DE1933394A1 - Process for finishing textiles - Google Patents

Description

MÖNCHEN 23 BWHMflKSfffffiMMIH TELEFON 34SO67 ■ TELEGRAM ADDRESS: INVENT / MÜNCHEN

Excretion from

P 19 12 879.I ■ * __ ν

The filing date is March 13, 1969

-1 July 1969

uZ: E 458 (Vo / Ni)
POS-18 535

SUMITOMO CHEMICAL COMPANY, ITD.
Osaka, Japan

"Process for finishing textiles"

Priority: March 14, 1968, Japan, No. 16 919/68 April 26, 1968, Japan _r No. 28 188/68

The invention relates to a method for finishing textiles using the polyether alcohols of 4,5-dihydroxy-1, S-dihydroxymethyl - ^ - imidazolidone compounds.

009822/1 888

Polyester fibers and their blends with other fibers are in are generally hydrophobic and, due to the absence of hydrophilic properties, have a wet part Soiling when wearing textiles made from it and insufficient removal of dirt heia Vaschen.

Eliminating these drawbacks is of great importance. Processes have already been proposed which are intended to eliminate these disadvantageous properties of textiles. BB is known to impart dirt-releasing properties to textiles made from synthetic fibers, such as polyester fibers, by impregnating them with a polyalkylene glycol, such as polyethylene glycol. However, the low reactivity of textiles made from synthetic fibers, such as polyester fibers, makes it difficult to improve the dirt-repellent properties if these properties are to remain permanent. On the other hand, it was proposed in US Pat. No. 3,049,446 to improve textiles made from hydrophobic synthetic fibers or hydrophobic synthetic fibers spun in a mixture with cellulose fibers by treating them with a reaction product of urea, formaldehyde and glyoxal. The use of such reaction products, however, did not result in any improvement satisfactory dirt removal from textiles.

It has been found that textiles made from hydrophobic synthetic fibers can be made crease-resistant and obtain dirt-releasing properties if they are combined with compounds _r 009822/1888

BATH ORIGINAL

that contain a group that has an affini

tat compared to the hydrophobic synthetic fibers, and a group which compensates for the disadvantages of ordinary hydrophobic synthetic fibers without sacrificing the excellent properties peculiar to synthetic fibers adversely affected. It has been found that certain polyether alcohols have such properties 4,5-dihydroxy-1,3-dihydroxymethyl-2-imidazolidone, which by Reacting certain alkyl ethers of this compound with a water-soluble polyalkylene glycol can be obtained can.

The inventive method for finishing textiles of synthetic fibers or mixed fibers of synthetic fibers and cellulose fibers is characterized in that the textiles are impregnated with an aqueous solution containing, in addition to an acidic catalyst, polyether alcohols from 4,5-bihydroxy-1,3-dihydroxymethyl-2-imidazolidone compounds contains, which by reaction of alkyl-substituted 4,5-dihydroxy-1, S-dihydroxymethyl ^ -imidazolidones of the general Formula I.

R 'OCK ₀ -K

² ! I ² (D

CH CH

oir or ⁵

in.der R, R, R ^ and R ^ are hydrogen atoms or alkyl groups with 1 "to 4 · carbon atoms and at least one '

of these groups is an alkyl group having 1 to 4 carbon atoms men, with a water-soluble polyalkylene glycol with a Molecular weight from 4-00 to 10,000 in a molar ratio 1: 0.2-2 have been obtained, the textiles are squeezed off, dried and then hardened.

The alkylated 4,5-dihydroxy-1,3-dihydroxymethyl-2-imidazolidone compound used as a starting material is known per se and is produced by reacting urea, formaldehyde, glyoxal and a lower aliphatic alcohol having 1 to 4 carbon atoms in the presence or absence of a solvent manufactured. The lower alcohol used has the general formula R ¹ OH, R ² OH, R ⁵ OH or R ^ OH, with methanol being preferred for economic and technical reasons. It

009822/188 8

it

■ I can give me one type of alcohol or / 2 to 4 types of alcohol in a mixture be used. Examples of solvents in this reaction are water, the alcohol used as a reactant, or a mixture of these solvents.

