DE2062559C2 - Process for flame retardant finishing - Google Patents

Description

R-

-S-C

where R is a substituted or unsubstituted hydrocarbon group or a heterocyclic group, and R ₁ , R ₂ , R ₃ , R _{4 represent} hydrogen, an unsubstituted or substituted hydrocarbon group or part of a heterocyclic group consisting of two of the groups R ₁ , R ₂ , R ₃ , R ₄ and R is formed and where A is an inorganic or organic anion and / 1 is an integer from 1 to 4 and m is the valence of A, impregnated and heat-set.

The invention relates to a method for the flame retardancy of fibers, film and foil material, Plates and other bodies.

There are already various inorganic salts such. B. sodium phosphate and sodium molybdate known as a means of flame retardant finishing. Various metal oxides such as B. Antimonyl Trioxide and various organic compounds such as. B. chlorinated hydrocarbons, urea, organic Phosphorus compounds can also be used as flame retardants and as flame retardants used for fibers.

However, these conventional agents for flame retardancy and flame retardancy leave much to be desired in many ways. In particular with regard to synthetic fibers and bodies synthetic materials such as B. made of polyamide, polyester and polyacrylonitrile.

It is therefore the object of the present invention to create a method for flame retardant finishing, which is not subject to any restrictions with regard to the materials to be treated and especially good for synthetic fibers and synthetic fiber blends, such as cellulose fibers !! and suitable and ins special also for Moquetle.

The subject of the invention is a method for flame finishing of fiber, film and foil material. Mats and other bodies, made of natural and synthetic polymers, characterized in that the body is treated with a compound of the formula

-S-C

where R is a substituted or unsubstituted hydrocarbon group or a heterocyclic group, and R ₁ , R ₂ , R ₃ , R _{4 represent} hydrogen, an unsubstituted or substituted hydrocarbon group or part of a heterocyclic group consisting of two of the groups R ₁ , R ₂ - R ₃ - R. » and R is formed and where A is an inorganic or organic anion and η is an integer from 1 to 4 and m is the valence of A, impregnated and heat-set.

Typical examples of the radical R include saturated and unsaturated alkyl groups. like methyl-. Ethyl, propyl, butyl, cyclohexyl. Vinyl and AIhI groups; Alkylene groups such as methylene. Ethylene and propylene groups; Aralkyl groups such as benzyl groups; Aryl groups such as phenyl, tolyl and XyIyI groups; heterocyclic groups such as pyridinyl, pyrimidinyl, triazinyl, thiazolyl imidazolyl. Oxazolyl, Isoxyazolyl, pyrazolyl, quinonyl and acridyl groups. These groups can be halogenated. Hydroxy, alkoxy, phenyl, epoxy, acyl, acyiamine, acyloxy, amino, imino, carbonyl, carboxyl, Carboxylic acid ester residues and groups containing phosphorus, such as ζ. B. Phosphoric acid esters and phosphorous acid ester residues may be substituted. In addition, R can be a polymeric hydrocarbon group be those with hydroxy, cyano, carboxyl. Carboxyl ester, carbamyl and halogen radicals substituted can be, such as B. polyvinyl alcohol. Polyacrylonitrile, polyacrylic acid, polyacrylic acid ester, polyacrylamide, Polystyrene and polyvinyl chloride.

Typical examples of the groups R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, saturated and unsaturated alkyl groups and alkylene groups. Aralkyl groups, aryl groups and heterocyclic groups, where the same applies to the substitution of these groups as to the radical R.

According to the invention, it is particularly advantageous. links of the following general formula:

S-C

ν -r;

rr;

Λ '"

In this formula, R 'denotes an alkyl group odci an alkylene group having 1 to 5 carbon atoms.

