DE1444122C - Process for imparting stiffness and dirt-repellent properties to fabrics made from polyester, polyacrylonitrile or partially acetylated cellulose fibers or mixtures of such fibers with cellulose or other fibers - Google Patents

Description

The previously impregnated fabrics made of nylon, cellulose fibers, Polyvinyl alcohol fibers and the like have functional groups that react with synthetic resins. As a result of this affinity can therefore easily be permanent dirt-repellent and the fabric a certain Making stiffness-imparting coatings from vinyl polymers.

In contrast, the invention has set itself the task of producing such coatings on fabrics, which have no such functional groups (e.g. polyethylene terephthalate) and where the previously known processes and catalysts therefore did not lead to satisfactory results. In the method according to the invention, the fabric is immersed in a resin bath, which is an aqueous one Solution of a vinyl polymer with hydroxyl and aldehyde groups in the molecule, which by saponification of a copolymer of vinyl acetate with acrolein or acrolein diacetate. the A special feature of this process is that the aqueous solution is magnesium chloride as Catalyst clogs. The fabric is then subjected to conventional resin treatment courses, such as preliminary Subjected to drying, hardening, dipping, etc.

The method according to the invention can also be used in combination with at least one aminoplast, and although dimethylolethylene urea, dimethyloluron, dimethylolglyoxalmonourein, tetramethylolacetylenediurea, Dimethyloltriazon and its alkylated compounds are carried out.

Synthetic fiber fabrics are popular because of their easy washability and their excellent quality Shrinkage or wrinkle resistance widely used as clothing. However, the notable ones persist Disadvantages of such fabrics are that it is difficult to control the feel of the fabric and that dirt tends to be adsorbed. Because of its easy washability, which is one of the Properties of fabrics made from synthetic fibers, they are mainly used for such garments which are repeatedly washed, such as white shirts, blouses and sport shirts. Therefore, ease of use and pollution resistance are indispensable requirements to synthetic fabrics. So far, however, it has not been possible to meet the requirements for polyester, polyacrylic and partially acetylated cellulose fiber fabrics, as polyester, polyacrylic and partially acetylated cellulose fiber fabrics have a low affinity for the resins applicable for this purpose. Therefore It is difficult to obtain permanent hardness by bonding such resins, as shown in Table 1.

Table 1
Effect of hardeners on various tissues ¹ )

Untreated

before the
To wash

after washing ⁵ ) Treated with resin ² '

before washing after
To wash

Treated with resin ³ )

before the
To wash

after
To wash

Treated with PVA ⁴ )

before the
To wash

after washing

Fine cotton fabric (40s)

Pure nylon

Fabric made of polyethyleneterephthalate

lat fibers

Fabric made of polyacrylonitrile fibers ..
Tissue made from partially post-acetylated

ten cellulose fibers

83

57

77
45

66

78

55

81
46

60

105
80

86

53

65

90
107

129
98

153

103

91
68

132
87

102
80

110

87
60

83
50

60

Remarks

The effect of each hardener was determined by measuring the bending lengths and adding up the values of the warp and weft directions (mm) (CCCT-19Ib method No. 5206).
Resin ² ) = a highly condensed urea-formaldehyde resin which was applied to the corresponding fabric according to the following recipe: 10 g resin, 1 g I-amino-I-methylpropanol hydrochloride as accelerator; the total was through

Added water to 100 cm ³ .
Resin ³ ) = a methylated trimethylol melamine. which was applied to the respective fabrics according to the following recipe:

Resin: 10 g, accelerator 2-amino-2-methylpropanol hydrochloride: 1 g, the total amount was increased by adding water

brought to I IfO cm ³ .

⁴ ) PV / \. is a 2% aqueous solution of polyvinyl alcohol.

⁵ ) Washing was repeated 5 times with a household washing machine.

Process for the preparation of the water-soluble ones used in the process according to the invention Vinyl polymers are made from the. U.S. Patents 2,569,932, 2,485,239 and 2,657,192 are known. Out These patents show that water-soluble vinyl polymers are used as adhesives for cell glass, paper or cloth or as a glue for nylon fabrics. But only with According to the present invention, it has been found that such a vinyl polymer is advantageously employed can be used to provide specific textile fabrics with permanent hardness and dirt-preventing properties.