The compound used as the starting material is preferably prepared according to the following methods:

a) by reacting urea, glyoxal, formaldehyde and a lower aliphatic alcohol having 1 to 4 carbon atoms in one stage, or

b) by reacting 4 _f 5-I> ihydroxy-2-imiäazoliaon _> which has been obtained from urea by reacting with glyoxal, with a lower aliphatic alcohol having 1 to 4 carbon atoms and then reacting the product obtained with formaldehyde, or

c) by reacting 4f5-dihydroxy-2-imidaaolidon, which by Reacting urea with glyoxal 1st, with formaldehyde and then reacting the product obtained with a lower aliphatic alcohol with 1 to 4 Carbon atoms, or

d) by reacting 4,5-dibydroxy-2 ~ imidasolidon, which by Reacting urea with glyoxal has been obtained with formaldehyde and a lower aliphatic alcohol with 1 to 4 carbon atoms in one stage, or

e) by reacting Ν, ϊΡ-bis-hydroxymethylbarnetoff or

0 0 9822/1188

by adding urea to formaldehyde Ila »

before

nen / condensate of this compound, with glyoxal and anaebliessendem Reacting the compound obtained using a lower aliphatic alcohol with 1 to 4 carbon atoms, or

f) by reacting N, N * -Bis ~ hydroxynethylurstoi: f or a formaldehyde obtained by converting urea bit

Yor ■■■■ · ■ '■■■ - · ■■■ ^ .- i; Ä - ■ -. ■

A condensate of this compound with a lower aliphatic Alcohol with 1 to 4 carbon atoms and then Reacting the product obtained with glyoxal, or

g) by reacting an alkylated N.N'-bis-hydroxyisethyl-

before

ureas or a ^ condensate of this compound, the by reacting urea, formaldehyde and a lower aliphatic alcohol with 1 to 4 carbon atoms in a stage has been obtained, with glyoxal, or

h) by reacting urea, glyoxal and formaldehyde in one step and then reacting the product obtained with a lower aliphatic alcohol sit 1 to 4 Carbon atoms, or

i) by reacting that obtained by one of the processes a) to h) Product with a lower aliphatic alcohol having 1 to 4 carbon atoms.

The water-soluble Polyalkylcnglykole used in the process are in particular Folyäthyleiiglykol,

_.:: -:. .., .. 0098 22/18 "·

BATH ORIGINAL.

Polypropylene glycol or a copolymer of ethylene glycol and propylene glycol.

The process is carried out in the presence of an acid · Terwendbare Examples of acids are p-toluenesulfonic acid _{(toluene-2,4-diaulfonaäure,} sulfuric _t nitric acid, salt · »acid and phosphoric acid. It does not necessarily need a solvent for reaction used to be. For However, for economic reasons may be the use of water as Lueungsaittel beneficial. the reaction temperature is "wipe 20 and 100 ⁰ C ·

The t »T« efsta «a 4er lrfia4« a | pWr7folyii alcohols from 4.5- Dibydroxy-1 _v > -dlhydroxyBethyl-2-lfiiidazolidone compounds

• soluble in water. An aqueous solution of these compounds can be used to sub-impregnate the textiles.

Textiles »dl · inventiongeaäS can be finished, are hydrophobic synthetic textiles »preferably polyester textiles and textiles made of hish fibers made of hydrophobic synthetic veins and cellulose fiber ^

The impregnation of the textiles is carried out according to the invention in water ger solution carried out. The concentration of the compounds in the aqueous solution is from 1 to 1% by weight, preferably from 1 to 10% by weight.

009822/1818 BAD

XNLe impregnation of the textiles is in the presence of acid fata · 'catalysts performed. The latelysators can be organic acids, inorganic acids or salts of a strong acid and a normal base, as is usually used for the hardening of textiles. Examples of catalysts that can be used are zinc nitrate, magnesium chloride, DlftjDJonlunhydrogenpbospbat »AaBoniunohlor Id ♦ Ilineraltäureealit clay 2-1» ino-2-netbylpropanol and xthanolaain »oxaleture or R ^ linic acid · Zinc nitrate or NtgneslUBOAlor in a catalyst 100 Gew .- ^, torsionally 5 to 50 Oew.-j4, related to the foly ether alcohol binding, can be used.