The alkyl groups or alkylene groups can also be combined with one another via one or more divalent radicals, such as ζ. Β via · —0—, -NH-, —CO—, —COO— or via a heterocyclic ring, such as ζ. B. via a triazinyl group. Rj, R ₂ , R ₃ and R; can denote hydrogen, alkyl or alkylene having 1 to 5 carbon atoms and, like R ', be substituted in the manner indicated above. Two of the group-fce n-Rl, Ri ^R i ^{and R} 4 may be combined together to form a heterocyclic ring, where z. B. the following connections can be formed:

Formula implements:

S = C

(HD

R'-S-C

NH-CH,

NH-CH,

CH ₂ OH

R'-S -C

CH,

N CH ₂

CH, O H

A means an inorganic anion such as a halogen anion e.g. B. a chlorine, a bromine or an iodine anion; an anion of an inorganic, oxygen-containing acid, ζ. B. sulfuric acid, phosphoric acid, phosphorous acid; a pseudo halogen anion, e.g. B. the anion of hydrofluoric acid or an anion of an organic acid, e.g. B. acetic acid, propionic acid, alkyl sulfonic acid. Dithiocarbamic acid, alkylphosphonic acid, alkylphosphonic acid monoesters, dialkylphosphinic acid, dialkylphosphinous acid, alkylphosphoric acid and dialkylphosphoric acid; in means the valence of A.

If at least one of the groups R ₁ . R ,. R ₁ and R _{4 is} a hydrogen atom, the formula (1) can also be written in the corresponding tautomeric form:

R -

NO,

S-C

HA

(D '

The compounds according to the general formula 1 or Γ can be prepared in various ways. A typical process for the preparation of this class of compounds is that one has a compound of the general formula

R - X ₁₁

(11)

with a thiourea of the following general

NR ₂

NO-,

R4

The radicals R, R ₁ . R ₂ , R ₃ and R ₄ have the same meaning as in formula 1. X denotes a halogen atom and "denotes an integer 1 to 6. The reaction is carried out in a suitable organic solvent, such as. B. in alcohol at room temperature or at a higher temperature. The radical X can also be any other alkylating agent radical, such as. B. a tosylate residue, a sulfate residue or the like.

Articles made of cellulose fibers, e.g. B. made of cotton, viscose rayon, cellulose ester or Cellulose ether, made from natural or synthetic fibers made from wool, silk, polyamide, polyester, polyacrylonitrile. Polyolefin or copolymers thereof or mixtures thereof are impregnated. Further Mixtures of fibers and fabrics made from mixed materials can be used in accordance with the invention Funds are treated. This results in a permanent flame retardancy of the fibers and Textiles. Films, foils, plates and other objects made of plastics, such as e.g. B. Polyvinyl chloride. Polystyrene, polyolefin, polyamide. Polyester. Polyacrylonitrile, polyurethane, polycarbonate. Phenolic resin, urea resin and melamine resin are treated according to the invention. It is also possible according to the invention to add the agents to the polymers or monomers before casting or spinning. The objects can be treated by dipping, coating, spraying or mixing. The effectiveness of the flame retardancy can be increased by heating. The following will be certain facilities for carrying out the process for flame retarding fibers in more detail explained.

When preparing a bath of the compounds used according to the invention, it is best to use water, organic solvents or mixtures thereof as diluents. Since the compounds are water-soluble, it is preferred to provide the treatment bath by dissolving or dispersing the compounds in an aqueous medium and to immerse the textile material continuously or in batches in the bath. This should take place at a temperature which is between room temperature and 100 "C. The textile material treated in this way is dried and heated to around 100 to 150 C. It is also possible to treat the textile material with other conventional textile auxiliaries during or after flame retarding, such conventional agents include 7, B. formaldehyde, methylolurea, methylolthiourea, methylolmelamine, methylolethyleneurea and tetramethylolphosphonium chloride.

The compounds used according to the invention can be used together with conventional flame retardants and flame retardants, e.g. B. with various organic phosphonic acid derivatives, organic phosphorous acid derivatives, organic phosphonic acid derivatives, organic Phosphinic acid derivatives, organic phosphinous acid derivatives, organic phosphines, organic Phosphine oxides, rhodan compounds, antimony oxide, titanium tetrachloride, zinc chloride, boric acid and borax.

The compounds used according to the invention are soluble in an aqueous medium and can with • Give ile fiber types excellent flame-retardant properties through simple treatments. In contrast the largest number of known flame retardant equipment is only suitable for a limited number Number of fiber types. For example, the conventional flame retardants are tetrahydroxymethylphosphonium chloride and tris-aziridinylphosphine oxide only effective on cellulosic fibers. With synthetic However, they have no effect on polymers such as polyesters and polyamides. On the other hand is thiourea of little effectiveness against polyamides and ineffective against polyester or Cellulose.

