JPS5939549B2 - Flame retardant processing method for fiber products containing cellulose fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for flame retardant processing of textile products containing cellulose fibers, and more specifically to textile products containing cellulose fibers, especially mixed fiber products consisting of cellulose fibers and polyester fibers. The present invention relates to a processing method that does not cause texture hardening and imparts durable flame retardancy.

Research to make organic combustible fibers flame retardant has been widely conducted for a long time, and although processing methods suitable for individual fiber materials have been established, there are still problems in terms of durability and texture hardening. have.

Furthermore, non-melting hydrophilic fibers such as cellulose fibers and meltable hydrophobic fibers such as polyester have fundamentally different flame retardant mechanisms and adhesion properties of flame retardant processing agents. It is extremely difficult to make mixtures of cellulosic fibers and polyester fibers flame retardant, and it has not yet been possible to impart durable flame retardancy without hardening the texture.

The present inventors have succeeded in imparting excellent durable flame retardancy to a mixture of cellulose fiber and polyester fiber, which is the most difficult to achieve durable flame retardancy, and creating a texture suitable for clothing. As a result of intensive research in order to obtain flame-retardant products, the method of the present invention was arrived at.

That is, the present invention provides fiber products containing cellulose fibers,
A phosphonium oligomer obtained by heating and condensing a tetrakis(hydroxymer)phosphonium compound and/or a water-soluble nitrogen-containing phosphonium oligomer obtained by heating and condensing a tetrakis(hydroxymethyl)phosphonium compound and an amino compound, aminoaldehyde and/or
Alternatively, it is characterized in that it is treated with a treatment liquid containing an amine compound (Bl and an unsaturated phosphonate or a derivative thereof) and then subjected to heat treatment.

Conventionally, durable flame retardant processing methods for polyester/cotton include processing methods using a combination of tetrakis(hydroxymethyl)phosphonium compounds (hereinafter abbreviated as THP compounds), aminoaldehyde and amine compounds, heating the THP compound,
A processing method in which a phosphonium oligomer obtained by dehydration condensation is used in combination with a polyfunctional compound such as an aminoaldehyde and/or an amino compound (JP-A-47-3345);
Alternatively, a processing method in which a nitrogen-containing phosphonium oligomer obtained by heating and dehydrating a THP compound and an amine compound is used in combination with a polyfunctional compound such as an aminoaldehyde and/or an amino compound (Kokai No. 47-25270, JP Showa 48-36489-36495, rib opening Showa 48-80
893 to 80897, etc.) are known.

However, the textile products obtained by these processing methods are not only unsuitable for use in clothing because of their extremely stiff texture, but also have drawbacks such as insufficient flame retardant durability.

On the other hand, a processing method in which a phosphorus-containing compound is fixed by copolymerizing on fibers, reaction between methylol groups, and reaction of methylol groups on cellulose fibers using a combination of vinyl phosphonate derivatives and N-methylol acrylamide was also proposed in JP-A No. 4.
6-5498, but in order to obtain durable flame retardancy, it is necessary to use a large amount of N-methylolacrylamide, which causes hand hardening and copolymerization reaction to proceed in the treatment solution. As a result, the texture of the treated product tends to change, making it difficult to obtain a reproducible and stable texture, and in some cases, the processing solution may gel, making it unusable. There is.

When the method of the present invention is used, hand hardening in THP processing is reduced by using an unsaturated phosphonate or its derivative in combination with the flame retardant processing formulation using such a THP condensate, and a flame retardant treatment particularly suitable for clothing is achieved. It provides processed products.

Furthermore, when used in combination, durable flame retardation can be obtained with little or no use of N-methylolacrylamide, so the stability of the treatment liquid is excellent and a stable texture can always be obtained.

Although it is not clear why the method of the present invention provides flexible and durable flame retardation, it is clear that unsaturated phosphonates or their derivatives have good compatibility with THP-amino aldehydes and/or amino compounds and have a plasticizing effect. It is thought that this is because it not only exhibits the properties of carbon dioxide, but also contributes to flame retardancy.

