JPS58120877A - Fire retardant processing of cellulose fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame retardant processing method for cellulose fibers.

Conventionally, flame retardants that have wash resistance for cellulose fibers include tris(1-aziridinyl)phosphine A oxide (APO), tetrakis(hydroxymethyl)phosphonium chloride (THPC), or phosphorus-containing N-methylol compounds [ For example, N-methyloldimethylphosphonopropionamide (Bilobatecus CP>) has been used. However, because APO has acute dermal and oral toxicity, its use was prohibited on January 1, 1971 (
Ministry of Health and Welfare Ordinance No. 40, September 24, 1978). THPC
THPC is dangerous because liver function impairment is observed, and bis(chloromethyl)ether, a carcinogen, is produced from formaldehyde and hydrogen chloride generated during processing. Condensation hardens the texture of the fibers.Furthermore, with phosphorus-containing N-methylol compounds, flame-retardant processing uses a processing agent at a higher concentration than normal resin processing, which causes problems during processing and in the product. In both cases, there are problems such as the release of high concentrations of formaldehyde.The current oil crisis calls for energy conservation.
For the reaction between N-methylol compound and cellulose, 15
Since a curing temperature of 0 to 160° C. is required, the development of a processing method for low temperature curing is eagerly awaited.

This invention was made in view of the above background, and
By using a graft copolymerization reaction other than the reaction using methylol groups, that is, by generating radicals on cellulose with cerium (IV) ions, bis(2-chloroethyl)
By graft-copolymerizing vinyl-containing hetamines such as vinyl phosphonates at low temperatures near room temperature and processing them into cellulose fibers, they have good wash resistance, do not release formaldehyde, and are similar to THPC. Because there is no mutual condensation reaction on the fiber surface, the texture is not impaired.
Moreover, since the reaction occurs at room temperature, the purpose is to obtain a cellulose fiber product that is useful for energy saving and has a high flame retardant effect.

In summary, this invention uses cerium (TV) ions to inject cellulose fibers with a phosphorus-containing vinyl monomer (A) such as bis(2-chloro5-loethyl)vinylphosphonate or vinylidene chloride. A binary comonomer of a halogen-containing vinyl monomer (B), or a vinyl monomer (C) copolymerizable with the above (A) or (B) such as vinyl acetate, or the above (A) or (B).
), (C) is a processing method that imparts flame retardancy to cellulose fibers by graft copolymerizing the ternary comonomers.

The fibers treated in the method of this invention include cellulose fibers (cotton, linen), regenerated cellulose fibers (rayon,
There are fibers having -08M such as (Cupro), or blended fibers or interwoven fabrics thereof. Also, like wool, silk, and nylon, there is an amino group, -8H! Fibers with I are also possible. In addition, flame retardancy can also be imparted to cellulose such as paper and wood.

Monomers to be graft copolymerized include phosphorus-containing vinyl septamers such as bis(2-chloroethyl)vinylphosphonate, diethylvinylphosphonate, diphenylvinylphos-6-phine, [·liphenylvinyl small sulfonium bromide, and vinylidene monochloride. , halogen-containing vinyl monomers such as vinyl chloride and vinyl bromide, nitrogen-containing vinyl monomers such as acrylamide and acrylonitrile, and vinyl acetate, which is easily copolymerized with the above monomers and graft-copolymerized onto cellulose with cerium (IV) ions. , methyl methacrylate, styrene, etc.

Phosphorus-containing vinyl monomers such as bis(2-chloro[]ethyl)vinylphosphonate alone are difficult to graft copolymerize onto cellulose with cerium (IV) ions in an aqueous solution. However, bis(2-chloroethyl)vinylphosphonate (M,) and vinyl acetate (M2
) (r, -0,19°r2=0.07), styrene (M2) (r, -000, r2-3.49
) Aru Iha 7') 'J Roni t-jJ Le (M2)
It is easy to copolymerize the binary = 1 monomer with (r + "0.13. is 50 mol% or more of bis(2-chloroethyl)
Vinylphosphonates can be graft copolymerized. Graft copolymerization of ternary comonomers of bis(2-chloroethyl) vinyl small sulfonate, vinylidene chloride, and vinyl acetate imparts sufficient flame retardancy to cellulose fibers.