It is therefore a major advantage of the invention that it has excellent flame retardant properties various types of fiber materials and other synthetic or natural materials results.

In the following, the invention is explained in more detail on the basis of exemplary embodiments.

In the examples, the flame retardancy tests were carried out according to the following method, which is similar to the Standard procedure conforms to JISL-1079-1966.

1. Test sample

A test specimen 50 mm wide and 250 mm long is at a relative humidity of 65 ± 2% held at 21 ± IC for 4 hours. The test is then carried out.

2. Test method

The test specimen is held in such a way that the longitudinal cables run in a vertical direction. It will a Bunsen burner is used, which has an inner diameter of 9.5 mm and a flame length of 34 mm. This burner is arranged so that between the lower edge of the specimen and the upper edge of the Bunsen burner there is a distance of 19 mm and the flame the Test specimen touched for about 12 seconds. After this contact with the flame, the Bunsen burner removed and the line to the EnI-flammung (Nachentllammung, seconds), the glow duration (Naehglülidaiicr. Seconds) and the length of the charred area (the melted area in i'alle \ on synthetic fibers, cm) measured. One good flummfcKUtus equipment leads to low values in post-lamming and post-glowing and / u a carburizing length or melting length of less than 12 cm.

example 1

1 mole of S-methylthiuronium sulfate becomes one 15% aqueous solution of 2.2Mol formaldehyde given. and the mixture is stirred for 24 hours. The mixture is diluted so that one aqueous solution with a Fesisloff content of 15% receives.

The sample fabrics were in the aqueous The flame retardant solution is dipped and then dipped until moisture is absorbed by 80% deficient. They were then dried at 70 C and heated to a permanent temperature To maintain the flame retardancy of the textiles.

The results of the flame resistance tests on the treated textiles are listed in Table 1.

Table I.

Textile material

After washing 10 times

Right away

after

treatment

F- G C F G C

sec sec cm sec «ic cm

Cotton 0 0

Polyester to cotton 0 0

Nylon 0 0

Polyester 0 0

4.8 0 0 5.9

6.8 0 0 8.1)

7.5 0 0 8.6

7.2 0 0 8.2

The following abbreviations have been used in the table:

Polyester = polyethylene terephthalate,

F = post-ignition,

G = afterglow,

C = along the charring zone.

Example 2

In an aqueous solution with 10% S-ethylthiuronium bromide and 7% trimethylol melamine, fabric coupons were immersed. These were subsequently Deficient up to a moisture absorption of 80%. After drying and 3 minutes Heating to 140 ° C became permanent flame retardant Textiles preserved. The results of the flame-retardant tests on the textiles are compiled in Table 2.

Table 2.

Textile material

Right away

after

Bchamllunu

After washing 10 times

lake

lake

cm

F.
sec

G
lake

Cotton 0 0 4.0 0 0 4.9

Polyester to cotton 0 0 6.0 0 0 7.3

Nylon 0 0 7.6 0 0 H.8

Polyester 0 0 7.1 0 0 8.0

The same treatment was carried out on a textile material made of polypropylene, but with Was heated to 110 C for 5 minutes. In addition, the same treatment has been applied to textile materials carried out from polyacrylonitrile, but steamed with supersaturated steam for 5 minutes would.

The results of the flame resistance tests are summarized in Table 3.

Table 3

Textile material

Immediately after lOmuligcm

after washing
treatment

1- G C F Ci C

sec sec cm sec sec cm

Polyacrylonitrile
Polypropylene

0 0 5.6 0 0 7.1

0 0 8.0 0 0 9.3

Example 3

Methoxymethyl thiourea was made with an excess of methyl iodide in dimethylformamide reacted at room temperature for 24 hours, S - methyl - N - methoxymelhyllhiuronium iodide was obtained as the main product.

Test gaps in textile material were immersed in a 20% strength aqueous solution of this product. This were then ironed to a moisture absorption of 80%. They were dried and Heated to 120 C for 5 minutes to make a permanent To achieve flame retardant wedge of textile materials.