As the phosphonium oligomer and/or nitrogen-containing phosphonium oligomer used in the present invention, tetrakis(hydroxymethyl)phosphonium compound (hereinafter referred to as T
HP compound) or a condensation product of a THP compound and an amino compound. Tetrakis(hydroxymethyl)phosphonium compounds include tetrakis(hydroxymethyl)phosphonium chloride (hereinafter abbreviated as THrC), tetrakis(hydroxymethyl)phosphonium protonium Mido, Tetrakis(hydroxymethyl)phosphonium iodide, Tetrakis(hydroxymethyl)phosphonium phosphate, Tetrakis(hydroxymethyl)
Phosphonium acetate, Tetrakis(hydroxymethyl)phosphonium propionate, Tetrakis(hydroxymethyl)phosphonium oxalate, Tetrakis(
hydroxymethyl)phosphonium hydroxide, etc., and these THP compounds are heated and condensed in advance to synthesize a phosphonium oligomer, and this is used in combination with an aminoaldehyde and/or an amine compound, or
A water-soluble nitrogen-containing phosphonium oligomer is synthesized by heating and condensing the HP compound and an amine compound and/or an amino aldehyde in advance, and an amino aldehyde and/or an amino compound is further added thereto for use.

However, water-soluble nitrogen-containing phosphonium oligomers and aminoaldehydes and/or amino compounds are used in combination because they are easily cured on the fibers, giving them excellent flame retardancy and durability, and giving a reproducible texture. The law is particularly clever.

The amount of phosphonium oligomer or nitrogen-containing phosphonium oligomer used as an active ingredient is usually 5% based on the weight of the fiber.
~30%, preferably 10-25%.

Further, examples of the amine compound used in the present invention include urea, thiourea, dicyandiamide, guanylurea, guanidine salt, alkylene urea, alkyl triazone, alkyl carbamate, etc. The amount of the amine compound used in the synthesis of the nitrogen-containing phosphonium oligomer is T, HP
The amount of the amine compound is usually 0.5 mol or less, preferably 0.001 to 0.2 mol per mol of the compound.

When a phosphonium oligomer or a nitrogen-containing phosphonium oligomer is used in combination with an amine compound, the amount of the amine compound used is usually 30% or less based on the weight of the phosphonium oligomer or nitrogen-containing phosphonium oligomer,
Preferably it is 2 to 20%.

Examples of aminoaldehydes include reaction products of the above amino compounds and aldehydes such as formaldehyde and glyoxal, and initial condensates obtained by further modifying the reaction products with lower alcohols.

The amount used is usually 15 parts or less, preferably 2 to 10 parts, based on the weight of the fiber.

Furthermore, unsaturated phosphonates or derivatives thereof used in the present invention include bis(chloroethyl)vinylphosphonate, bis(bromoethyl)vinylphosphonate,
Bis(chloromethyl)vinylphosphonate, diethylvinylphosphonate, diisopropylvinylphosphonate, polycondensed vinylphosphonate obtained by condensation of bis(chloroethyl)vinylphosphonate described in JP-A-46-5498 (where X = an integer of 1 to 20%) ), polycondensed vinylphosphonates having one or more unsaturated groups, such as (X: alkoxy group, cycloalkoxy group, allyloxy group, aryloxy group, N-dialkylamino group, etc.).

R: divalent or polyvalent aliphatic or aromatic group having 2 to 12 carbon atoms m: integer from 2 to 6 R': divalent substituted or unsubstituted alkylene group, arylene group, n: 2 - an integer of 100), etc., and these may be used alone or in combination of two or more.

However, unsaturated phosphonates have a molecular weight of 300 to 1000.
Polycondensed vinyl phosphonates are particularly preferred.

If the molecular weight is low, the volatility will reduce the processing effect and cause odor generation, while if the molecular weight is high, it will inhibit penetration into the fibers, reduce the plasticizing effect, and reduce texture hardening. It becomes difficult to do so.

The amount used is usually 5 to 30% based on the weight of the fiber,
Preferably it is 10-25%.

