invention As described above, when the reaction between the resin finishing agent and the fibers is slow, or when the local concentration of the resin finishing agent alone is high, condensation of the resin finishing agents may occur. If the self-condensate of a resin finishing agent has a large molecular weight and is deposited on fibers after heat treatment, it is generally difficult to remove it. In addition, it is considered that protein stains with a molecular weight exceeding 10,000 cannot be removed by washing alone (Journal of Japan Oil Chemists' Association, p. 361!754 (1987)), and resin finishing agents. Self-condensation deposits generally stiffen the hand of the fiber and result in reduced tear strength.

The present invention provides a method for efficiently modifying natural fiber products by causing such a resin finishing agent to react with natural fibers without adversely affecting the texture and strength.
This will be the I topic.

! As a result of intensive research, the inventor of the present invention has developed a method for solving the problem by using a resin processing agent as a processing liquid containing a specific catalyst and an aprotic polar solvent.
It has been found that by impregnating natural fibers and heat-treating them under conditions that minimize the volatilization of the solvent, the natural fibers can be reacted quickly and the desired problem can be solved.

Aprotic polar solvents have a high swelling property for fibers, so when a resin finishing agent is reacted in the presence of an aprotic polar solvent, the reaction inside the fibers becomes easier due to the swelling of the fibers. The self-condensation product of the processing agent does not deposit (remains) on the fiber surface and can be easily removed in the washing process. Therefore, in the present invention, it is possible to achieve excellent resin processing effects without impairing the original physical properties of the fiber. Obtainable.

In addition, in the reaction between natural fiber-reactive resin finishing agents and natural fibers, hydroxyl groups, amino groups, carboxylic acids,
Functional P, groups such as mercapto groups react with resin processing agents as nucleophiles, but aprotic polar solvents selectively solvate the internal force of the ion pair, leaving the anion (generally the nucleophile) naked. The aprotic polar solvent has the effect of significantly increasing the reactivity of the nucleophile, that is, the functional group on the natural fiber.

Furthermore, since aprotic polar solvents generally have a high boiling point, it is necessary to prevent the volatilization of the solvent at the heat treatment temperature of the resin finishing agent by a simple means to prevent migration of the resin finishing agent and prevent unevenness in the modification effect. In addition, since the solubility of the aprotic polar solvent in the resin finishing agent is high, it is also possible to prepare a highly concentrated resin finishing agent solution, and a sufficient amount of the resin finishing agent can be added to the tIIA in one impregnation. It also has the advantage of being able to be applied roughly.

Aprotic polar solvents are generally said to have a dielectric constant of 15 or more, but in the present invention, it is preferable to use an aprotic polar solvent with a dielectric constant of 29 or more. However, it is preferable to use one having a boiling point of 100°C or higher.

Examples of aprotic polar solvents useful in the present invention include acetonitrile, dimethylformamide, dimethylsulfoxide, methylethylsulfoxide, hexamethylphosphoric acid amide, nitromethane, dimethylacetamide, sulfolane, N-methylpyrrolidone, and the like. These may be used in combination, or a small amount of water, a known resin processing agent, a softener, a penetrating agent, etc. may be added.

In the present invention, natural fiber products are processed with resin using a processing liquid in which such an aprotic polar solvent is combined with a natural fiber-reactive resin processing agent and a catalyst that promotes a solid-liquid interface reaction. However, as resin processing agents, amino resin,
Epoxy resin, ethyleneimine resin, urethane resin,
Any conventional reactive resin processing agent such as esterifying resin can be used.

Furthermore, as the catalyst for promoting the solid-liquid interfacial reaction, any catalyst generally known as an interfacial reaction catalyst or a phase transfer reaction catalyst can be used. These include, for example, surfactants which are amphiphilic compounds, crown ethers (oxa, aza, thia congeners), polybutane l-[, amine oxides, amine imides, etc.

It has been found that when a small amount of these catalysts is added to an aprotic polar solvent, the reaction between the resin finishing agent and the fibers is promoted, and the modifying effect of the resin finishing agent is significantly increased. In the present invention, a two-phase reaction between the solid phase fiber and the liquid phase aprotic polar solvent solution is progressing, and it is thought that this heterogeneous reaction is promoted by a catalyst that promotes the solid-liquid interface reaction. It will be done.

