KR840001402B1 - A process for producing crease-resistant textiles - Google Patents

Abstract

Crease-resistant textiles are produced by reacting a stoichiometrical amt. of glyoxylic acid with at least one cyclic urea of formula (I); impregnating the textiles with an alkylated product soln.; and heating the impregnated texties to harden to above reaction product. R1, R2 R3, R4, R5, and r6 are the same or different; H, OH, COOH, R, OR, or COOR where R is alkyl or substd. C1-4 alkyl; X is C, O, or N; R3 and R4 are O fox X=O; and either R3 or R4 is O for X=N.

Description

Method of manufacturing fusiform fabrics

The present invention relates to a process for producing fusiform fabrics using new fabric processing agents that impart permanent press properties to the fabric.

It is known in the art to impart fusiformity and dimensional stability to fabrics for use in thermosetting resins or reactants. These materials, known as “aminoplast resins”, include, for example, reaction products of formaldehyde with compounds such as urea, thiourea, ethyleneurea, dihydroxyethyleneurea, melamine and the like. One major drawback in using these materials is that they contain free formaldehyde. The free formaldehyde is formed on the treated fabric and the processed garment during the manufacture and storage of the processing agent or during the processing of the fabric. Fabrics or garments made therefrom also produce incidental free formaldehyde even when stored under wet conditions.

The presence of less than 1% free formaldehyde, based on the total weight of the fabric, is undesirable because it has an unpleasant odor as well as allergic and irritant properties, in particular for the manufacture of processing agents, for the handling of treated fabrics, and It adversely affects people who handle or wear outerwear made of treated fabrics.

The above-mentioned problems due to the presence of free formaldehyde on the treated fabric are well known. Therefore, those skilled in the art have done a lot of research to produce a formaldehyde-free fabric. One solution to the above-mentioned problems has been to use scavengers in glass formaldehyde. U.S. Patent No. 3,590,100 describes cyclic ethylene urea and propyleneurea as scavengers. In addition, US Pat. No. 3,723,058 describes that formaldehyde can be removed by reacting with phthalimide, while US Pat. No. 4,127,382 exemplifies specific nitrogen-containing heterocyclic compounds as scavengers.

Methods of treating fabrics with resin compositions containing or releasing formaldehyde are also known, US Pat. No. 3,260,565, which illustrates a processing agent produced by reaction of alkyl or arylurea or thiourea with glyoxal, have. However, these processing agents have the drawback that their permanent press characteristics are limited. The processing agent produced by the reaction of ethylene urea with glyoxal is described in Japanese Patent Publication No. 53044567, but this processing agent is also unsatisfactory in properties.

Therefore, the inventors have found that the alkylation product by the reaction of glyoxal with cyclic urea is a resin having excellent crosslinking ability to the fabric, and also contains no formaldehyde.

The new alkylated glyoxal cyclourea condensates produced according to the invention are useful for crosslinking fabrics. The usable cyclic urea has the following general formula.

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each is H, OH, COOH, R, OR or COOR, where R is alkyl or carbon number 1 to 4 X is C, O or N, R ₃ and R ₄ are each 0 when X is 0, and R ₃ and R ₄ are 0 when X is N.

Representative examples of the aforementioned compounds include ethylene urea, propylene urea, uron, tetrahydro-5- (2-hydroxyethyl) -1,3,5-triazin-2-one, 4,5-dihydroxy-2 Imidazolidinone and mixtures thereof. Alkylcondensates can be prepared by other suitable conventional methods. Cyclic urea and glyoxal generally react in stoichiometric amounts, even when either of the reactants is used in excess. The general range of glyoxal: cyclic urea is about 0.08 to 1.2: 1. The reaction may be carried out for about 2 hours at room temperature, preferably at about 50 ° C. to 60 ° C. until reflux. The pH is in the range of about 2 to 7.0, preferably about 5.0 to 7.0. The product is a water soluble oligomer. These glyoxal cyclic urea condensates are then partially or wholly alkylated by reacting alcohols such as methanol, ethanol, n-propanol, butanol and the like and mixtures thereof.

Another method involves the reaction of glyoxal with an alkylated cyclic urea.

