DE1444122A1 - Resin compound to make fabrics made of polyester, polyacrylic and partially acetylated cellulose fibers stiff and dirt-repellent - Google Patents

Description

PATENT LAWYERS

DIPL..ING. H. LEINWEBER dipl-ing. H. ZIMMERMANN

Postschedc account: Bank account: Telephone Tel.-Adr. ,

Munich 22M5 Dreidner Bank ag. Munich (0811) 1619U Lelnpat MUnchon

Munich 2, Marlenplalz, account no. 92790

Our reference: S 81 984 Lw / XIII / C _{8 MUndlen2} . _{Rose Valley 7} . , _Auffl .

(Kustermann paisage)

June 26, 1968

Sumitomo Chemical Company, Ltd., Osaka / Japan

Resin compound to fabric made of polyester, polyacrylic and partially acetylated cellulose fibers! to make it stiff and dirt-repellent

The present invention relates to a resin composition to fabricate polyester, polyacrylic and partially acetylated fabrics To make cellulose fibers stiff and dirt-repellent, consisting essentially of a magnesium chloride containing catalyst Solution of a water-soluble vinyl polymer with hydroxyl and aldehyde groups in the molecule, which is produced by saponification of a copolymer obtained from vinyl acetate and acrolein or acrolein diacetate, as well as a method for producing such fabrics.

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809807/0359

UliWMUlUttH l * n- '*' * »ua, * ι«. » OdU ύ des Anüeiunw & sjvo. *. H. S.

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

The invention has set itself the task of producing such coatings on fabrics that do not have such have functional groups (e.g. polyethylene terephthalate) and for which 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 contains an aqueous 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 peculiarity of this procedure consists in adding magnesium chloride as a catalyst to the aqueous solution. Then the tissue subjected to the conventional resin treatments such as preliminary drying, curing, dipping, etc.

809807/0359

The method according to the invention can also be used in combination with at least one aminoplast, such as dirnethylolethylene urea, Dirnethyloluron, dirnethylolglyoxalmonourein, tetramethylolacetylenediurea, Dimethyloltriazon and its alkylated compounds are carried out.

Synthetic fiber fabrics are popular because of their easy washability and excellent shrinkage or wrinkle resistance Widely used as clothing. However, the most notable drawbacks of such fabrics are that it is difficult to control the grip of the fabric and that dirt tends to be adsorbed. Because of her ease of washing, which is one of the properties of synthetic fiber fabrics, they are mainly for such Garments which are repeatedly laundered, such as white shirts, blouses, and other sports shirts. Therefore include, easy handling and dirt resistance to the essential requirements for 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 that can be used for this purpose exhibit. Therefore, as shown in Table 1, it is difficult to obtain permanent hardness by bonding such resins. ■ · - .- °. - 4 -

Table 1: Effect of hardeners on different tissues (1)

untreated treated m. handling m. handling m.
(2) "Sumi- (3)" Sumi- PVA
tex syrup tex (4)
250 cone "resin M-3" i
78
55
81
46
60 115
89
101
75
125 after
, dW ü before
dW d.W. before
dW after
dW fine tree
woolen fabric (40ei
pure nylon
pure tetron
(5)
Exlan Muslin
(5)
Alon tropical before * after * before
Washing <*. W. dW 105
80
86
53
65 90
107
129
98
153 88
103
91
68
90 132
87
102
80
110 87
60
83
- 50
60 ) 83
57
77
45
66

Notes: 1) The effect of each hardener was determined by measuring the bending lengths and adding up the values of warp and weft directions (mm).
(CCCT-191b Method No. 5206)

2) "Sumitex Syrup 250 cone." iit a highly condensed urea-formaldehyde resin from Sumitomo Chemical Co., Japan and was applied to the respective fabrics according to the following Prescription applied:

809807/0359

"Sumitex Syrup 250 cone." 10g, accelerator ACX (2-amino-2-methylpropanol hydrochloride): 1g,

Total amount was increased by adding

3 brought water to 100 cm.

3) "Suaitex Besin M-3" is a methylated trimethylol melamine from Sumitomo Chemical Co., Japan and was applied to the appropriate fabrics according to the following recipe applied:

"Sumitex Resin M-3 ^H : 10g, accelerator ACX: 1g,

Total amount was increased by adding

3 brought water to 100 cm.

4) P.V.A. is a 2 # aqueous solution of polyvinyl alcohol.