The reactive resin finishing agent is preferably used in a proportion of 0.1 to 12% by weight based on the natural fiber product to be treated, and the catalyst that promotes the solid-liquid interfacial reaction is used in an amount of 0.1 to 12% by weight of the resin finishing agent.
．． It is preferable to use about 0.05 to 5% by weight.

In addition, a general catalyst for resin processing may be used in combination with the treatment liquid.

Impregnation of the treatment liquid into natural fiber products may be carried out by a dipping method, a padding method, a coating method, etc., but the subsequent heat treatment, that is, the reaction step, should be performed to prevent the aprotic polar solvent from volatilizing (the reaction will not proceed). It is important that the process be carried out under the following conditions: (proceeding in an aprotic polar solvent).

Since the boiling point of the aprotic polar solvent is relatively high, even in an open state, the desired purpose can be achieved by setting the heat treatment temperature to an appropriate temperature below the boiling point. The product may be heated in a closed container or wrapped in a film or the like.

As a heat treatment method, any heat source such as hot air, infrared rays, microwaves, steam, etc. may be used. Although the number of heat treatments is not limited, the preferred heat treatment temperature is 50 to 19
0° C., and the preferred treatment time is 1 to 30 minutes. The heat treatment conditions may be appropriately selected so that the resin finishing agent is fixed to the fabric and does not damage the fabric.

After the heat treatment, it is preferable to wash the fabric to remove non-fixed needles from the fabric.

The fiber products processed in the present invention may be made of protein fibers and cellulose fibers alone, or may be blends or combinations of protein fibers and cellulose fibers with other fibers.
Examples of protein fibers include silk, wool, mohair, cashmere, etc., and examples of cellulose fibers include viscose rayon, Kiepura, polynosic, cotton, linen, etc. can.

In addition, the shape of the textile product may be any of yarn, woven fabric, knitted fabric, non-woven fabric, sewn product, etc. Furthermore, these may be pre-processed with other processing agents to the extent that it does not interfere with the processing of the present invention. It may be processed.

Next, examples will be shown, and the materials and physical property measurement methods used in the examples are as follows.

S1) Test fabric Silk (Palace crepe); Warp 21, 3 out of 3 flat threads, weft 2
4 out of 1 3,200t/m (twisting constant 2.9 XI
O') Silk (-Koshisumen): 21 out of 3 warp threads, 3 flat threads, weft 21 out of 14 threads, 3,200t/Mongolia (twisting constant 4.OXIO') Navy blue (satin old rimen): 3 out of 21 warp threads, 3 flat threads 6 out of 21 wefts
Book (3,500t/m, 600t/■) Cotton (TI Nakin No. 3): warp 20 tex weft 16 t
ex Wool (Muslin): warp 19tex, weft 15tex 2) Resin processing agent and corresponding catalyst 3) Catalyst that promotes reaction at solid-liquid interface 4) Solvent water 5) Other reagents Soda carbonate (special grade reagent made by Wako Pure Chemical Industries) Nonipole #2
00 (Nonionic surfactant manufactured by Sanyo Chemical Industries, Ltd.) 1"L1" L tip 2) Wrinkle prevention rate (χ) Measured according to JIS L 1095-85 B method (sensant method).

3) Texture and bending properties According to the KES method bending property test, bending rigidity B (g cm
”/as) and bending hysteresis (g-cm/am) were measured.

4) Shrinkage rate (χ) Measured according to JIS L 1042-83 B method.

5) Alkali resistance test The weight loss rate (χ) of the test cloth was expressed when the test cloth was immersed in a 1N-NaOH aqueous solution at 25° C. for 10 minutes.

6) Yellowing resistance test cloth is irradiated with ultraviolet rays for a predetermined period of time using a fade meter (manufactured by Suga Test Instruments), and the x, y, and zl at that time are measured with a color computer (manufactured by Suga Test Instruments). Degree △
Y1 was calculated.