The processing agents of the present invention are used for cellulose fabrics, wovens or nonwovens, including 100% cellulose fabrics (e.g. cotton, rayon and linen) and blends (e.g. polyester / cotton or polyester / rayon). Suitable. This blend is not essential but preferably contains at least 20% cellulose. White and colored (printing, dyeing, dyeing, cross dyeing, etc.) fabrics can be effectively treated with the resins of the present invention. The resin of the present invention can also be used for fabrics containing fibers having a free hydroxy group.

When the resin of the present invention is treated to a fabric, there will generally be a suitable catalyst. Representative catalysts include acids (eg, hydrochloric acid, sulfuric acid, fluoroboric acid, acetic acid, glycolic acid, maleic acid, lactic acid, citric acid, tartaric acid and oxalic acid); Metal salts (eg, magnesium chloride, nitrate, fluoroborate or fluorosilicate, zinc chloride, nitrate, fluoroborate or fluorosilicate, ammonium chloride, zirconium oxychloride, sodium or potassium sulfite); Amine hydrochlorides (eg, hydrochlorides of 2-amino-2-methyl-1-propanol); And mixtures thereof. The amount of catalyst is about 0.01 to 10%, preferably 0.05 to 5%, based on the weight of the padding bath.

The processing agent can be treated to the fabric by known conventional methods (eg dipping or padding) and also generally in aqueous or alcoholic solutions. The solvent may be water, aliphatic alcohol (eg methanol, ethanol or isopropanol), or a mixture of water and aliphatic alcohol. Other conventional additives such as, for example, lubricants, softeners, thickeners, water repellents, flame retardants, antifouling agents, insect repellents, wet antifouling agents, fluorescent polishes and the like can be used in the treatment bath in conventional amounts. However, these preparations should not prevent the proper action of the processed resin or adversely affect the fabric, and preferably should not contain formaldehyde.

The amount of treatment aid used in the fabric depends on the form of the fabric and the intended use, but is generally about 0.5 to 10% based on the weight of the fabric. Preferably it is 2 to 5%.

In the method of treating the fabric with the resin of the present invention, the fabric is immersed in an aqueous solution or an alcohol solution of the processing resin, and then the immersed fabric is dried and cured, where the drying and curing steps can be carried out continuously or simultaneously.

If desired, the fabric may be processed by a post-cure method (known as a delay cure method). The method consists of immersing the fabric with a solution of processing resin and catalyst, carefully drying the immersed fabric so that the processing agent does not react, and then heating the fabric to a temperature at which the processing agent reacts by the action of a catalyst. .

Although the alkylation product by reaction of cyclic urea and glyoxal is used as a textile processing agent in this invention, the scope of this invention is not limited only by this, This processing agent is a dry strong resin or wet strong resin in paper; Hand builders in fabrics; Binders such as particle boards, medium density fiberboards, plywood, mold and shell molding, insulating materials including glass fiber mats, friction materials, coatings and adhesive abrasives; Components of molding materials; Wood and laminate adhesives; Film-forming resins for coatings and printing inks; Additives of fibers (e.g. rayon); Additive in friction process; Preparation in leather tanning; Fabric inhibitor; Fabric dry binders; It is also suitable for use in applications such as dipping agents in filters (eg, autofilters).

The present invention will be described in more detail with reference to the following examples, which should not be construed as meaning that the contents of the present invention described in the appended claims are limited only. In the examples below, all parts and percentages are by weight unless otherwise indicated.

Example 1

290 parts (2 mol) of 40% aqueous glyoxal solution was adjusted to pH 6.5 with sodium bicarbonate, and then 176 parts (2 mol) of ethyleneurea were added to raise the temperature to 55 ± 5 ° C. The mixture is stirred for 2 hours at this temperature and the pH is maintained between 6.0 and 7.0. After 2 hours, 200 parts (6.25 mole) of methanol is added and the pH is adjusted to about 3.0 with concentrated sulfuric acid. The reaction was carried out at reflux for 3 hours to effect methylation, then the resin solution was cooled to 30 ° C. and the pH was adjusted to 7.0 with 25% caustic soda solution. The product is pure viscous liquid, pale yellow and odorless. Measurements with IR and NMR analyzers show that the reaction is nearly complete. This IR analyzer indicates that a methylation reaction has taken place.

