JPH01239166A - Processing agent for synthetic fiber product and processing using the same - Google Patents

Abstract

PURPOSE:To provide the title flame-retarding processing agent capable of giving synthetic fibers good feel and suitable durability without impairing color fastness, containing a specific phosphoric triester, a dispersant and a protective colloid. CONSTITUTION:The objective flame-retarding processing agent containing (A) a phosphoric triester of pentaerythritol of the formula (X is chlorine or bromine) with three hydroxyl groups in the four hydroxymethyl groups substituted by chlorine or bromine, (B) a dispersant consisting of an ethylene oxide adduct of a fatty acid alcohol etc., and (C) a protective colloid such as PVA. A synthetic fiber, esp. polyester- or polyamide fiber product is imparted with this agent followed by drying and then heat treatment at 170-220 deg.C. Said agent is especially suitable for polyester and polyamide synthetic fibers, and does not impair their color fastness. The fiber products treated with this agent are good in feel and excellent in resistance to domestic washing and dry cleaning.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a processing agent for synthetic fiber products, particularly a processing agent suitable for flame retardant processing of polyester or polyamide fiber products, and a processing method using the same. be.

Conventional technology of synthetic fiber products! As a fuel modifying agent, 1, 2, 5, 6
゜9.10-Hexabromocyclododecane and tris(l
, 3-dichloropropyl) phosphate, etc. are generally used, but although these can provide wash resistance and flame retardancy, they have problems such as reduced color fastness. In particular, aliphatic bromine-based flame retardants such as the former tend to cause problems in the sunlight fastness of processed products, and the use of phosphate ester-based flame retardants such as the latter causes oil stains and bleeds on processed products. This has the drawback of causing problems such as: and significantly reducing color fastness to rubbing.

Furthermore, when using these methods, there was a risk of adhesion of dregs and tar to the processed cloth and contamination of the housing.

OBJECTS OF THE INVENTION The object of the present invention is to provide a processing agent and a processing method that impart flame retardancy with good texture and performance to synthetic fibers without adversely affecting color fastness.

Structure of the Invention The present invention provides (a) an orthophosphoric triester of pentaerythritol in which three water M groups of four hydroxymethyl groups have been replaced with chlorine or bromine, that is, an orthophosphoric triester which is solid at -temperature; This objective was achieved by using esters.

The processing agent of the present invention combines the orthophosphoric acid triester of (a) above with at least one of a dispersant and a protective colloid agent (b). Note that the processing agent of the present invention may contain water.

Typical examples of the component (a) above include di(tribromoneopentyl)trichloroneopentyl phosphate, tris(dibromochloroopentyl)phosphate, tris(tribromoneopentyl)phosphate, and especially tris(tribromoneopentyl)phosphate. Preference is given to using tribromoneopentyl) phosphate.

Next, as the component (b) above, for example, dispersants and protective colloids commonly used in the textile processing and dyeing industries can be used, and representative examples include aliphatic alcohols, fatty acids, or aliphatic amines. ethylene oxide adduct,
Dispersants such as ethylene oxide adducts of phenols and their phosphonates, aromatic sulfonic acids and their formaldehyde condensates, phosphoric acid di- or triesters of ethylene oxide adducts of alkylphenols, or polyvinyl alcohol, polyvinylpyrrone, Protective colloid agents include water-soluble vinyl polymers such as polyacrylic acid and water-soluble modified celluloses such as carboxymethyl cellulose and hydroquine ethyl cellulose.

The processing agent according to the invention is normally used as an aqueous processing agent. The aqueous treatment agent is, for example, 5 to 75% by weight of component (A).
, preferably 20-600-60 weight, preferably 30-60 weight
500 to 50% by weight) of ingredients 1 to 25% by weight (however,
0 to 25% by weight of a dispersant and 0 to 5% by weight of a protective colloid,
Preferably 3-15% by weight of dispersant and 0-15% of protective colloid.
It is produced by charging the remaining water with the remaining water into a glass pole pulverizer, sand pulverizer, steel ball pulverizer, etc. to form an aqueous dispersion.

/The protective colloid may be added after grinding,
In addition, the component (a) has a particle size of 0.5 to 20 by pulverization.
．． cam, preferably 0.5 to 10 μm. Particularly good dispersions are obtained with particle diameters of 0.5 to 5 μm.