Example 1 DMSO containing 30% by weight resin processing agent and 3% by weight catalyst
A liquid I and an aqueous solution were prepared, and a pares crepe was immersed in the solution and squeezed at a squeezing rate of about 90%.

Thereafter, those immersed in the aqueous solution were dried at 80°C for 3 minutes and heat treated, and those immersed in the DMSO solution were directly heat treated as they were.
Soap with a hot water solution containing a small amount of 200, wash with hot water,
After thoroughly washing with water, it was dried.

The types of resin finishing agents and catalysts used, as well as the heat treatment temperatures were varied as shown in Table 1, and the resin adhesion rates (χ) on processed fabrics were compared. The results are shown in Table 1, and the heat treatment time was 5 minutes.

From the results in Table 1, it can be seen that according to the present invention, an aprotic polar solvent (DMSO) and a catalyst (T
When using B A B and DDAO), the adhesion rate of the resin finishing agent to the fibers is significantly better than when water is used as the solvent or when a metal catalyst is used as the catalyst. I understand that.

Example 2 A DMF solution and an aqueous solution containing 30% by weight of a resin finishing agent and 3% by weight of a catalyst were prepared, and lacquered crepe or satin crepe was immersed in the solutions and squeezed at a squeezing rate of about 90%.

Thereafter, those immersed in the aqueous solution were dried at 80°C for 3 minutes and heat-treated, and those immersed in the DMF solution were directly heat-treated, and then treated with soda carbonate and Noniball #20.
After soaping with a hot aqueous solution containing a small amount of 0.0 and thoroughly washing with hot water and water, it was dried.

The types of resin finishing agents and catalysts used, as well as the heat treatment temperatures were varied as shown in Table 2, and the resin adhesion rates (χ) on processed fabrics were compared. The results are shown in Table 2, and the heat treatment time was 5 minutes.

From the results in Table 2, it can be seen that according to the present invention, an aprotic polar solvent (DMF) and a catalyst promoting solid-liquid interfacial reaction (T B
When using A B and DDAO), the adhesion rate of the resin finishing agent to the fibers is significantly better than when water is used as the solvent or when a general metal catalyst is used as the catalyst. Recognize.

Example 3 DMSO containing 30% by weight resin processing agent and 3% by weight catalyst
A solution and an aqueous solution were prepared, and a cotton cloth or wool cloth was dipped in the solution and squeezed at a squeezing rate of about 90%.

Thereafter, those immersed in the aqueous solution were dried at 80°C for 3 minutes and heat-treated, and those immersed in the DMF solution were directly heat-treated, and then treated with soda carbonate and Noniball #20.
After soaking with a hot aqueous solution containing a small amount of 0, the sample was thoroughly washed with hot water and water, and then dried.

The resin finishing agent, catalyst, and heat treatment temperature used are as shown in Table 3 (the heat treatment time was 5 minutes). Table 3 shows the resin adhesion rate (χ) of the processed fabric. Also, according to the present invention, an aprotic polar solvent (DM
SO) and a catalyst that promotes solid-liquid interfacial reaction (T B A
It can be seen that when using B and DDAO), the adhesion rate of the resin finishing agent to the fibers is significantly better than when water is used as a solvent or when a general metal catalyst is used as a catalyst. .

Example 4 Pares crepe was immersed in a DMSO solution containing 30% by weight of resin finishing agent and 3% by weight of catalyst, squeezed at a squeezing rate of about 90%, and then heat treated at 100°C, 120°C, and 140°C for 5 minutes. After that, it was soaped with a hot aqueous solution containing small amounts of soda carbonate and Nonipol #200, thoroughly washed with hot water and water, and then dried.

As a resin processing agent, Aceron MF 9 and the Elastron MF9 are distilled under reduced pressure to remove the alcohol content, and then an amount of DMSO corresponding to the removed alcohol content is added.
The adhesion rate (%) of resin to processed fabric was compared using Gatsudo Slon MF9m with added The results are shown in Table 4.

This result confirms the effect of the catalyst in the present invention, and at the same time shows that the coexistence of the alcohol component, which is a protic solvent, reduces the solvent effect of DMSO.