Maleic acid, glycolic acid and others are described as catalysts in the aforementioned patents. However, it was only with the catalyst used according to the invention that it was possible to make these water-soluble Effective application of vinyl polymers to polyesters / polyacrylonitrile and partially acetylated cellulose fiber fabrics. Magnesium chloride has been found to be surprising compared to other catalysts can give remarkable hardness and dirt-preventing effect.

Table 2 shows a curing effect obtained by using a vinyl polymer resin "A" (produced according to the example described later) in combination with various catalysts will.

table

By treating partially acetylated cellulosic fabric with a vinyl polymer resin "A" of the example Hardening effect achieved in combination with catalysts (bending length, mm).

Catalysts U.N-
treated
cloth Maleic acid (NHJ ₂ HPO ₄ 2-amino
2-methyl-
propanol
hydrochloride Zn (NO ₃ J ₂ MgCl ₂ MgCl ₂ + Di-
methyloluron Before washing ...
After washing ... 62
55 92
71 O OO
Os VO 98
81 93
77 114
100 120
112

The water-soluble vinyl polymers used in the invention have the structure:

- CH ₇ - CH -

CHO
f _{- CH 9} - CH -

OH

35

which, as mentioned above, are obtained by using a copolymer of vinyl acetate with acrolein or acrolein diacetate, in which X and Y are integers and the ratio of X: Y is 5 to 20:95 to 80, saponified.

Particularly suitable vinyl polymers contain acrolein units in an amount between about 5 and 20 mole percent, usually about 10 mole percent, based on the vinyl polymer.

The water-soluble vinyl polymers used should have a molecular weight between about 20,000 and about 1,000,000.

The magnesium chloride catalyst used in the process according to the invention is, for example prepared by adding more than about 15% of an aqueous 30% magnesium chloride solution to a 15% paste of these vinyl polymers is added.

In combination with the vinyl polymer, one or more aminoplasts, namely dimethylolurea, dimethylolethyleneurea, dimethyloluron, dimethylolglyoxalmonourein, tetramethylolacetylenediurea, dimethylolacetylenediurea, dimethyloltriazone and their alkylated derivatives in an amount of from about ^{1 to} ₂ times, can be used in combination with the vinyl polymer can be applied.

If other aminoplasts, for example melamine resins, are used, it will not be permanent Hardening effect achieved although such an effect is shown in the initial stage. Hence it is hardly possible to achieve the object of the present invention.

Vinyl polymers are obtained according to the following operations:

Resin A

172 parts of vinyl acetate and 32 parts of acrolein diacetate are added together with 0.1 part of polyvinyl alcohol (a dispersant) dispersed in 320 parts of water. Become the resulting dispersion 0.2 part of benzoyl peroxide is added, and the mixture is allowed to polymerize at 70 ° C. for 5 hours.

The resulting polymer granulate is separated, dried and then dissolved in methanol, so that a 20% solution is formed. 18 parts of caustic soda are added to the solution, and saponification is carried out at 35 ° C for 2 hours. The powdery resin thus obtained (molecular weight about 200,000) is filtered from the methanol and dissolved in water to form a 15% paste. This Paste is referred to as resin "A".

Resin B

To a mixture of 150 parts of vinyl acetate, 54 parts of acrolein diacetate and 44 parts of methanol 0.2 parts of benzoyl peroxide are added. After 48 hours of polymerization with stirring at 60 ° C the reaction mass is mixed with 750 parts of methanol and 10 parts of caustic soda and 2 hours saponified at 40 ° C. The resulting powdery resin (molecular weight: 73,000) is separated and dissolved in water to form a 15% paste. This paste is called Resin "B".

Resin C

7.5 parts are added to a mixture of 13 parts of acrolein, 237 parts of vinyl acetate and 62 parts of methanol «, U'-azobisisobutylnitrile added, and one la LH the mixture with stirring at 60 ° C for 20 hours

polymerize. The resulting polymer is subjected to the same saponification as for resin B, and a resin (molecular weight: about 22,000) is obtained, which is then used to form a 15% Paste is dissolved in water. This paste is called Resin "C".