5) "Tetron * (trade name of Toyo Rayon Co., and Teijin Co., Japan), '! Elian" (trade name of Japan Exlan Co. »Japan), and" Alon "(trade name of Toho Rayon Co. _for Japan) are polyethylene terephthalate, polyacrylonitrile or partially post-acetylated cellulose fiber fabrics.

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

Process for the preparation of the water-soluble vinyl polymers used in the process of the invention are known from U.S. Patents 2,569,932, 2,485,239 and 2,657,192. From these patents it follows that that water-soluble vinyl polymers are used as adhesives for Celluphan, Paper or cloth or as a glue for nylon fabrics can be applied. However, it was not until the present invention discovered that such a vinyl polymer Can advantageously be applied to specific textile fabrics with permanent hardness and dirt-preventing properties equip.

Maleic acid, glycolic acid and others are described as catalysts in the aforementioned patents. Only succeeded with the catalyst used according to the invention. however, these water-soluble vinyl polymers on polyester, To apply polyacrylonitrile and partially acetylated cellulose fiber fabric effectively. It was found that magnesium chloride, compared to other catalysts, a surprisingly remarkable hardening and dirt-preventing effect can result.

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

Table 2: By treating partially acetylated cellulose fiber fabrics with a vinyl polymer resin "A" of the example achieved hardening effect in combination with catalysts. (Bending length, mm.)

Kataly- untreated- Maleint- (NHJ ₂ HPO. 2-Amino-

sators

deltes; acid cloth

2-methylpropanol

hydrochloride

Zn (NO _x ),

Mg CL

MgGl ⁺

D-methyl

oluron

before washing

after d. To wash

62

55

92

71

90

68

98

81

77

114

100

120

112

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COPY

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

(- CH ₉ - CH -) _Y (- CH ₉ - CH -) ■ _Y .CBD ^and OH '

which, as mentioned above, are obtained by adding a copolymer of yinylaoetate with acrolein or aerolein 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 mol, usually about 10 M0I56 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 exhibit.

The magnesium chloride catalyst preferred in the process according to the invention is prepared, for example, by more than about 15 # of an aqueous 3QS * magnesium chloride solution added to a 15 # fast of these vinyl polymers. ,

In combination with the vinyl polymer, the permanent hardening and dirt prevention properties can be increased further kung one or more aminoplasts, such as dirnethylolurea,

809807/0359 · _ ■ 9 _

Dimethylolethylene urea, dimethyloluron, dimethylolglyoxalmonourein, Tetramethylolacetylenediurea, dimethyloltriazone and their alkylated derivatives in an amount of about 1/2 to 10 times the amount of the vinyl polymer can be used.

If other aminoplasts, for example melamine resins, are used, there is no lasting hardening effect achieved although such an effect is shown in the initial stage. Therefore, it is hardly possible to achieve the aim of the present invention to reach.

The invention is further illustrated by the following examples

Vinyl polymers are obtained according to the following operations?

Resin A

72 parts of vinyl acetate and 32 parts of acrolein diacetate are dispersed together with 0.1 part of polyvinyl alcohol (a dispersion medium) in 320 parts of Kasser. To the resulting dispersion, 0.2 part BenzqjLperoxid are added and the mixture is allowed 5 hours at 7O ⁰ C to polymerize.

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The resulting polymer granules are separated, dried and then dissolved in methanol to form a 20 # solution. 18 parts of caustic soda are added to the solution and saponification is carried out at 55 ° 0 for 2 hours. The powdery resin obtained in this way (molecular weight about 200,000) is filtered from the methanoi and dissolved in water to form a 15 # strength paste. This paste is referred to as Resin "A".

Resin B

0.2 part of benzoyl peroxide is added to a mixture of 150 parts of vinyl acetate, 54 parts of icrolein diacetate and 44 parts of methanol. 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 saponified at 40 ° C. for two hours. The resulting powdery resin (molecular weight: 15,000) is separated and dissolved to form a 15 # by weight paste in water. This paste is referred to as Resin "B".

Resin C

7.5 parts of solder azobisisobutylnitride are added to a mixture of 13 parts of acrolein, 251 parts of vinyl acetate and 62 parts of methanol, and the mixture is allowed to stir

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Polymerize at 60 C for 20 hours. The resulting Polymer is subjected to the same saponification as in resin B and a resin is obtained (molecular weight: approx 22,000), which is then dissolved in water to form a 15 # 3 branch. This paste is referred to as Resin "C".