To explain the treatment method of the present invention in more detail, an aqueous solution of a phosphonium oligomer or a nitrogen-containing phosphonium oligomer is preferably adjusted to pH 4 to 8 with an inorganic or organic alkali such as caustic alkali, alkali carbonate, alkanolamine, or alkylamine. After that, 'amino aldehyde and/or amino compound is added, and further, to the unsaturated phosphonate or its derivative, preferably the polymerization initiation catalyst, and optionally the vinyl phosphonate or its derivative, 25 weight φ or less of acrylamide,
Nitrogen-containing derivatives of acrylic acid or methacrylic acid such as N-alkyl acrylamide, N-methylolacrylamide, N-alkoxymethylacrylamide, and if desired, small amounts of softening and smoothing agents, penetrants, and known agents within the range that do not impair the texture. A treatment liquid obtained by adding a flame retardant and the like is applied to a textile product by any means such as a pad method, a spray method, a coating method, a transfer method, etc., and then it is usually preferably dried and then heat treated.

Examples of the polymerization initiation catalyst used include organic or inorganic peroxides such as persulfates, perborates, benzoyl peroxide, and azoisobutyronitrile, but from the viewpoint of solubility and discoloration during processing, particular Potassium persulfate is preferred.

The heat treatment may be either dry heat or wet heat, but dry heat treatment is preferred from the operational and versatility standpoint, and the heating conditions are usually 120~120℃.
0.5 to 10 minutes at isoC is sufficient, preferably 3 to 5 minutes at 150 to 160C.

After heat treatment, it is usually oxidized, then soaped, and then dried.

The cellulose fiber-containing fiber products to which the present invention is applied include not only 100% cellulose fiber products such as cotton, hemp, regenerated cellulose, and copper ammonium rayon, but also cellulose fibers and synthetic fibers such as polyester, polyamide, and polyacrylonitrile. , cellulose acetate, semi-synthetic fibers such as protein-acrylonitrile graft copolymers, mixed fiber products with protein fibers such as wool and camel, but especially cellulose/polyester fibers that are difficult to make durable and flame retardant. The effect is remarkable when applied to blended textiles, mixed knitting, mixed knitted fabrics, nonwoven fabrics, etc.

Of course, the polyester fiber is flame retardant modified polyester,
It may also be a modified polyester fiber, such as a modified polyester dyeable with ionic dyes.

The present invention will be described below with reference to examples.

Note that parts and parts in the examples are by weight unless otherwise specified.

Example 1 A polyester/i (65/35) blended broadcloth was padded with eight types of treatment liquids shown in Table 1, and after squeezing the liquid to a squeezing rate of 80 inches, it was pre-dried at 80°C and then dried at 160°C for 3 minutes. After heat treatment, a conventional wet oxidation treatment was performed, followed by soaping and drying.

Cantilever method JISL-10 for hardness of the obtained treated fabric
04), flame retardant (JIS L 1091A-1 method 45)
° Microburner method) was evaluated and the results are shown in Table 2.

By the method of the present invention, it was possible to reduce the hardening of the texture caused by the THPC-amide condensate treatment, and to obtain an excellent flame-retardant fabric that was rich in durability.

Example 2 Flame-retardant modified polyester (manufactured by Toyobo Co., Ltd., Heim) / Cotton /
A 65/35 blended broadcloth was treated in the same manner as in Example 1 using the treatment liquid shown in Table 3.

By the method of the present invention, an excellent flame-retardant fabric that is flexible and durable was obtained.

Example 3 A polyester/cotton (65/35) blended broadcloth was treated in the same manner as in Example 1 using a treatment solution having the following formulation.

THPC-amide condensate used in Treatment Solution Example 1 30 parts Trimolecular compound of bis(chloroethyl)vinylphosphonate
10 parts Sumitex Resin M-
33 parts N-methylol acrylamide 2 parts Eleganol SRT Part B DIC Silicone Softener TS (manufactured by Dainippon Ink Co., Ltd., softener) 1 part Potassium persulfate 0.5 part Water
50.5 parts As a result, an excellent flame-retardant fabric that was flexible and durable was obtained.

Claims (1)

[Claims] 1 Phosphonium oligomer obtained by heating and condensing a tetrakis(hydroxymethyl)phosphonium compound and/or a water-soluble nitrogen-containing phosphonium obtained by heating and condensing a tetrakis(hydroxymethyl)phosphonium compound and an amine compound on a cellulose-based fiber-containing textile product A flame-retardant processing method for textile products containing cellulose fibers, which comprises treating with a treatment liquid containing an oligomer (5), an aminoaldehyde and/or an amino compound (B), and an unsaturated phosphonate or a derivative thereof, followed by heat treatment. .