The results of the flame resistance tests are in Table 4 compiled.

Table 4

Textile material Right away G C. After lOmaligcm G C. after lake cm To wash lake cm 0 5.4 0 6.8 treatment 0 6.1 } - 0 7.2 I- 0 6.8 lake 0 7.7 cotton SCC 0 7.5 0 0 8.4 Polyester to cotton 0 0 nylon 0 0 polyester 0 0 0

Example 4

In a 15% aqueous solution of methylol pseudolhiourea the formula

CH ₃ O-CH ₂ -SC

NH

NH,

an aqueous solution of hydrogen bromide was added dropwise with stirring and cooling with ice so that no gel formed.

The same reaction was performed using

CH ₃ O-CH ₂ -SC

N-CH ₂ -OCH ₃

NH,

accomplished. Test samples of textile material were immersed in the solutions obtained and up to lacked a moisture absorption of 80%. The samples were saturated with supersaturated for 5 minutes Steamed and washed and dried, permanently flame-retardant Textilmatcrialicn received.

Example?

In aqueous solutions with 20% of the following flame retardants and 7% dimethylolthiourea and 1% accelerator (Sumitcx accelerator ACH) Test pieces of textile material immersed. These samples were then subjected to a fluid absorption deficient by 80%. They were dried at 80 C for 5 minutes and then during Heated for 3 minutes to 140 C to make the textiles permanent flame retardant.

CH,

S-C

NH,

NH, 2 y

CH, -

S-C

NH,

NH-CH ₂ S-CH ₃

NH-C = NH,

2Y

The compound (a) was prepared by reacting thiourea with methylene iodide, and the compound (b) was prepared by reacting methylenedithiourea with methyl iodide in methanol.

<o

10

The results of the flame resistance tests. which were achieved with the aid of compound (b) are in Table 5 compiled.

Table 5

Textile material

however, treated with supersaturated steam for 5 minutes.

The results of the flame resistance tests are shown in Table 6.

Nad G C Table 6 Right away sec cm after h lOmaligem treatment To wash _{| 0} Tcxi'W 'file FGC sec sec cm F. sec

Cotton 0 0 4.5 0 0 5.2, ₅

Polyester to cotton 0 0. 6.7 0 0 7.8 polyacrylonitrile

Nylon 0 0 7.9 0 0 9.0 polypropylene

Polyester 0 0 7.3 0 0

20th

Right away
after
treatment C.
cm After lOmuliticm
To wash G
sec C.
cm FG
sec sec 5.1
7.8 F.
sec 0
0 6.7
9.2 η ο
0 0 0
0 Example 6

The same treatment was applied to textile material

stirred from polypropylene, but 5 Mi- 1 mole of ethylene dibromide and 2 moles of ethylene thio-

was heated to 110 ⁰ C slots. In addition, urea was refluxed in ethanol for 10 hours

the same treatment also applied to textile materials from ₂₅ , the following compound being formed

Polyacrylonitrile performed using these materials:

CH ₂ -NH

C-S-CH ₂ -CH, -SC

CH, - NH NH- CH,

NH- CH,

2Br

A 40% formalin solution containing 1 mole of the bis-thiuronium salt and 4 moles of formaldehyde, was stirred at room temperature and then at 50 to 60 ° C. for 5 hours with stirring held. The obtained methylol compound was diluted with water to prepare the treatment bath, which had 15% solids content.

Test pieces of textile material were immersed in the bath and then ironed (humidity table 7th

recording 100%). They were dried and heated to 130 ° C. for 5 minutes, whereby a textile material obtained with a permanent flame retardancy, im In the case of polyacrylonitrile fibers, the dried sample was treated with supersaturated steam for 5 minutes In the case of polypropylene fibers, the dried sample was heated to 100 ° C. for 5 minutes.

The results of the flame retardancy tests are shown in Table 7.