The present invention also provides a method for single-combustion processing of synthetic fiber products, particularly polyester (including cationically dyeable polyester) or polyamide fiber products, using such an aqueous treatment agent. This method can be achieved by diluting the aqueous treatment agent with water to obtain a processing liquid, applying it to the synthetic fiber product by dipping treatment, etc., drying it, and then heat-treating it.

It is preferable to process the synthetic fiber product so that the amount of component (a) attached is 0.5 to 8% by dry weight, and after the processing liquid is attached, the drying temperature of the synthetic fiber product is ,1
2 (preferably at 1°C or lower, for example 80 to 120°C, and the heat treatment temperature is preferably 170 to 220°C).

Generally, for polyester fiber products, the heat treatment temperature is 1
Preferably it is 75-220°C, especially 190-210°C, and in the case of polyamide fiber products it is preferably 170-190°C, especially 175-180°C. In addition, the heat treatment time may normally be about 10 to 180 seconds, and generally 20 to 180 seconds.
About 90 seconds is preferable.

In addition, in the case of polyester fiber products, by exhausting the aqueous composition containing the processing agent of the present invention under heating,
Effective processing becomes possible. For example, in a high-pressure dyeing machine, a processing liquid with a bath ratio of 1:5 to 1:50 (preferably 1:8 to 1:20) is used, and the temperature is 110 to 140°C (preferably 130
-135° C.) for 20 to 60 minutes (or may be treated in the same bath as disperse dyes and fluorescent dyes).

The polyester and polyamide fiber products that can be flame-retardant according to the present invention may be filament or stable cotton, yarn, tow, woven fabric, knitted fabric, non-woven fabric, etc., and may be dyed.

In the present invention, polyester means polyethylene terephthalate-based polyester, and polyamide means 6-nylon or 6.6-nylon.

Polyester and polyamide fiber products treated with the finishing agent of the present invention exhibit excellent flame retardancy that is durable even after multiple home washings and dry cleanings. There are no oil spills, bleeds, or low color fastness problems that are common when using aliphatic brominated flame retardants.

° "Burn, ~ ・no-1, Notice I A)) Lis(tribromoneopentyl) phosphate) 4
00g, 40g of adduct of 1 mol of lauryl alcohol and 13 mol of ethylene oxide (hereinafter referred to as EO)
, and 500 g of water to a steel ball crusher with an average particle size of 5 μm.
It was crushed until the following. After that, 5% water i9 of polyvinyl alcohol? &60g was added and mixed well. The resulting dispersion is stable for a long time and can be diluted as desired.

B) Tris(tribromoneopentyl)phosphate 3
60g, formaldehyde condensate of naphthalene sulfonic acid 58g, carboxymethyl cellulose sodium 2g
1 and 580 g of water in a steel ball crusher with an average particle size of 5 μm.
It was crushed until the following. The resulting dispersion flows easily and can be diluted as desired.

C)) Lis(tribromoneopentyl)phosphate 3
00 g, 1 mole of styrenated phenol and 20 moles of E
40 g of O adduct and 660 g of water were ground using a glass pole grinder until the average particle size was 3 μm or less. The resulting dispersion can be diluted and will form a precipitate if left to stand for a long time, but can be reconstituted by simple stirring.

D)) Lis(tribromoneopentyl)phosphate 3
60 g, 30 g of jetanolamine salt of phosphoric diester of alcohol with 4 moles of EO added to 1 mole of nonylphenol, 35 g of formaldehyde condensate of naphthalene sulfonic acid, and 475 g of water were milled using a glass pole mill until the average particle size was 2 μm or less. crushed to. After pulverization, 100 g of a 5% aqueous solution of hydroxyethyl cellulose was added and mixed. The resulting dispersion is stable for a long time and can be diluted as desired.

E) Tris(dibromoneopentyl) instead of 360 g of tris(tribromoneopentyl) phosphate
A dispersion liquid was obtained in the same manner as in B) above, except that 360 g of phosphate was used.

The resulting dispersion flows easily and can be diluted as desired.