Example 2

360 parts (2.5 mol) of 40% aqueous glyoxal solution was added to 905 parts (2.5 mol) of 44% methanol solution of dimethylmethoxy propyleneurea. The mixture is heated to 55 ± 5 ° C. for 2 hours and the pH maintained between 6.0 and 7.0. After cooling at 30 ° C. a 45% solid, weakly sticky, white aqueous solution (without formaldehyde odor) is obtained. Measurements with IR and NMR analyzers show that the reaction is nearly complete.

Example 3

Propylene urea, uron, tetrahydro-5- (2-hydroxyethyl) -1,3,5-triazin-2-one, and 4,5-dihydroxy-2-imide instead of ethylene urea The method of Example 1 is repeated except that the dazolidinone is reacted with glyoxal. The result is similar to that described above.

Example 4

The method of Example 1 is repeated except that each of the following alcohols, ethanol, n-propanol and isopropanol, is used instead of methanol. The result is similar to that described above.

Example 5

The resin product of Example 1 was used to treat 100% cotton fabrics. The test results are shown in the following table and can be compared with the same fabric samples treated with a processing agent containing conventional formaldehyde. In each case the solution of resin and catalyst may be padded with about 60% wet pick-up based on the weight of the fabric and used for the fabric sample. The treated fabric is dried by heating at 107 ° C. for 3 minutes and heated at 171 ° C. for 90 seconds to cure the resin on the fabric.

Wrinkle recovery is measured by AATCC Test 66-1978 (“Wrinkle Recovery of Fabrics: Recovery Angle Method”).

Tensile strength is measured by ASTM Test Method D-1682-64 (Reissue 1975, “Tensile-Grab-CRT Pendulum Type”).

TABLE I

A is the product of Example 1.

B is 1,3-bishydroxymethyl-4,5-dihydroxy-2-imidazolidinone (45% aqueous solution).

(C) is untreated 100% cotton fabric.

Catalyst 531 (Sun Chemical Corporation) is an activated magnesium chloride catalyst.

RWD(썬 케미칼 코포레이션 제품)은 비이온성습윤제이다.Sulfanole

Sun Chemical Corporation (RWD) is a nonionic wetting agent.

AHL is average home laundering.

According to Table I, the fabric (a) treated with the product of the present invention has similar tensile strength and wrinkle recovery as compared to the fabric (b) treated with a conventional formaldehyde-containing processing agent, but does not contain formaldehyde. It can be seen that there is.

Example 6

The method of Example 5 is repeated using the resin products of Examples 2, 3 and 4.

The result is similar to that described above.

Example 7

An aqueous solution containing 15.0 parts of the resin product of Example 1 and 5314.0 parts of the catalyst is treated to a 65/35 polyester / cotton sample by padding. The treated fabric is then dried and then heated at 150 ° C. for 5 minutes, at 177 ° C. for 5 minutes and at 193 ° C. for 1 minute to cure the resin on the fabric. Fabric smoothness is measured by AATCC Test Method 124-1978 (“Apppearance of Durable Press Fabhics after Repeated Home Launderings”). The results are shown in the table below.

TABLE II

(d) is untreated 65/35 polyester / cotton fabric.

Fabric (a) has excellent whiteness and also shows no chlorine scorch even at the beginning or after 5 rounds.

Example 8

The following solution was prepared to treat 100% cotton and to measure the tensile strength and wrinkle recovery as in Example 5.

TABLE III

A is the product of Example 1.

C is the stoichiometric reaction product of glyoxal with dimethylurea (as described in US Pat. No. 3,260,565).

(C) is untreated 100% cotton fabric.

According to Table III, it can be seen that the fabric (a) treated with the product of the present invention is similar in tensile strength to the fabric (e) treated with the reactants described in US Pat. .

Example 9

The method of Example 5 is then repeated with each 50/50 polyester / cotton, 65/35 polyester / cotton, 50/50 polyester / rayon and 65/35 polyester / rayon fabric instead of 100% cotton. The result is similar to that described above.