Textile material

After treatment F G

After washing 10 times

Cotton 0 0

Reyon 0 0

Acetate 0 0

Wool 0 0

Polyvinyl chloride 0 0

Nylon 0 0

Polyester 0 '0

Polyacrylonitrile 0 0

Polyester to cotton 0 0

Nylon to rayon 0 0

Polyacrylonitrile to wool 0 0

Polypropylene 0 0

C cm

4.0 4.3 4.5 2.0 3.0 5.0 4.5 6.0 4.8 5.3 4.8 5.5

0 0 0 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 0 5.2
5.5
5.8
3.0
3.7
5.8
5.5
7.0
5.3
6.0
5.6
6.0

After 3 times chemical cleaning

F G C

see see

0 0 0 0 0 0 0 0 0 0 0 0

0 0 0 0 0 0 0 0 0 0 0 0

cm

5.0 4.9

5.2 2.5 3.5 5.5 4.8 6.3 5.1 5.5 5.3 5.9

example

1 mol of ethylene dibromide and 2 mol of guanylthiourea were refluxed H) Slundcn in ethanol, resulting in the following connection:

NH ₂

CS -CH ₂ -CH ₂ - SC

NH ₂ -C-NH

NH

NH ₂

NH-C-NH ₂ · 2Br
NH

A 40% formialin solution with 1 mole of the bisthiuronium salt and 6 Mo '! Formaldehyde was stirred at room temperature and then during Maintained at 50 to 60 ° C. for 5 hours with stirring.

The compounds obtained were washed with water diluted after 0.2 mol of guanidyl phosphate to Table 8

were set. In this way a treatment bath of 20% solids was obtained.

Test pieces of textile material were dipped into the bath and ironed (100% moisture absorption). As in Example 6, they were subjected to a heat treatment. The results of the atx flame resistance tests are summarized in Table 8.

TcMilni Material To treatment C. To IQmahgcm To wash To 3nial chemical ch « C. F. G cm F. G C. F. ü cm lake lake 3.8 lake lake cm lake lake 4.5 cotton 0 0 4.0 0 0 5.0 0 0 4.5 Reyon 0 0 4.1 0 0 4.8 0 0 5.0 acetate 0 0 2.0 0 0 5.2 0 0 2.6 Wool 0 0 2.8 0 0 2.8 0 0 3.1 Polyvinyl chloride 0 0 4.8 0 0 3.2 0 0 ' 5.2 nylon 0 0 4.3 0 0 5.7 0 0 5.0 polyester 0 0 6.0 0 0 5.3 0 0 6.5 Polyacrylonitrile 0 0 4.5 0 0 6.8 0 0 4.9 Polyester to cotton 0 0 5.0 0 0 5.2 0 0 5.2 Nylon to rayon 0 0 4.8 0 0 5.9 0 0 5.0 Polyacrylonitrile to wool 0 0 5.3 0 0 5.0 0 0 5.5 Polypropylene 0 0 0 0 5.9 0 0

Example 8

1 mole of benzyl chloride and 1 mole of N.N'-dimethylthiourea were refluxed in ethanol for 10 hours, S-benzyl-N.N'-dimethyl-thiuronium chloride originated. A 40% formalin solution with 1 mole of the thiuronium salt and 1 mole of formaldehyde was stirred at room temperature and then

Table 9

5. Maintained at 50 to 60 ° C. for 2 hours with stirring. The reaction product was diluted, a treatment bath having a 15% solids content being obtained.

Samples of textile material were dipped into the bac and ironed (100% moisture absorption would take). They were made according to the heat treatment; Subjected to Example 6. The results of the flame strength tests are summarized in Table 9.

Textile material N / A ch treatment C. To lOmaligcm To wash To 3 times cr Dry cleaning university F. G cm F. G C. F. G C. lake lake 6.0 lake lake cm lake lake cm cotton 0 0 6.8 0 0 6.8 0 0 6.5 nylon 0 0 6.3 0 0 7.9 0 0 7.3 polyester 0 0 7.0 0 0 7.8 0 0 7.0 Polyacrylonitrile 0 0 7.5 0 0 8.2 0 0 7.9 Polypropylene 0 0 0 0 8.5 0 0 8.0

Example 9

Example K)

Textile samples were each of the textiles treated according to Example 6 in an 8% strength aqueous solution

one of each of the following compounds was sampled in an aqueous solution with 7 ° / ί each

dipped in the following compounds and mangled with soda (moisture absorption 80%). Each dei Samples were dried and heated to 130 ° C. for 5 minutes. Furthermore, the samples were washed in order ίο dried, being textile materials with permanent Flame resistance were obtained.

submerged.