F) 250 g of di(tribromoneopentyl)trichloroneopentyl phosphate, 8 of styrenated phenol
50 g of sulfate ester sodium salt of 020 mole adduct,
and 700 g of water were pulverized in a porcelain bead (diameter 6 mm) pulverizer until the average particle size was 5 μm or less. The resulting dispersion can be diluted, and although it will form a precipitate if left to stand for a long time, it can be reconstituted by simple stirring.

G)) Lis(tribromoneopentyl)phosphate 3
(iog, jl with styrenated phenol and 20 moles of EO
40 g of substance D, 50 g of sulfuric acid ester sodium salt of styrenated phenol and 20 mole adduct of EO, and 450 g of water
g was pulverized using a steel ball pulverizer until the average particle size became 5 μm or less. After pulverization, 100 g of a 5% aqueous solution of sodium salt of acrylic acid/maleic acid copolymer was added and mixed.

The resulting dispersion is stable over dilution periods and can be diluted as desired.

+1) Produce a dispersion in the same manner as in Production Example D) except that 360 g of 1,2,5,6.9.10-hexabromocyclododecane is used instead of 360 g of tris(tribromoneopentyl) phosphate. (known flame retardant).

I) 360 g of l-lith(1,3-dichloropropyl)phosphate), 40 g of tJU product with 20 moles of EO of styrenated phenol, and 20 g of styrenated phenol.
50 g of the 20 mole adduct sodium sulfate salt was mixed and emulsified in a homomixer while adding 550 g of water to obtain an emulsion with an average particle size of 0.5 μm (known flame retardant).

Examples 1 to 5 and Comparative Examples 1 to 4 Dispersions obtained in Production Examples A, C, D, and E (processing agents of the present invention)
as well as! ! ! Using the dispersions obtained in Preparation Examples H and I (known processing agents), aqueous processing solutions shown in Table 1 were prepared, and polyester fabrics (220 g/mJ) were thermosol-processed using these.

The polyester fabric was padded with the above aqueous processing solution, dried at 1°C for 5 minutes, and then heat treated under the conditions shown in Table 1, and then mixed with 2g of soda ash and 0.0% of an 8010 mole adduct of nonylphenol in 10100O. Washed with an aqueous solution containing 5 g for 5 minutes, rinsed with running water and dried.

The physical properties of the obtained product were measured by the following method.

The results are shown in Table 1.

1 star 1 hill 1 A fabric weighing approximately 50g that was melted and cut around the perimeter to prevent fraying was dried at 105℃ for 1 hour, and the weight increase at each stage was calculated based on the weight accurately weighed to two decimal places. Shown in %.

In the early period of 1 Kasayu and dated February 21, 1986, products after washing with water and dry cleaning 5 times each were subjected to the 45° micro burner method (JIS L-1091D method) according to Fire Department Notification No. 1.
A flame retardant test was conducted.

Digital color measurement color difference meter N according to JIS P-8123
Measured using D-1010 (manufactured by Rohon Denshoku Kogyo Co., Ltd.).

JL Hikari” 1 Carbon Arc Illuminated Fade-O-Meter F A
It was exposed for 100 hours using L-3II model (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 83° C., and evaluated using a gray scale for discoloration.

As is clear from the results in Table 1, the finishing agent according to the present invention not only gives polyester fabrics excellent JF flammability, but also has good white skin, texture, and light resistance.

Examples 6 to 9 and Comparative Examples 5 to 9 Using the dispersions obtained in Production Examples C and G (processing agents of the present invention) and the dispersions obtained in Production Examples H and I (known processing agents), Under the conditions shown in Table 2, a 265 B7 m2 polyester fabric was subjected to dyeing and exhaustion treatment in the same bath.

Note that a blank test without using flame retardant was also conducted at the same time.

The treatment bath (1000ml) listed in Table 2 was added to Minicolor-12
Using a dyeing tester (pot capacity 1800 ml), the temperature was raised from 50°C to 130°C at a heating rate of 2°C/min, and the same temperature was maintained for 30 minutes.

After observing the residual bath, it was drained and the fabric was washed with 8 ml of water containing 2 g of sodium hydrosulfide, 2 g of soda and 0.5 g of EOIO molar adduct of nonylphenol per 10,100 O.
Reduction cleaning was performed in a solution at 0° C. for 5 minutes, rinsed with running water, and dried. Sumikalon UL Blue F (Sumitomo Chemical Co., Ltd.) was used as the dye, and Disper N was used as the dispersion and leveling agent.
-700 (manufactured by Kaisei Chemical Industry Co., Ltd.) was used.