Bae impregnation is thermoset at cold temperature

IeprMgnierlöeung Wejaee Oblioa "auxiliary ssilttel" ltrer-

are used »Examples of auxiliary agents and methylolurea, I> Uiethylolftthylenharastoff, DlMsthyloluron, Dl- ■ stbyloltriason »Olaethylolglyosal-aono-ureld, propylene urea or an alkylation product of these compounds. The use of one of these symbols or of The use of various auxiliary agents at the same time results in an excellent effect, best of all the durability of the treatment on the textiles. The quantity ratio of the help " aittele su the polyether alcohol compound can be 20 6ew.-ji or very amount.

0 09 8 2 2/18 S 8

BATH

-The impregnated textiles are squeezed out to remove excess solution until the desired absorption occurs the polyether alcohol compound is D * »extent of The uptake is not particularly critical. The uptake of the compound is preferably from 0.5 to 10% by weight, based on the textiles.

The impregnated textiles are then dried and hardened. If Palis is desired, drying and hardening can take place at the same time. The drying is / BE i ° a temperature of 12O ⁰ C or lower, and requires about 1 to 10 * Hin Subsequently, the dried fabrics are

B _Ä Bo

hardened. Curing is / carried out at a temperature of 130 to 17O ⁰ C, and usually requires about 30 sec. To 5 min. Here, the Polyätheralkoholverbindungen be cured into insoluble materials.

The textiles finished according to the invention have improved hydrophilic properties, resistance to renewed soiling and dirt-releasing properties on the basis of of the polyalkylene glycol chains in the molecule of the finishing agent, the imidazolid, onring of the compounds has a great affinity for hydrophobic synthetic fibers such as polyester fibers and, because of its reactivity with cellulose fibers, results in a finishing of excellent durability, If there are many hydroxymethyl groups in the polyether alcohol compounds, textiles finished with them can do so

009822/1809 '"'' ^Λ V' BAD ORIGINAL

- IU -

have improved crease resistance

The production of the connections is more detailed through the examples A Me Y.

Example ι

It was 4,5-dimethoxy-2-imidazolidone, which was replaced by methyl

ren of 4 »5-Dihydro3cy-2-imidazolidon had been obtained, au 1 _t 3-dihydroxylaethyl-4,5-dilπethoxyπβthyl-2-iπ ^ idazoliöon methylolated. G to a 62 Genisch from this compound and 180 g of polyethylene glycol having a molecular weight of 600 1.2 g p-toluenesulfonic acid were added and heated under reduced Druok of about 50 mm Hg at 60 ⁰ C · It the mixture 40 min. Distilled 14.5 g methanol from the mixture AB, corresponding to 75 1 * of the theoretical amount · the resulting product was immediately diluted with water and bit 5N sodium hydroxide solution ψ neutralized in water. 450 g of a 50% aqueous solution were obtained.

The resulting solution was slightly yellow in color and transparent and viscous.

B e is ρ i -e 1 B

There were 2.5 mol of 37 fSige pin aldehyde solution, 1.0 mol of 40

009622/1888

Olyoacallösung, 1.0 mol of barnstoff and 5 mol of isopropanol aiteln- «aitraetct and it was bit propyl groups substituted!, Y-Dihydroxyeethyl-1 ^ J-dihydroxy-a-iaidasolidon old 1.7 mol isopropoxy groups obtained 57 g of these compound ait 300 g of molten PolyHthylmglykol ait elnea molecular weight of 2,000 mixed "warning BetttlojMfeeäaoa wnii 0.5 eugesetet al konsentrierte hydrochloric acid and the erhitst Beaktionagealsoh under drilling for 1 hour at 60 ⁰ C. The solution obtained was 50 μl of water and then 1.2 μl of a 5N sodium hydroxide solution and neutralization sugesetst · The solution was heated under reduced pressure until 50 μl of distillate separated out. The Isopropanolaenge la distillate was 10 g corresponding to 56 i "of the theoretical amount · The resulting product represented a compound in which zai dasolldlnonringe to both ends of the polyethylene glycol were bound.