Table 4 Resin adhesion rate (%) Example 5 30% by weight of tolylene diisocyanate and 3% by weight of catalyst were added as a resin processing agent into DMSO, and a pares crepe was immediately immersed in this solution to reduce the coating to about 90%. After squeezing, 1
Heat treatment was performed at 00°C for 3 minutes.

Thereafter, it was soaped with a hot aqueous solution containing small amounts of soda carbonate and Noni Ball #200, washed with hot water and water, and then dried.

Table 5 shows the resin adhesion rate (χ) of the product.

Several measures have been taken to ensure that commercially available resins can be stored stably as products for long periods of time (six months to one year).

Most resins are made by dissolving the components in alcohol (methanol, ethanol, propatool). This alcohol solution is then dissolved in water and used. Therefore, when a product is dissolved in DMSO instead of water and used, the processing liquid contains some alcohol (more than the usual content). In Examples 1 to 3, this is the data used. By the way, since alcohol is a protic solvent like water, D is an aprotic solvent.
It is believed to reduce the solvent effect of MSO. Example 4
Then, the alcohol content is removed from the product by vacuum distillation with as little heat as possible, and the removed amount of DMSO is
is added, and this operation lowers the alcohol content in the processing fluid. In Example 5, one of the components, trilene diisocyanate itself, was dissolved in DMSO. Therefore, the alcohol content in the processing fluid is 0%.

However, as seen in Example 4.5, the inclusion of protic solvents in the processing fluid reduces the solvent effectiveness of aprotic solvents. Therefore, we believe that even when other resins and other fibers are used, even better results than those of Examples 1 to 3 can be obtained by removing the protic solvent (alcohol II) from the processing fluid. It will be done.

Example 6 (Anti-wrinkle effect on cotton) An aqueous solution containing 30% by weight of resin finishing agent Sumitex Resin 901 and 3% by weight of catalyst accelerator X80,
Alternatively, a cotton cloth is soaked in a DMSO solution containing 30% by weight of the resin finishing agent Sumitex Resin 901 and 3% by weight of the catalyst TBAB, squeezed to about 90%, and then immersed in an aqueous solution at 80°C for 3 minutes. Those that have been dried, heat treated, and immersed in DMF solution are directly heat treated as they are, and then
The sample was soaped with a hot aqueous solution containing small amounts of soda carbonate and Noniball #200, thoroughly washed with hot water and water, and then dried to prepare a sample with a resin adhesion rate of 8%.

The heat treatment conditions were 140° C. for 5 minutes for both the aqueous solution treatment and the DMF solution treatment.

Next, a wrinkle resistance test was conducted on each sample. Table 6 shows the results for warp and weft directions for each treatment method.

When using Sumitex Resin 901, which is an anti-wrinkle finishing agent for cotton, a metal catalyst and water are used as the solvent.A catalyst that promotes solid-liquid interface and an aprotic polar solvent are used as the solvent. It was found that the anti-wrinkle effect was better.

Table 6 Example 7 An aqueous solution containing 30% by weight of the resin finishing agent Sumitex Resin M-6 and 3% by weight of catalyst accelerators A and CX, or 30% by weight of the resin finishing agent Sumitex Resin M-6.
DMSOfJ containing 3% by weight and catalyst TBAB
After immersing the wool cloth in the solution and squeezing it to about 90%, the wool cloth immersed in the aqueous solution was dried at 80°C for 3 minutes, and the woolen cloth immersed in the DMSO solution was dried at 130°C as it was. Then, carbonated soda, Noni Ball #2
The sample was soaped with a hot aqueous solution containing a small amount of 00, thoroughly washed with hot water and water, and then dried to prepare a sample with a resin adhesion rate of 5%.

These samples were subjected to a shrinkage test, a bending property test, and an alkali resistance test. The results are shown in Table-7, Table-8, and Table-9, respectively.

Table 9 Results of alkali resistance test The purpose of resin processing of wool is wrinkle resistance, chemical resistance (especially alkali resistance), etc. However, wool has a naturally soft texture, and when treated with resin, its texture becomes hard. Therefore, it is necessary to perform a softening treatment, but washing washes away the fabric softener, making the fabric hard.