Using these Resins A, B and C, the following 12 types of resin baths are prepared:

Resins
(Parts) Dimethyldimethyloluron,
50% aqueous solution
(Parts) . Components Dimethylolglyoxalmono-
urein,
50% aqueous solution
(Parts) 30% magnesium
chloride
(Parts) Harzbader Resin A
10 Dimethylolethylene urea,
50% aqueous solution
(Parts) 3 A. 7.5 8th 4.5 A-I 7.5 3.8 A-2 7.5 8th 8th 4.5 A-3 Resin B
10 3 B. 7.5 8th 4.5 BI 7.5 3.8 B-2 7.5 8th 8th 4.5 B-3 Resin C
10 3 C. 7.5 8th 4.5 C-I 7.5 . 3.8 C-2 8th 8th 4.8 ■ C-3

The

Note The volume of each bath was brought ^{to 100 cm 3 by adding water.}

Then partially post-acetylated cellulose fiber fabric (cellulose muslin) and a mixed-spun, fine fabric made of polyethylene terephthalate fibers and cotton immersed in each of these baths, squeezed off, dried at 80 ° C. for 2 minutes, heated to 140 ° C. for 4 minutes, with an alkaline cleaning agent washed and then dried.

The hardening and soil prevention effects are shown in the following tables:

Table 3

Result of the tests with partially acetylated
Cellulose muslin

treatment Bending length before
washing ³ )
(Warp and weft)
mm Bending length according to
washing
(Warp and weft)
mm Untreated cloth
Resin bath A ....... 65
130 62 ·
107

Resin bath A-I Bending length before Bending length according to Resin Bath A-2 washing ³ ) washing 35 40 resin bath A-3 (Warp and weft) (Warp and weft) Resin bath B mm mm Resin bath B-I 146 132 Resin Bath B-2 135 114 ₄₅ resin bath B-3 141 121 Resin bath C 125 100 Resin bath C-I 139 130 Resin Bath C-2 129 114- Resin Bath C-3 141 120 ⁵ resin M-3 ¹ ) 119 97 PVA ² ) 137 128 124 115 133 120 110 70 112 69

Table 4 Results of the tests with mixed-spun fabric made of polyethylene terephthalate fiber with cotton

Treatment ' Bending length before
washing
(Warp and weft)
mm Bending length according to
washing
(Warp and weft)
mm Dirt test before
washing ⁴ ) Dirt test after
washing ⁴ ) Untreated cloth ....
Resin bath A
Resin bath AI
Resin Bath A-2
Resin Bath A-3 76
100
121
110
118 72
90
115
103
113 X
0
0
0
0 X O O O O

Continuation '

treatment Bending length before
washing
(Warp and weft)
mm Bending length according to
washing
(Warp and weft)
mm S. dirt test before
washing ⁴ ) Dirt test after
washing ⁴ ) Resin bath B
Resin bath BI
Resin Bath B-2
Resin Bath B-3
Resin bath C
Resin bath CI
Resin Bath C-2
Resin Bath C-3
HarzM-3 ¹ )
PVA ² ) 98
111
107
112
95
109
102
107
90
89 89
104
99
106
88
103
96
101
77
77 0
_0
0
O'
0
0
0
0
A.
A. 0
0
0
, 0
0
0
0
0
X
X

Remarks

') Resin M-3 is a methylated trimethylol melamine. The bath shown in the table was prepared by dissolving 5 parts of this resin paste and 0.5 part of 30% 2-amino-2-methylpropanol hydrochloride in water to make the volume of the resulting solution 100 cm ³ .

² ) The PVA bath was made by dissolving 1.5 parts of polyvinyl alcohol and making up the. resulting solution to a volume of 100 cm ³ .

³ ) Washing was repeated 5 times according to the household washing method by means of an electric motor washing machine.

⁴ ) Each soil test was carried out by placing a test cloth (5 × 5 cm) in a washing device which, at a bath ratio of 1:50, contained the soil bath below. Remove the cloth after working for one minute, wash the cloth with water, dry it and assess the degree of soiling with the naked eye. The foul bath was made by dissolving 1 g of carbon black, 0.5 g of beef tallow and 2 g of liquid paraffin in 250 cm ^{3 of} carbon tetrachloride.

0: hardly dirty, J: a little dirty, X: dirty.