Example C

Binea Geaisoh of 42 g of 1,3-dinethoxyiethyl-4,5-dihydroxy-2-laidasolid on which had been obtained by reacting H, N '~ bis (methoxyaethyl) -harnetoff with olyoxal, and 10 g of Vaeeer and 400 g a gesohaolsenen Copolyaerisats of 80 5 * polyethylene glycol and 20 f> ait polypropylene glycol having a molecular weight of 10 000 was 0.5 ml sulfuric acid 70 ftiger sugeftigt and the resultant solution heated for 1 hour at 80 ⁰ G "

Kaoh of the Xtoeetsung was the neutralized reaction odor

009822/1888

Purified from a solvent system of diisopropyl ether and water . Elemental analysis of the product obtained showed that 1 * 7 inidazolide rings were bound to one molecule of polyalkylene glycol.

For β ρ ie 1 D iX

The 1,3-dimethoxymethyl-4,5-di in Example Q. ^w hydroxy ~ 2-imidazolidone was treated with excess methanol and a methylated l ^ -dihydroxymethyl ^ fS-dlhydroxy-2-imidazolidone with a degree of methylation of 3.5 was obtained. Ee 45.5 g of the obtained compound methyllerten with 320 g of a copolymer of 50 5 "Polyethylene glycol and 50 i» polypropylene glycol having a molecular weight of 800 according to Example 0 implemented. Ee distilled from 18 g of methanol, corresponding to 80 ^c /> of the theoretical amount · The resulting product was a viscous solution which was miscible with water W ser.

Example B.

Urea, a 40% glyoxal solution and a 37% formaldehyde solution were mixed in a molar ratio of 1.0: 1.0: 2.5. The resulting mixture was heated for 3 hours at a pH of 7.0 to 7.5 at 6O ⁰ C and then the reaction product obtained to a solids content of

009322/1888

BATH ORIGINAL

90 # drained and narrowed. To the obtained compound were added 10 * 0 mol of methanol and uageeetet the resulting mixture at a pH of 2.0 for 1 hour at 3O ⁰ C, and receive a condensate of urea, glyoxal, formaldehyde and methanol with a degree of methylation of 1.5 . 50 g of a Θ0% aqueous solution of this condensate were mixed with 300 g of polyethylene glycol with a molecular weight of 1,500. Bern resulting mixture was added 0.5 ml of 70 jSige sulfuric acid and reacted for 1 hour at 70 ⁰ C. The conversion ratio was determined from the methanol formed to be approximately 80 fi .

Example y

A mixture of 4.5-dihydroxy-2-imidazolidone 37 5% formaldehyde solution and methanol in a molar ratio of 1.0: 2.5: 5.0 was refluxed for 90 minutes at a pH of 5.2 and a condensate was added a value of CH ₅ O - / * -0.55. The reaction was carried out as in Example 5, except that 41 g of a 95 sSigen aqueous solution of the condensate were used instead of the condensate. A product with a degree of unetherification of 73 1 »was obtained.

009822/1888

Example 1·

Its 50% aqueous solution of the reaction products obtained according to Examples A, 1 and 0 was prepared. In each 100 zdl of an impregnation solution of water and 15 g of this 50% resin solution as well as 4 »5 g of a 30% aqueous solution of magnesium chloride, a cloth made of Tetoron and cotton in a proportion of 65« 35 was immersed and expressed with the help of a deficiency} until the uptake of the compound 7 wt .- ^ ₁ based on the cloth was. Thereafter, the cloth was dried for 2 Hinuten at 8O ⁰ C and cured for 3 minutes at 16O ° C. The cloth was washed once and three times in a household washing machine and the resistance to soiling of the treated cloth was tested in each case. The crease resistance of the cloth obtained was also measured. The results are given in Table I below. As the results show, the treated cloth had a clearly recognizable favorable durability and strength ge r gen fouling and improved wrinkle resistance "

00 9822/1888

SAD

TABLE I.