NaSO ₄ - CH ₂ -CH ₂ -SO ₂ -CH ₂ -CH ₂ -SO ₄ Na

NaSO ₄ - C ₂ H ₄ - SC ₂ H ₄ - SO ₄ Na
C ₂ H ₄ -SO ₄ Na

BrCH ₂ CH ₂ CH ₂ O- POjNa ₂

NaOOC-CHBr-CHBr-COONa

(C)

Each fabric sample was lacking (Moisture absorption 80%) and dried at 60 to 70 ⁰ C.

Each of the treated fabric samples was dissolved in a 20% aqueous solution of a compound of the following formula

NH ₂ NH ₂

CS-CH ₂ -CH ₂ -CH ₂ -SC -2Br
NH, NH,

ClCH, CH, O

P-CH ₇ COONa

ClCH, CH, O O

Ammonium salt of polyvinyl alcohol phosphate

Zinc borate

35

immersed. Each sample was wrapped around (80% moisture absorption), dried and heated to 130.degree. The treated samples were washed and dried and made permanently flame retardant textile materials. The results of the Flammfestig- ₄ o Table! Performance tests are compiled in Table 10.

The results of the flame resistance tests are shown in Table 11.

Sub- To C.
cm To lOmaliucm C.
cm 45 Fiber material medium To cm According to I. Omalij: C. Table 10 slan7 To wash To wash cm H
lake treatment 4.8 F. 5.0 6.1 F. 4.9 lake 5.2 Textile material 5.1 6.1 5 ° lake 6.9 5.4 (a) 6.5 0 7.9 cotton (a) 0 8.0 (a) treatment 0 Reyon (a) 0 10.1 0 (a) 1-
lake 7.1 0 9.6 Polyester too (a) 0 5.0 0 11.3 5.2 6.1 cotton 0 5.0 5.1 cotton (a) 5.4 0 6.0 55 polyester (a) 7.2 0.8 5.3 Reyon (b) 0 6.4 0 8.0 cotton (b) 0 0 8.1 Polyester too (b) 0 0 Reyon (b) 0 10.5 0 cotton (b) 0 7.2 0 10.1 Polyester too (b) 0 5.1 0 11.6 nylon 4.4 5.7 6o cotton 0 5.2 7.2 cotton (b) 0 4.4 0 5.5 polyester (b) 7.1 0.7 7.5 Reyon (C) 0 6.2 0 10.0 cotton (C) 0 0.1 9.7 Polyester too (C) 0 0 Reyon (C) 0 4.9 0.1 cotton (C) 0 0 Polyester too (C) 0 4.8 0.3 5.3 nylon cotton 0 7.6 5.4 cotton 0 cotton <d) 0 8.8 Reyon 0 Reyon (d) 0 0 Polyester too 0 Polyester too (d) 0 0 cotton 0 cotton 0

Example Π

In each case, an aqueous solution of 15% of the following compound was obtained

5 CH ₅ O NH- CH, OCH,

P-CH-, CH, -S- C Br

C ₂ H ₅ OO NH-CH ₂ OCH.,

and 5% of the compound listed in each case. Samples of fabric were immersed and then ironed (80% moisture absorption). They were dried and heated to 130 C and then washed and dried. Textile materials with permanent flame resistance were obtained.

(a) trimethylolmelamine,

(b) dimethylolthiourea,

(c) tetramethylolphosphonium chloride.

The results of the flame retardancy tests are shown in Table 12.