Using these resins A, B and C, the prepares the following 12 types of resin baths:

809807/0359

Components

Sarz
baths Resins Dimethy1-
(Parts of) dimethylol
uron 50 $
- ■ wss. Sol.
(Parts) B. 10 8th i 8th ^! Dimethylt ^; Dimethyl
ethylene urine glyoxal mono-
fabric 50 ^ ige urein 50 # ige
<wss. Sol. Wss. Sol.
! (Parts) (parts) 8 ^: 8th I. 8th 8th j 30 # iges
magnesium
chloride
(Parts) ι
Resin A B-1 7.5 A - 10. B-2- 7.5 3 A-1 7.5 8 B-3. 7.5 4.5 A-2 7.5.1 Resin C i 8 3.8 A-3 7.5 y C. 10 · i 8 4.5 . Resin B C-Γ 7.5 C-2 7.5 3 C-3 • 4.5 3.8 4.5 3 4.5 H ^8th 4.8

Note: The volume of each bath was increased by adding water

brought to 100 cm.

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Thereafter Άΐοη Muslin "(partially nachacetyliertes Celulosefasergewebe of Toho Rayon Co., Ltd., Japan) and a mixed-spun, · fine fabric from PoIyäthylenterephthalatfasern and cotton in each of these baths are dipped, squeezed by a mangle, dried for 2 minutes at 8O ⁰ C, 4 minutes at 14O ⁰ C heated, washed with an alkaline cleaning agent and then dried.

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

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Table 3: Results of the tests with partially acetylated cellulose muslin

treatment Bending length before
Washing (3)
(Chain and weft)
mm Bending length after
To wash
(Chain and weft)
mm untreated
I cloth 65 62 Resin bath A 130 107 ¹¹ A-1 146 132 Yes 2 135 114 ¹¹ A-3 141 121 ¹¹ B 125 100 "B-1 139 130 j "B-2 129 114 ¹ "B-3 141 120 _: "C 119 97 "CL1 137 128 : "c-2 124 115 ¹¹ C-3 133 120 Sumitex j ^ *
resin, / ^ 110 70 P.V.A. (2) 112 69

80 9807/0359

- 15 Table 4: Result of the tests with mixed-spun

Polyethylene terephthalate fiber fabric with

cotton

treatment t
Bending length before
washing
(Warp and weft (
TOTTI ' Bending length according to
washing
(Chain and weft)
mm dirt
test vd
To wash
(4) dirt
test nd
To wash
(4) im treated
cloth 76 72 X X Resin bath A 100 90 0 0 "A-1 121 115 0 0 ¹¹ A-2 110 103 0 0 ^M A-3 118 113 0 0 98 89 0 0 ¹¹ B-1 111 104 0 0 ^f! B-2 107 99 0 0 "'B-3 112 106 0 0 " C 95 88 0 0 ^M C-1 109 103 0 0 "C-2 102 96 0 0 "C-3 107 101 0 0 "Sumitex
resin H-3 "
(D
PVA (2) 90
89 77
77 X
X

Notes: 1) "Sumitex resin M-3" is a methylated one

Trimethylolmelamine from Sumitomo Chemical Co. and the bath shown in the table was made by dissolving 80 9807/03 5 9

5 parts of this resin paste and 0.5 part of 30 # strength 2-amino-2-methylpropanol hydrochloride in water, the volume of the resulting solution being .100 cm was brought.

2) The P.V.A. bath was made by Dissolve 1.5 parts of polyvinyl alcohol and make up the resulting solution

3 to a volume of 100 cm.

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

4) Each dirt test was carried out by inserting a test cloth (5 cm 5 cm) in a washing device, which with a bath ratio of 1 ι 50 the below Contains soiling bath, remove the cloth after working for 1 minute, wash the cloth with water, dry and judging the degree of dirt with the naked eye. The pollution bath was

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made by dissolving one

Grams of penance, 0.5 grams of beef tallow and 2

Grams of liquid paraffin in 250 cm

Carbon tetrachloride.

j hardly dirty Λ : a little dirty X: dirty.

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The resin composition according to the invention is traded, for example, under the name Sumitex resin "H-15. The dirt-repellent Properties of this mass result from the following experiment:

Dirt-repellent treatment with Sumitex resin H-15

With Sumitex resin H-15, fabrics made from hydrophobic synthetic fibers can be used for excellent durability Achieve dirt-repellent properties. For example, fibers are suitable for treatment with Sumitex resin made of polyester-polyamide and mixtures of these fibers with cellulose fibers. This makes it easier to wash normally soiled fabrics or even work clothes that are, for example, stuck machine oil is soiled, very relieved.