^ - ^ Impregnated cloth Rs 3 untreated Cloth after Cloth with Cloth with Cloth with deltes ST pre product product product Degree of he 1 cloth writing from Bei from Bei from 3ei- test neuten impräg game k game B apiel C Dirt waste j) _ß j ned impregnated impregnated impräg
ned Impassiveness Ro fermentation, % 03.0 02.5 03.5 83.5 03.5 zunga- Reflection Ra 1 63.0 63.0 78.0 79.5 80.0 strength value CD 65.0 63.0 "77.5 78.0 79.0 CJ Crease resistance
(Warp + weft) (O 24.0 23.7 6.0 4.8 3.0 CO K)
KJ 21.7 23.7 7.2 6.0 5.4 IXi co 276 311 309 307 298

-2.

CO CjO CjO CO CD

The ST-Voreehrift refers to the use of 1,3-Dihy <JroxyTDethyl-4,5-d / hydroxy-2-imidaeolidon in β-parts of the reaction products prepared according to the invention.

Resistance to recurrence was measured as follows:

It was an artificial oily dirt from a mixture of V2.5 wt. Stearic acid, 12.5% by weight oleic acid, 12.5% by weight hydrogenated coconut oil, 12.5% by weight olive oil. 8.5% by weight; » Cetyl alcohol, 21.5 parts by weight of solid paraffin Ji ^ 5.0 wt. -F "cholesterol and 15i0 wt .- ^ soot produced. .

An artificial solid dirt was made from a mixture 55% by weight of clay, 17% by weight of silica anhydride, 0.5% by weight of 5% by weight Zisen-III oxide, 17% by weight portland cement, 8.75% by weight Ji n-heptane and 1.75 wt .- ^ carbon black produced

The artificial oily Sohmutz was mixed with the firm snout in a weight ratio of 3: 1. Three parts of this mixture and 7 parts of a nonionic detergent were dispersed in water and an aqueous dispersion having a concentration of 0.25 μl was prepared. The impregnated cloth was verachnutzt 20 Hinuten at 40 ⁰ C using a "Launder-o-meter ^M Verauchsgeräts with the dispersion auegedrückt and dried. It was the reflection at 550 mu Ewert

QO 98 22/188 8

BATH ORIGINAL

of the impregnated tucha with the help of a spectrophotometer. measure up.

The degree of redeposition was determined according to the formula Ro - Hs 1 (or Ro 3), .. Ds 1 (or Ds 3) = —— ~ V, - ~ i χ ioo (f °)

determined, where

Ro * reflection: of the impregnated cloth before the ben- · dirty,

Rb * Reflection of the impregnated cloth after soiling and

Rs 1 and Rs 3 - reflection values of the impregnated cloths, the one or. washed three times and then soiled. ■. ·>

The wrinkle resistance was determined according to the Monsanto method JIS L-1041 C measured with the recovery angles of chain and Shot can be specified in degrees

009822/1888 _BA 0

B e i β ρ

There was an impregnation bath of 100 ml of 8 g of the product prepared according to Example B, 15 g of a 50 l £ en aqueous solution of 4,5-dihydroxy-1, ^ - dihydroxymethyl ^ -imidazolidone and 4.5 g of a 30 # aqueous solution of magnesium chloride prepared by the addition of water, in the impregnating bath, a cloth made of Tetoron and cotton in the ratio 65x35 was dipped and printed out using a mangle, until the uptake of product 7.5 wt. f _»f based on the cloth was . The doing became 2 Hin. dried at 80 ⁰ O and 3 min. at 16O ⁰ C cured. The resistance to renewed dirt and the stiffness of the impregnated cloth have been improved. The results are shown in Table II.

TABBLLB II

^ * "" ** - N * ^ _ Impregnated Tech
Check ^ ^N "*** ^% '- * ^^^ Ds 1
Ds 3 stiffness
(g / 20 ram) not ia-
impregnating
tes cloth Do after
ST pre
sohrift
impräg
ned Cloth ge
according to
game 2
impräg
ned Degree of recurrence
Schnutz excretion, % 25.0
23.5 26.0
25.0 6.0
6.6 89 100 83

009822/1888

BATH ORIGINAL

The cloth impregnated according to the ST regulation was impregnated with bit 4 »5-dihydroxy-1f> -dihydrozyinethyl-2-iiiidaEolidon alone according to example ft.