Table 12
Fiber material

cotton

Reyon

Polyester too

cotton

cotton

Reyon

Polyester too

cotton

nylon

cotton

Reyon

Polyester too

cotton

polyester

16

Treatment after hand- treatment lunsis-

niiltel H C

see cm

(a) O (a) O (a) O

(b) (b) (b)

(b)

(C)

ic)

(C)

0 0 0

0 0 0 0

5.6 5.8 8.0

5.4 5.5 7.9

8.1

4.5 4.4 6.7

After 100% washing

lake

0 0 0

0 0 0

0 0 η 0

(c) 0 8.5

cm

6.3 6.5 9.2

5.9

5.8 9.1

10.4 5.3 5.0 8.8

11.0

example

In each case an aqueous solution of 20% of the compounds listed below was prepared. In these Solutions were immersed in fabric samples. These were then ironed (i! 0% moisture absorption), they were dried and heated to 130 ° C. for 5 minutes and then washed and dried. There were textile materials obtained with permanent flame resistance.

CH ₃ SC

NH,

NH-CH ₂ -CONH-CH =

HIGH ₂ -NHCOCh ₂ - SC

Cl

NH, N NH ₂

CS-CH ₂ CH ₂ -OC C-OCH ₂ CH ₂ -SC

NH ₂ NN NH ₂

c 'NH,

I / "s-c

2Br Cl

The compound (a) was prepared by adding thylformamide at room temperature for a

Acrylamide, thiourea, and formaldehyde were treated at the day. The compound (b) was

Compound by reacting N-methylol-chloroacetamide with

Made of thio resin. The compound (c) was

CH ₂ = CH-CONH-CH ₂ -NHCSNh ₂ by condensation of 1 mol of cyanuric chloride with

2 mol Äthylenbromliydrin and subsequent conversion

implemented. which are then obtained with an excess of 3 moles of thiourea. The result

17th

The results of the flame resistance tests are summarized in the table.

Table 13

Fiber lvp

Fiber type

Cotton Re yo ^
Polyester to Cotton Polyester Cotton Rayon
Polyester to cotton

After hand- treatment luiigs-

Hiittel F C

see cm

(a) (a) (a)

O O O

O O O O

According to lOnmlmem

Washing cotton

P c rayon

see cm ίο p _o ly _es ter ZU

cotton

5.0

5.1 7.7

8.6

6.3

6.2 10.5

6.7

6.9

10.4

13.0

9.6

10.0

13.3 18

After

hand-treatment

lung

mean F C

Rope to IOn Wa

lake

(C) 0 (C) 0 (C) 0

6.0 0

6.0 0

10.1 0

cm

12.9

Example 13

, ₅ A 20% solution of the substance listed below was prepared in each case. Samples of textile material were immersed in these solutions. These were then ironed (100% moisture absorption). They were dried and left on for 3 minutes

140 ⁰ C heated and then washed and rocked. Textile materials with permanent flame resistance were obtained in this way.

CH ₃ O

NH ₂

NH ₂

/ \ CS-CH ₂ CH ₂ -NH-C C -C _{-NH-CH 2} CH _{2 -SC}

3Br

CH ₃ O

N
\ N
// H -CH ₂ - \ '/
C. -NH ®N (CH ₃ /
C. N
' V
C- N N
// ₂ OH a
NH \ V
C.
I. NHCH N

XIII

^NH 2

NH,

Br

NH,

NH ₂

CS-CH ₂ CH ₂ -OC CSC Br ⁰ 2Cl

/ Il I \

NH ₂ NN NH ₂

\ / C NH ₂

I / s-c

NH ₂

/ \ BrCH ₂ CHCH ₂ -OC CO-CH ₂ CHCH ₂ Br

Br NN Br

C NH ₂

I // s - c Br

NH,

19th

The results of the flame retardancy tests are shown in Table 14.

20th

1,3,5-triazine obtained. This triacin was brominated which led to the following connection:

Table 14

Fiber type

cotton

Polyester too

cotton

cotton

Polyester too

cotton

polyester

cotton

Polyester too

cotton

cotton

Polyester too

cotton

After

hand-treatment

lung

mean F C

(a) 0

(a) O

(a) O

(b) 0 (b) 0 (b) 0

(b)

(C) (C) (C)

(d) (d) (d)