Example 10

A sample of 65/35 polyester / cotton fabric is immersed in an aqueous solution containing 20 parts of the product of Example 1, 5 parts of catalyst KR (Magnesium Chloride Catalyst from Sun Chemical Corporation) and 0.25 parts of sulfanol RWD. The fabric is dried at 100 ° C. and then stored for several weeks at elevated temperature. The wrinkles are pressed onto the fabric and allowed to cure at 150 ° C. for 15 minutes. Wash the fabric and measure it using AATCC Test Method 88C-1975 (“Apppearance of Creases in Wash-and-Wear Items after Home Laundering”). This fabric has an appearance ratio of 5, while a blank has an excess ratio of 3.

Example 11

In order to demonstrate that alkylated glyoxal / cyclic urea condensates are superior to non-alkylated glyoxal / cyclic urea condensates, the following experiments are carried out.

(1) 176 parts of ethylene urea (2 moles) were reacted with 320 parts of 40% glyoxal (2.2 moles) at pH 6 and a temperature of 50 ° C to 60 ° C for 2 hours. The product is then reacted with 200 parts of methanol (6.25 moles) at pH 3.0 and then adjusted to pH 6.0 to give a 45% solid. The temperature is further lowered and maintained at 48 ° C., and then the viscosity is measured at regular intervals using a B-field viscometer.

(2) 176 parts of ethylene urea (2 moles) were reacted with 320 parts of 40% glyoxal (2.2 moles) at a pH 6 and a temperature of 50 ° C to 60 ° C for 2 hours. This product is then made 45% solids with water. The temperature is further lowered and maintained at 48 ° C., and the viscosity is measured at regular intervals using a type B viscometer.

TABLE IV

(1) is an alkylated glyoxal / cyclic urea condensate.

(2) is a nonalkylated glyoxal / cyclic urea condensate.

According to Table IV above, it can be seen that the non-alkylated product (2) gels in one week and is unstable, whereas the alkylated product (1) remains stable even after 10 weeks at 48 ° C.

Example 12

The following experiments were conducted to demonstrate that alkylated glyoxal / cyclic urea is superior to non-alkylated glyoxal / cyclic urea condensates as fabric processing agents.

(1) Example 1 of Japanese Patent Publication No. 53044-567

300 g of ethylene urea are placed in a flask (four necks) with a reflux condenser, thermometer and stirrer and dissolved with 450 g of water. Then 1 kg of 40% glyoxal (glyoxal / ethylene urea ratio 2: 1) and 2 g concentrated hydrochloric acid are added. The mixture is reacted at 40 ° C. for 3 hours. After cooling, the pH is adjusted to 5.0 with sodium hydroxide solution. The slightly colored clear product has a solids content of 40%.

(2) Example 2 of Japanese Patent Publication No. 53044-567

300 g of ethylene urea is placed in a flask as in (1) above, dissolved in 450 g of water, and then 750 g of 40% glyoxal (glyoxal: 1.5: 1 of ethylene urea) and 2 g of concentrated hydrochloric acid are added. The mixture is reacted at 40 ° C. for 3 hours. After cooling, the pH is adjusted to 5.0 with sodium hydroxide solution. The slightly colored clear product has a solids content of 40%.

These products and 15 parts of the product of Example 1 were mixed with 3.75 parts of activated magnesium chloride catalyst and 0.25 parts of sulfanol RWD, respectively, and then the solution was padded and treated with fabric samples. The treated fabric is dried at 107 ° C. for 3 minutes and then heated at 177 ° C. for 90 minutes to cure the resin on the fabric. Each blue and white color is measured by AATCC test method 110-1975. The results are shown in the following table.

TABLE V

(a) is the product of Example 1 of the present invention.

(f) is the product of Example 1 of Japanese Patent Publication No. 530444-567.

(g) is the product of Example 2 of Japanese Patent Laid-Open No. 53044-567.

(h) is untreated fabric.

According to Table V, it can be seen that the product (a) of the present invention is superior in both blueness and whiteness as compared to products (f) and (g) of the Japanese Patent Publication. In addition, it can be seen that fabrics treated with products (f) and (g) have extremely poor dry scorch.

Claims (1)

A room characterized by immersing the fabric in a solution of a reactant consisting of an alkylation product by reaction of an almost stoichiometric amount of glyoxal with at least one cyclic urea, and heating the immersed fabric to cure the reactant on the fabric. Method of manufacturing chute fabric.