The stiffness became old a "handle-o-meter" of the company Thwing Albert Instrument Co.

From Table II it can be seen that the combined impregnation with a known resin together with the reaction product prepared according to Example β has a resistance to receive re-pollution of superior durability without the cloth losing its grip.

Daa according to example | obtained reaction product shows similar favorable results in the impregnation as the reaction product according to Example B.

Example 5

The reaction product prepared according to Example O was used together with an agent to achieve permanent ironing creases for Used to impregnate a cloth. The impregnation was carried out according to Example 2. The results obtained are given in Table III.

0 0 9 8 2 2/1888 _ßAD ORIGINAL

TABBIiLB III

^^ * "^ - ^^^^ Impregnated cloth
Examination ^^^^. ^^^ Ds 1
Ds 5 looks in
concise
ten! cloth Do after
Sl-fore
Drill bit
impräg
ned Tuoh ge
according to
game 3
impräg
ned Degree of recurrence
Dirt build-up
. (*) Wash-and-wear properties 24.0
23.0 27.0
24.0
• 4.5
7.0 N - - '
stiffness
(g / 20 on) 3.5 4.0 4.7 Removable it for engines
oil
I. 90 105 78 1 - 2 1 - 2 4th

The releasability for engine oil is measured by applying a! Drops of engine oil (Herateller Maruzen Sekiyu KK, Ho.40) is placed on the cloth and the cloth is then washed once in a Haushaltawaschmaechine. The replacement

OC 9 8 22/18 8 * 8

BATH ORIGINAL

Ability is assessed according to the following values:

1 ■ not replaced by Rollatand «

2 »somewhat detached.

3 - Relieved in an Ublioher manner.

4 «almost completely replaced.

5 a completely replaced.

From Table III it can be seen that the impregnation with a combination of a reaction product prepared according to the invention with a known equipment for Permanent ironing creases a favorable Veetigkeit against renewed Soiling and a good ability to remove engine oil results in »without the wash-and-wear properties and the The grip (stiffness) of the impregnated cloth is disadvantageous to be influenced.

009822/1888

Claims (5)

1. Process for finishing textiles made of synthetic see fibers or mixed fibers made of synthetic fibers and Cellulose fibers, marked thereby et that the textiles with an aqueous solution impregnated, which, in addition to an acid catalyst, polyether alcohol / 4,5-dihydroxy-1,3-dihydroxymethyl-2-imidazolidone compounds contains, by reaction of alkyl-substituted 4,5-Dihydroxy-1, J-cLihydroxymethyl ^ -iniidazolidonen of the general formula I. It in which R, R, R and R ^ "hydrogen atoms or alkyl groups with 1 to 4 carbon atoms and at least one of these groups is an alkyl group with 1 to 4 carbon atoms is, with a water-soluble polyalkylene glycol having a molecular weight of 400 to 10,000 in molar ratio 1: 0.2-2 have been obtained, the textiles are squeezed off, dried and then hardened. 009822/1888 " ²³ " 1 93339Λ 2. The method according to claim 1, characterized in that the acid catalyst is used an organic acid, an inorganic acid or a salt of a strong acid with a weak base is used. 3. The method according to claim 1 and 2, characterized in that the acid catalyst Zinc nitrate or magnesium chloride is used. 4. The method according to claim .1 to 3, characterized in that the polyether alcohol the ^ S-dihydroxy-i ^ -dihydroxymethyl ^ -imidazolidone compound used in a concentration of 1 to 20 wt. 5. The method according to claim 1 to A _1, characterized in that the acidic catalyst is used in an amount of 1 to 100 wt .- ^, based on the polyether alcohol of the 4,5-dihydroxy-1,3-dihydroxymethyl-2-imidazolidone compound . 009 8227 1888