0 0 0 0

0 0 0

6.1 6.0 9.8

5.3 5.3 6.4

8.7 6.5 6.4 7.1

5.9

5.8 8.0

After washing 10 times

F see

0.1 0.1 0.2

0 0 0

0.3 0.3 0.5

0.1 0.2 0.4

cm

8.9

9.1

13.0

8.0 8.0 9.0

12.4 10.6 10.8 14.1

9.0

9.7

14.0

Example! 14th

1 mole of cyanuric chloride was mixed with 2 moles of allyl alcohol in dioxane in the presence of an alkali catalyst implemented. This 2,4-bis-allyloxy-6-chloro

BrCH ₂ CHCH ₂ -OC CO-CH ₂ CHCH ₂ Br

Br N N Br

Cl

Moles of this compound were reacted with 3 moles of thiourea to obtain an excellent agent for flame retarding textile materials, and textile samples were immersed in an aqueous solution of 15% of this compound. These have been lacking (70% moisture absorption) and dried, followed by 3 minutes 14O ⁰ C heated. The textile materials were given permanent flame resistance. The results of the flame retardancy tests are shown in Table 15.

table

Textile material

40

Cotton polyester to cotton nylon polyester Immediately after ten times after washing

treatment

FGCFGC
sec sec cm sec sec cm

0 0 5.2 0 0 6.1

0 0 6.5 0 0 7.8

0 0 7.5 0 0 8.5

0 0 7.0 0 0 8.3

example

1 mole of bromoethoxy-trichloro-pyrimidine was reacted with 3 moles of thiourea, the following compound originated:

NH ₂

©
NH,

CS-CH ₂ CH ₂ -OC C-S-C

NH,

2Cl ⁽ⁱ Br °

Cl-C N

C NH ₂

i /

s -c NH,

This connection is a good means of creating permanent flame resistance.

/1%

A compound of the formula

Example 16

CH ₂ BrCH ₂ CH-CO-N ^ -CO-CH = CH ₂

CH, CH,

CO-CH = CH ₂

(Hexahydro-triazine derivative) was reacted with thiourea to give a compound of the following Formula:

NH ₂ CH,

C-S-CH, -CH-CO-N N-CO-CH = CH ₂

NH,

CH ₂

2Br

S-C

NH,

NH,

CO-CH = CH ₂

which is an excellent means of providing permanent flame retardancy.

Example 17

Melamine was added to an aqueous formaldehyde solution with a pH of 8 to 9 and a content of sodium carbonate in such an amount that 1 mole of melamine per 3 moles of formaldehyde. This addition was carried out with stirring, and the resolution took place at about 6O ⁰ C. The mixture was then heated to 80 to 90 ° C. in order to bring about the reaction. The reaction product was a transparent syrup of melamine resin. Ethyl pseudo-thiourea hydrobromate (15% solids content) was added to this syrup, whereupon rayon pulp was mixed in and the whole was kneaded. After kneading, the mixture was ^{dried with air at 60 to 80 °} C. and pulverized. A hardener was then added. The melamine resin powder was molded under a pressure of 105 to 150 kg / cm ² at 135 to 15O ^'J C. The molded product had excellent flame resistance compared to molded articles without the addition of ethyl pseudothiourea hydrobromate.

Example 18

A basic amount of 1 mole of polyvinyl alcohol and 1 mole of thiourea was _{reacted in the presence of 12 moles of 80% H 3} PO ₄ at 125 ° C. for 13 hours to give a polymer in which about 27% of the hydroxyl groups of the polyvinyl alcohol were substituted by thiuronium salt groups. Textile samples were immersed in the aqueous solution containing 7% of this thiuronium salt of polyvinyl alcohol. These were then ironed (80% moisture absorption). After drying, heating was carried out at 130 ° C. for 5 minutes, followed by washing with water and drying, whereby textile products excellent in permanent flame resistance were obtained. The test results are shown in Table 16.

Table 16

Textile material To G C. Nai Ci C. lake one : h lOmahucm lake em treatment 0 10.0 To wash 0 11.0 F. 0 6.7 F. 0 7.1 nylon lake 0 8.2 lake 0 8.8 cotton 0 0 Po lyes! ·. ■ to 0 0 7.1 0 0 8.2 cotton 0 0 Polyvinyl type 0 0

Claims (1)

Claim: Process for the flame retardancy of fiber. Film and foil material, plates and others Bodies made from natural and synthetic polymers, characterized in that man the body with a compound of the formula