Treating fabrics with Sumitex resin H-15 has the following advantages:

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

2) The static charge of synthetic fabrics is prevented.

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brought in

3) By appropriate dosage of the vtosgeßBSZtö & i amount

Sumitex resin H-15 can be used with a fabric give a hard grip.

4) There are hardly any water stains.

5) The thermal stability is very high and the whiteness of those colored with fluorescent dyes is very high Tissue is somewhat reduced. Since the resin does not contain nitrogen in the molecule, the chlorine resistance becomes the fabric is not affected by the resin.

6) The resin is water-soluble, so it can be used together with conventional resins.

7) The finished treated fabric is not sticky.

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

9) The resin is particularly suitable for non-iron and dirt-repellent fabric treatment and has a negative effect by no means the inherent characteristics and durability of the non-iron creases when washing and wearing.

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co ο οο

The general properties of Sumitex resin H-15 are summarized belowϊ

Appearance: light yellow, viscous, aqueous solution.

* Solid content: 15 #

Solubility: soluble in water in any ratio pH value: 7-8 Stability: very good Note: Since the resin contains methanol, the

Application no naked flames are used,

Example of a treatment ?

A fabric made of polyester / cotton (65/35) was dipped into the resin solution and pressed out. Then, 2 minutes at 80 ⁰ C was pre-dried and cured for 3 minutes at 16O ⁰ C. '

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

* "* ■" drive itfix I. O II O NS-2 resin (g) 15, I. 15, 5 ■ Sumitex resin H-15 (g) 5 1, 5 Accelerator MX (g) 4, 4, Total (ecm) 100 100

As a result, the following results were obtained;

valuation

I.
ι
I. Fabric I fabric II original 5 HL
.after I.
"^^ • ^^^^ finished product Properties when washing
and wearing
(Procedure with small
Crease angle)
Crease resistance
o ,, (Monsanto procedure)
r>
^ Wrinkle resistance
-V original 3-4
4-5 3-4
4-5 1 - 2
1 - 2 6.0 7.0 Dirt repellent
Properties at
old engine oil
lipstick 30.0 4.5
300
4.4 - Protection from again
pollution
(Degree of pollution) (#) 4.5
304
4.3

Note: The experiments were carried out with ketchup, coffee, mayonnaise, sauce, wine, butter, curry powder; the stains could be removed very easily.

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Procedure for checking the removability of stains

A fabric soiled by stains was subjected to household laundering; the spots left like remove as follows:

Assessment condition

2 something

removed

almost removed

valuation State 1 at all
not
removed 3 removed 5 fully
removed

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

Degree of re- pollution = ο ~ s

^R o

whereby

R = reflection of the unpolluted tissue

⁰ MgO = 100.550 mu.

R_ = reflection of the soiled fabric

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809807/0359

Claims (4)

Patent claims: ^; . 1. Method of making fabrics of polyester, polyacrylic; nitrile or partially acetylated cellulose fibers or Mixing such fibers with cellulose or other fibers by treatment with an aqueous solution of a water-soluble, Hydroxyl and aldehyde groups in the molecule erit- 'containing vinyl polymer obtained by saponifying a copolymer Made from vinyl acetate and acrolein or acrolein diacetate, stiffness and stain resistant To give properties, characterized in that the aqueous solution magnesium chloride as a catalyst clogs. 2. The method according to claim 1, characterized in that in addition to the water-soluble vinyl polymer at least one aminoplast from the dimethylolethyleneurea group, Dimethylοluron, dimethylolglyoxalmonourein, Tetrathylolacetylenediurea, dirnethyloltriazone or their alkylated derivatives are used. 809807/0359 - 24 - lArt.7ilAfafc2Nr.1Sau3de «Amendment« uno8ae3.v.4.9.1.> _t 3. Resin compound, 'around fabric made of polyester, polyacrylic and partially acetylated cellulose fibers stiff and dirt-repellent To make e, consisting essentially of a magnesium chloride as. Aqueous catalyst containing Solution of a water-soluble vinyl polymer with hydroxyl and aldehyde groups in the molecule, which is produced by saponification of a Copolymers of vinyl acetate and acrolein or acrolein diacetate was obtained. 4. Resin composition according to claim 3, characterized in that it additionally contains at least one of the compounds dimethylolurea, Dimethylolethylene urea, dimethyloluron, di-Dimethylolglyoxalmonourein, Tetramethylolacethyleimamatoff, Contains dimethyloltriazon or its alkylated derivatives as aminoplast.