The dirt-repellent properties of the applied by the method according to the invention Resin result from the following experiment:

Dirt-repellent treatment

With the resin applied by the method according to the invention, a fabric made of hydrophobic synthetic fibers achieve excellent permanent dirt-repellent properties. For example fibers are suitable for the application of the resin by the process according to the invention Polyester, polyamide and mixtures of these fibers with cellulose fibers. This will stop washing normally soiled fabrics or even work clothes that are e.g. B. with firmly adhering machine oil is dirty, very relieved.

The treatment of tissues according to the method according to the invention has the following advantages:

1. Re-soiling can be prevented during the washing process.

2. The static charge of synthetic fabrics is prevented.

3. By appropriately metering the amount of resin applied, one can create a fabric give a hard grip.

4. There are hardly any water stains.

5. The thermal stability is very high, and the whiteness of the fluorescent dyes dyed fabric is somewhat diminished. Since the resin does not contain any nitrogen in the molecule, will the chlorine resistance of the fabric is not affected by the resin.

6. The resin is water-soluble and can therefore be used together with conventional resins will.

7. The finished fabric is not sticky.

8. The effect occurs with a very small amount of resin.

9. The resin is ideal for non-iron and dirt-repellent fabric treatment and in no way affects the properties and durability of the non-iron wrinkles when washing and wearing.

The general properties of the aqueous solution of a saponified copolymer applied according to the invention from vinyl acetate and allylidene acetate with a content of 15% solids are in the following compiled:

Appearance pale yellow, biscose,

aqueous solution.

Solids content 15%

Solubility soluble in water

in every proportion

pH 7 to 8

Stability very good

Note: Since the resin contains methanol, do not use open flames be used.

Example of treatment

A polyester / cotton (65/35) fabric was dipped twice in the resin solution and pressed out. This was followed by predrying for 2 minutes at 80.degree. C. and curing for minutes at 160.degree.

The composition of the resin solution results from the following list:

proceedings I. II 50% aqueous dimethyl
glyoxalmonoureide solution (g) 15.0 15.0

209 639/31

Continued 10

proceedings I. II Aqueous solution of a ver soap mixed polymers made of vinyl acetate and Allylidene acetate with a Content of 15% solid substance 1.5

proceedings I. II MgC ^ catalyst in the form
5 an aqueous solution with
a content of 30%
active ingredient (g)
Water up to (ecm) 4.5
100 4.5
100

The following results were obtained:

evaluation

Finished product according to method I.
originally

Procedure II originally

After washing five times **)

Dirt-repellent properties *) for old engine oil

lipstick

Protection against re-pollution (degree of pollution) (%)

Wear during washing (method with small crease angle AATCC 88 A 1964)

Wrinkle Resistance (Monsanto AATCC tentative test method 66-56)

Wrinkle resistance, AATCC 88 C 1964 T,

Compare the condition and appearance of the wrinkles with the standard photograph

3 to 4

4 to 5

6.0

4.5 300

4.4

3 to

4 to

7.0

annotation

*) The experiments were carried out with ketchup, coffee, mayonnaise, sauce, wine, butter, curry powder; the stains could be great

easily removed.

**) After washing five times with a household washing machine using a 0.25% solution of a neutral detergent at a bath ratio of 1:30, a water temperature of 40 ° C and a washing time of 10 minutes and then rinsing three times with water at 40 ° C with a rinsing time of 2 minutes each time.

To test the dirt-repellent properties (removability of stains), dirty things are used Fabric subjected to household laundering.

evaluation

evaluation Status evaluation Status 1 at all
not ent
far away 2 something ent
far away

45

evaluation Status evaluation Status 3 '
5 removed
completely ent
far away 4th almost ent
far away

The calculation of the degree of re-soiling was done as follows:

Degree of re-pollution =
R ₀ = reflection of the unpolluted tissue

Ro

MgO = 100,550 ηΐμ.