In addition, the physical properties of the product are shown in Table 2. Among the fabrics to be treated, 2.
Dry 0g of fabric at 105°C for 1 hour, with 2 decimal points
The increase in heavy electricity is shown as a percentage based on the weight accurately weighed to the nearest digit. Further, W Tanuki expressed the weight increase after reduction cleaning and drying as a percentage of the theoretical weight of the flame retardant in the dispersion liquid added to the bath only when the flame retardant was subjected to exhaustion treatment alone. The same method as in Example 1 was used for setting up and closing. Next color ¥r was measured using a Gakushin type friction fastness tester (JIS L-0849II method).

As is clear from the results in Table 2, according to the processing agent of the present invention, extremely excellent flame retardance can be obtained, and the stability of the dispersion in a high-temperature exhaust bath is good, so that the agent can be efficiently absorbed. It has the advantage that there is less risk of adhesion of dregs and tar to the processed fabric and leta staining of the case, which are common with conventional processing agents.

Examples 10 to 11 Using the dispersion obtained in Production Example G, 150 g/m'' of 6-
A nylon fabric and a 180 g/m'' 6,6-nylon fabric were thermosol treated in the same manner as in Example 1.

The treatment conditions are shown in Table 3.

All physical property tests were conducted in the same manner as in Example 1.

The test results are shown in Table 3. As is clear from this result,
The processing agent of the present invention can impart sufficient flame retardancy to nylon fabrics, and shows good results in terms of white discoloration, texture, and light resistance.

Effects of the Invention The processing agent of the present invention can be used with good workability without worrying about tar adhesion to processed fabrics or contamination of the casing, and the method of the present invention can improve color fastness of synthetic fiber products. It can provide excellent flame retardancy with good texture and wash resistance without any sudden effects.

Patent Applicant: Meisei Chemical Industry Co., Ltd. Agent: Takeshi Arata (and one other person) Procedural Amendment July 220, 1985 Commissioner of the Patent Office: I Tsubaki 1, Indication of Case: 1988 Patent Application No. 66171 2 , Title of the invention Processing agent and processing method for synthetic fiber products 3, Relationship with the case of the person making the amendment Patent applicant name Meisei Chemical Industry Co., Ltd. 4, Agent 604 Address Miyukimachi-dori Sanjo Umaru Maruya-cho, Nakagyo-ku, Kyoto City Address 330-16, Number of inventions increased by amendment 7, Target of amendment Description, Detailed explanation of invention column 8, Contents of amendment +1. l In the specification, line 8 from the bottom of No. 5, the word "phosphonate" is corrected to "sulfonate."

(2) S1, page 6, line 9 from the bottom, [protective colloid (
3) The same book, page 1O, lines 3-2 from the bottom, “Tris (
"Dibromoneopentyl) phosphate" is corrected to "Tris(dibromochloroneopentyl)phosphate J."

(4) In the same book, 9 lines from the bottom of No. 13, after the words ``show,'' add a new line and add the following sentence.

The weight increase after soaping and drying with respect to the theoretical adhesion amount of flame retardants "11" and "Jiga" is shown in weight %. (5) In the same book, 5th line from the bottom of No. 13, the phrase ``micro burner method'' is corrected to ``coil method.''

(6) In the same book, page 16, line 5, the phrase "dyeing bath exhaustion treatment" is amended to read "flame retardant sole exhaustion treatment and dye bath exhaustion treatment."

Claims (3)

[Claims] (1) (a) An orthophosphoric acid triester that is solid at room temperature and has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where X represents chlorine or bromine), and (b) a dispersant and a protective colloid agent. A processing agent for synthetic fiber products characterized by containing at least one of the following. (2) A method for flame-retardant processing of synthetic fiber products, which comprises applying an aqueous composition containing the processing agent according to claim 1 to synthetic fiber products, drying and then heat-treating at 170 to 220°C. (3) A flame retardant processing method for polyester fiber products, which comprises exhausting the aqueous composition containing the processing agent according to claim 1 at 110 to 140°C.