As a cerium (IV) ion, cerium nitrate (■)
There is ammonium, cerium (IV) sulfate, and ammonium. Cerium (■
) ion naturally has a higher monomer grafting efficiency than other water-soluble initiators that generate free radicals in aqueous solution, such as ammonium persulfate and potassium persulfate, and can graft copolymerize onto cellulose even at around room temperature. In addition,
Ce(NOs)4-2 (N84 NO#) is better than Ce(SQ,)2 ・2 (Nl-1,)2So
, ・Generates radicals on cellulose at a lower temperature than 2H20. The cerium NV) ions generate radicals on cellulose in the following reaction.

The general formula for the reaction of cerium (IV) ion to a compound having H2O3 1)-101-I CH20)19--OH group is as follows.

RCH20H+　Ce” →[RCH20H-Ce1v] ← ■ 1+RCHOH+Ce+H” The decombustion process is expressed as a formula: \ OCH2C82C1 \. 1 +CH2-CH 0-CCH.

1 e1v −→Craft cellulose underwater becomes. Processing methods are solution reaction, pad, and dry.

This can be done using the cure method. Next, in a solution reaction, 10- The conditions are shown below.

In the graft copolymerization of comonomers of bis(2-chloroethyl)vinylphosphonate and vinyl acetate onto cellulose in aqueous solution with Ce(NO,)4-2(NH,No, ) at temperatures between 20°C and 40°C. In the range shown in graph 1, the rate increased linearly as the temperature increased. Therefore, it is preferable to carry out the graft copolymerization at 40°C. In graft copolymerization at 40°C, the graph 1~ rate increases with polymerization time. Comonomer of bis(2-chloroethyl)vinylphosphonate 3+l and vinyl acetate 21, cellulose 0.4Q, water 10°C
In the graft copolymerization with luster, [Ce1V] = 4
At a cerium (■) ion concentration of X 1 O 1 mol/fL, the grafting rate is maximum. This means that [Ce]<4
In the case of :T'Cori, [Ce]>4XIO-
In the case of "tl/l, cerium (IV) ions participate in the initiation reaction by reaction with cellulose, the termination reaction by reaction with propagating radicals as shown in the following equation, and the oxidation reaction of primary radicals on cellulose. It shows that

to Cl-12-CH~Ce -+-CH=CH+Ca
+H+1 X× From the above results, the cerium (IV) ion concentration is 4
It should be used at less than 10-' mol/min.

In the case of the comonomer of bis(2-chloroethyl)vinylphosphonate and vinyl acetate, the grafting rate was highest when no nitric acid was added, and decreased as the nitric acid concentration increased.

Ce at ffff1 (No, ), -2(NH4No
,) bis(2-chloroethyl)vinylphosphonate, vinyl acetate binary comonomers and their ternary comonomers with vinylidene chloride, by 4 x 10-' mol/Q,
The results of graft copolymerization on cotton sateen of 20% by volume are the first results.
Shown in the table. In Table 1, A is bis(2-chloroethyl)vinylphosphonate, B is vinyl acetate, and C is vinylidene chloride.

] Mono 7- Polymerization graph LOI Carbonized area b) Time Rate a) C intestine 2 mol% hr
% Flaming after 1 minute and 3 seconds Heating 8 51 24. 43 21.
5 o.

B /19 33 8 31 25 73 26.5 8,0 99,
6 36 34 8 25 25 80 9.1 30.7
41 A34 c) B 24 43 131 28.5 27
．． 4 42 a> m cloth 101 is 18.1.

b) 45° Micro Burner Fk (JIS, L-109
1-1973R, A-1 method) C) Molar composition of ternary copolymer: A (bis-13-(2-chloroethyl)vinylphosphonate) 40%, B
(vinyl acetate) 15%, C (vinylidene chloride) 45%.

From Table 1, flame retardancy was imparted to cotton sateen by graft copolymerization of these monomers. Processing using this method imparts flame retardancy that is superior to, but not inferior to, conventional products.

Next, examples of this invention will be described.