On the other hand, if a catalyst that promotes the reaction at the solid-liquid interface is used and an aprotic polar solvent is used as the solvent, the texture will not become so hard.

Furthermore, the anti-wrinkle effect and the alkali resistance effect are almost the same as those of the conventional method.

Example 8 An aqueous solution containing 30% by weight of a resin finishing agent and 3% by weight of a corresponding catalyst, and a DMSO solution containing 30% by weight of a resin finishing agent and 03% by weight of a catalyst DDA were prepared, and -koshirimen was immersed in these. , narrowed it down to about 90%. Items immersed in an aqueous solution were dried at 80°C for 3 minutes and then heat treated. Items immersed in a DMSO solution were heat treated as they were, then soaped with a hot aqueous solution containing small amounts of soda carbonate and Noniball #200, and washed with hot water. After thoroughly rinsing with water and drying, samples with resin adhesion rates of 1%, 3%, and 5% were prepared.

Note that the heat treatment temperature was 120 to 140°C, and during drying and heat treatment, the fabric was fixed to the width before processing using a pin tenter.

Next, a shrinkage rate test was conducted on these samples. The results are shown in Table 10.

Furthermore, in the conventional method, the same method as above was carried out for methylolmelamine resin processing which gives a hard texture. The results are shown in Table 11.

Table 10 Shrinkage test results - Koshirimen has a large amount of shrinkage due to the use of highly twisted yarns for the weft, and the anti-shrunk technology has not been known until now.
However, if a catalyst that promotes the solid-liquid interfacial reaction and an aprotic solvent are used as the solvent, an even better anti-shrinkage effect than before can be obtained.

In addition, even when using methylolmelamine resin, which has a very hard texture in conventional methods, it has become possible to process it relatively softly.

Example 9 A paresque was immersed in an IN aqueous solution of DDAO, squeezed to about 90%, and then dried at 80° C. for 5 minutes. after that,
Resin processing agent ethylene glycol diglycidyl ether 3
90% by weight again in a DMSO solution containing 0% by weight.
After squeezing the mixture, it was cured at 80°C. Thereafter, they were soaped with a hot aqueous solution containing small amounts of soda carbonate and Noniball #200, thoroughly washed with hot water and water, and then dried to prepare samples A1 and A2 with resin adhesion rates of 1% and 5%, respectively.

On the other hand, a pares crepe was immersed in an IN aqueous solution of KSCN, squeezed to about 90%, and then dried at 80° C. for 5 minutes.

After that, it was immersed again in an aqueous solution containing 30% by weight of the resin finishing agent ethylene glycol diglycidyl ether, and
%, and then cured at 90°C. After that, soap with a hot water solution containing small amounts of soda carbonate and Nonipol #200, wash thoroughly with hot water and water, and then dry.
Samples B1 and B2 were prepared with resin adhesion rates of 1% and 5%, respectively.

Next, the degree of yellowing (ΔYl) was determined for each irradiation time for the unprocessed cloth, AI, A2, B1, and B2.

The results are shown in FIG.

It is known that epoxy resin processing is excellent for preventing yellowing of strings, but using a catalyst that promotes the reaction at the solid-liquid interface and an aprotic polar solvent as the solvent can provide even better prevention of yellowing. It turned out that it was effective.

Effects of the Invention In the present invention, a resin finishing agent is rapidly reacted with natural fibers to modify the shrink resistance, yellowing resistance, chemical resistance, etc. of natural fibers without adversely affecting the texture and strength. Can be done.

[Brief explanation of the drawing]

The drawing is a graph showing the yellowing prevention effect when palace crepe is processed with resin.

Claims (1)

[Claims] A treatment liquid containing a reactive resin finishing agent, a catalyst that promotes solid-liquid interfacial reaction, and an aprotic polar solvent is attached to a natural fiber product, and the process is heat-treated under conditions that suppress the volatilization of the solvent. Characteristic resin processing method for natural fiber products.