R, = reflection of the soiled fabric

Comparative experiments

The inventive use of MgCl ₂ as a catalyst for a vinyl polymer solution of the type specified for the permanent stain-repellent and stiffening finish of polyester, polyacrylic and partially acetylated cellulose fibers with a low affinity for the vinyl polymer shows surprising improvements over that for the same vinyl polymers according to US Pat. No. 2 569 932 used catalyst NH ₄ Cl, which comes closest to the invention, as can be seen from the following comparative experiments:

Procedural conditions

Sample material: polyester fiber fabric

Diving and squeezing 2 χ diving, 2 χ squeezing; recorded Amount of impregnation agent 55% of the weight of the material

i 444 IZZ

12th

Pre-drying

80 ⁰ C, 2 minutes (needle web dryer)
Hardening

140 ⁰ C, 3 minutes (needle web dryer)

Soap

0.2% soda ash, 0.2% detergent

45 ° C, 1 minute drying: 80 ° C, 2 minutes

Impregnation solution
Table la

1 2 3 4th 5 6th Vinyl polymer *), g
30% MgCl ₂ g ....
30% NH ₄ Cl, g
Total, ml 10
0.75
100 .10
1.5
100 10
3
100 10
0.75
100 : ^10
: 1.5 ^:
100 10
3
100

*) Vinyl polymer: The vinyl acetate-allylidene acetate copolymer resin A given in the description as an aqueous paste with a solids content of 15%.

The overall grip (hand) improvement achieved in this way is shown in the following Measurements:

Table 2 a

Total grip (hand) *) in grams

Untreated 1 2 3 4th 5 6th Before washing **) 83
85 145
140 169
164 175
170 130
116 134
118 135
120 After washing**)

*) Total grip (hand): The "Handle-o-meter" device from Thwing Albert Instrument Co. (USA) was used for this determination.

Higher values mean greater hardness, measured at a distance of 2 mm. **) Washing: Wash twice, as usual in the household.

From these results follows the significant advance achieved by the treatment of the present invention regarding the effect and durability of the treatment.

The process according to the invention is applicable to partially acetylated cellulose fibers. Neither these cellulose fibers nor polyester or polyacrylic fibers are _{damaged by the MgCl 2} catalyst. With regard to the partially acetylated cellulose fibers, this is evident from the following comparative tests. For comparison, partially acetylated cellulose fibers and 27 ₂ -acetate fibers with the following properties were used:

Table 3 a

Partly acetylated cellulose fibers 2 '/ ₂ acetate fiber - 14.0 Flexural Strength .. Well weak Degraded by strong acids, Abrasion resistance O
Well weak saponified by strong alkalis, specific weight 1.34 1.32 insoluble in acetone Water absorption (at 95% rela Loss of strength at 90 ⁰ C, tive humidity) 9.6 softens at 200 ^° C., decomposition Chemical resistance ......... Degraded by strong acids, at 230 ° C saponified by strong alkalis, insoluble in acetone Heat resistance Resistant to dry and moist heat, no firmness loss of ability at 130 ⁰ C more humid Heat, yellowed at 200 ⁰ C, charred at 300 ° C

The table above shows that partially acetylated cellulose fibers are inherently superior in strength to 272 acetate fiber. MgCl ₂ has no damaging effect even on 2V2 acetate fibers at room temperature, but this can occur under certain circumstances at higher temperatures because the heat resistance of these fibers is low. In contrast, the heat resistance of the partially acetylated cellulose fiber is good, and these fibers are not damaged under the process conditions according to the invention, as can be seen from the following comparison of the tensile strengths of untreated fibers and fibers treated according to the invention:

Table 4 a

Tensile strength of a muslin tissue made of partially acetylated cellulose fiber (width of the sample 2.5 mm)

sample Tensile strength (kg) Untreated 32.1
31.8 Treated with the fiction
appropriate resin bath A

Claims (2)

Patent claims: 1. Process for fabrics made of polyester, polyacrylonitrile or partially acetylated cellulose fibers or mixtures of such fibers with cellulose or to give stiffness and dirt-repellent properties to other fibers, whereby one the tissue with an aqueous solution of a water-soluble, hydroxyl and aldehyde groups in the Molecule-containing vinyl polymer obtained by saponifying a copolymer of vinyl acetate and Acrolein or acrolein diacetate has been produced, impregnated and then in the usual way aftertreated, characterized in that the aqueous solution magnesium chloride adds as a catalyst. 2. The method according to claim 1, characterized in that the water-soluble vinyl polymer at least one aminoplast from the group dimethylolethylene urea, dimethyloluron, Dimethylolglyoxalmonourein, tetramethylolacetylenediurea, dimethyloltriazone or their alkylated derivatives are added. 25th