Bis(2-chloroethyl)vinyl small sulfonate 34 mol%, vinylidene chloride 42 mol%, vinyl acetate 24 mol%
Cotton satin (mesh tf 125.8 g/l') was added to a 20% by volume aqueous solution of a ternary comonomer consisting of
(-soaked, Ge (No, >4 -2(NH4NO
a) 4X10-'-EL/α was exposed at room temperature for 43 hours to react, and after the reaction, the treated fabric was washed with water. The grafting rate was 131%, and the composition of the grafted copolymer was bis(
2-chloroethyl)vinylphosphonate was 40 mol%, vinylidene chloride was 45 mol%, and vinyl acetate was 15 mol%. The oxygen index of the treated fabric is 28.5, and the result of testing by heating for 1 minute using the 45' micropar 14-Chi method (JIs, L-1091-1973R, A-1 method) shows that the carbonized area is 27.
．． 4 Cm2, passing the flammability Category 3 standard.

The texture of the treated cloth was soft.

In addition, bis(2-chloroethyl)vinylphosphonate 3
3 mol%, vinyl chloride 91236 mol%.

When a ternary comonomer containing 31 mol% of vinyl acetate was graft copolymerized for 25 hours under the same conditions, the grafting rate was 7.
A 3% treated fabric was obtained. The oxygen index of this treated cloth is 2
The carbonized area was 99.6 CIll' when tested using the 45° micro burner method (heating for 1 minute).

Also, bis(2-chloroethyl)vinylphosphonate 3
4 mol%, vinylidene chloride 41 mol%.

When a ternary comonomer containing 25 mol% of vinyl acetate was graft copolymerized for 25 hours under the same conditions, the grafting rate was 8.
A 0% treated fabric was obtained. This treated cloth was tested using a 45° micro burner method (heated for 1 minute) and the carbonized area was 30.7 cm2.

As described above, according to the method of the present invention, the problem of formaldehyde generation is solved by treating cellulose fibers using a reaction other than the reaction with N-medylol groups. That is, in order to generate radicals on cellulose fibers using cerium (1v) ions and graft copolymerize phosphorus-containing vinyl monomers, processing is carried out in a chamber m.
It is produced at a f-1 level, does not emit formaldehyde during or after processing, has a soft texture, and is bonded to fibers through covalent bonds, so it has good wash resistance and excellent AM properties. You can get a good product.

Claims (11)

[Claims] (1) Using cerium (IV) ions, add phosphorus-containing monomer (A) or halogen-containing vinyl monomer (B) to cellulose fibers, or apply the <A), (B)
) and at least one vinyl monomer (C) copolymerizable with at least one vinyl monomer (C) selected from the group consisting of vinyl acetate, styrene, methyl methacrylate, methyl acrylate, acrylamide, and acrylonitrile, or <A), A flame-retardant processing method for cellulose fibers, which comprises graft copolymerizing the ternary comonomers (B) and (C). (2) The phosphorus-containing vinyl monomer (A) is at least one compound selected from the group consisting of bis(2-chloroethyl)vinylphosphonate, diethylvinylphosphonate, diphenylvinylphosphine, and triphenylvinylphosphonium bromide. The processing method according to claim 1. (3) The halogen-containing monomer (B) is at least one compound selected from the group consisting of nylidene chloride, vinyl chloride, and vinyl bromide, according to claim 1 or 2. Processing method. (4) There is no monomer or comonomer in the processing solution.
．． Claim 1 containing 5 to 60% by weight
The processing method according to any one of Items 1 to 3. (5) Cerium (IV) ion is cerium nitrate (I
V) The processing method according to any one of claims 1 to 4, which is either ammonium or cerium sulfate (■) ammonium. (6) Cerium (IV) ions are present in the treatment solution at 5X
The processing method according to any one of claims 1 to 5, wherein the content is 10'mol/U to 1.6X10-2 mol/11. (7) The processing method according to any one of claims 1 to 6, wherein the graft copolymerization is carried out in water or an aqueous solution such as a dilute aqueous nitric acid solution or a dilute aqueous sulfuric acid solution. (8) The processing according to any one of claims 1 to 7, wherein the bath ratio (fiber amount to treatment liquid amount) when performing graft copolymerization is 1:5 to 1:100. Method. (9) The processing method according to any one of claims 1 to 8, wherein the graft copolymerization temperature is 10°C to 70°C. (10) The processing method according to any one of claims 1 to 9, wherein washing with water or washing with a solvent is performed after graft copolymerization. (11) The processing method according to any one of claims 1 to 10, wherein the cellulose fiber is cotton, hemp, rayon, cupro, or a blended fiber or a woven fabric thereof.