JPS6128075A - Melt-proof processing of synthetic fiber product - 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 method for melt-proofing synthetic fiber products.

More specifically, the present invention imparts melt-proofing properties to textile products made of synthetic fibers, particularly polyamide fibers or polyester fibers, so that they can be resistant to melting when they come into contact with high-temperature objects such as cigarette flames or welding sparks, or when they slide or fall. The present invention relates to a melt-proof processing method that effectively prevents the phenomenon of pitting caused by contact friction.

In recent years, textile products such as knitted fabrics made of synthetic fibers have been widely used in various fields such as industrial materials and clothing.

Even in the field of clothing, there are a variety of purposes and uses, from formal wear such as work clothes and suits to casual and training wear, mainly knitwear. However, especially polyamides,
Because textile products made of synthetic fibers such as polyester are thermoplastic, they may come into contact with small flame sources such as cigarettes, pine cinders, welding sparks from ironwork, irons, or other high-temperature objects for a short period of time. When sliding or falling in a gymnasium or the like, the friction of contact with the floor causes the fibers to melt and create holes, which is currently a major problem in practice.

Conventionally, for such synthetic fiber products, fibers with a large number of aromatic nuclei introduced into the skeleton have been developed in order to make the fiber material itself heat resistant. There are many problems such as coloring, and it has not reached the level where it can be called a general-purpose product. In addition, as post-treatment agents, dimethylpolysiloxane, paraffin wax, fatty acid amide, and heat-resistant resin agents such as melamine resin and acrylic resin, which have been conventionally used as fiber smoothing agents, are known, but their effectiveness is limited. At present, it is insufficient for practical use, or the texture is significantly impaired, so that excellent anti-melting effects cannot always be achieved.

Generally, when fabrics made of synthetic fibers are treated with organopolysiloxane, the phenomenon of holes caused by melting can be significantly prevented, but if you want to achieve a practical effect,
A large amount of organopolysiloxane must be attached to synthetic fiber cloth, which not only increases the cost, but also gives an unpleasant impression due to the slimy feel unique to organopolysiloxane. However, it was not suitable for general clothing.・In order to eliminate these drawbacks of organopolysiloxane, the present inventors combined use of a halogen-free pentavalent phosphorus compound, which is significantly different from the case of organopolysiloxane alone, and has an excellent anti-melting effect. A fabric that does not have a slimy feel and can be practically used for general clothing, is made with a pentavalent phosphorus compound that does not contain halogen, and the weight ratio of (b) / (a) is 0.1 or more. The present invention provides a melt-proof processing method for synthetic fiber products, which is characterized by treating the synthetic fiber products in a similar manner and subjecting them to heat treatment.

The organopolysiloxane (a) used in the present invention is preferably one having a hydroxyl group at the end that can form a film after processing into textile products. For example, organopolysiloxanes having a hydroxyl group at the end such as dimethylpolysiloxanediol, methylphenylpolysiloxanediol, diphenylpolysiloxanediol; methylhydrodienepolysiloxane, dimethylpolysiloxanemethylhydrodienepolysiloxane cocondensate, diphenylbolysiloxane methyl Organopolysiloxanes with hydrogen directly bonded to silicon atoms, such as hydrogen polysiloxane cocondensates, dimethylborisiloxane phenylhydrodiene polysiloxane cocondensates; diphenylpolysiloxanes, dimethylpolysiloxanes, methylphenylpolysiloxanes, and epoxy-modified dimethylpolysiloxane,
Examples include amino-modified polysiloxane, which can form a film after being processed into textile products, and has a viscosity of 10 to 50.
More preferred is one of 10,000 cst.

Among these, organopolysiloxanes having hydrogen directly bonded to a silicon atom are particularly preferred. In addition, these organopolysiloxanes can be used alone or in combination. When organopolysiloxanes having hydrogen directly bonded to silicon atoms are used, curing catalysts such as tetrabutyl titanate, tetrapropyl Titanate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, tin octylate, cadmium stearate, lead naphthenate, zinc octylate, zinc octobe, zirconium oftate,
Preference is given to using organometallic compounds such as zirconium stearate.

These organopolysiloxanes and curing catalysts are made into a homogeneous mixture and applied to textile products as they are, or in the form of a solution, an emulsion, or the like. In the case of an emulsion, it is preferable to emulsify it with the help of an emulsifier and, if necessary, combine it with a separately prepared emulsion of a curing catalyst. In the case of 8 liquids, the solvents include percrene, trichlene, 1.1.1-trichloroethane, chloroform, methyl chloride, toluene, xylene, benzene,
Methyl cellosolve, methyl ethyl ketone, acetone, butyl cellosolve, ethyl cellosolve, turpentine, etc. are used.

Examples of pentavalent phosphorus compounds (b) that do not contain halogens include triallyl phosphate, alkylene (having 2 carbon atoms)
-5, hereinafter represented as C2-C5) bis(dialkyl (C2-C4)) orthophosphoric acid ester, phosphoric acid trianthine (poly(degree of polymerization 2-20) ethylene glycol mono(nonylphenyl) ether) Acid triesters; butoxyethyl acid phosphate, mono- or diisopropyl phosphate, mono- or di- or (and) monoesters such as mono(or di)butoxyethyl hydrogen phosphate; alkyl acindophosphate amine salts, diethyl Nitrogen-containing pressure phosphoric acid esters such as -N,N-bis(2-hydroxyethyl)aminomethyl phosphate, acidic phosphoric acid -N,N-distearylamide, monomethyl phosphoric acid/urea condensate; alkyl phosphates ( CaSMg,
Na5Ba), poly(polyoxyethylene) phosphate-sodium salt, phosphoric acid ester of ethanolamine and its salt (NaSK), alkyl (or alkenyl, C6~Cap) polyoxyethylene phosphate ester metal salt (Mg, Ba5Zn), Metal salts of orthophosphoric acid esters such as sodium phenyl phosphate; phosphoric acid and inorganic compounds of phosphoric acid such as phosphoric acid, aluminum phosphate, boron phosphate, ammonium phosphate, ammonamide polyphosphate, tin phosphate; phenyl Alkyl phosphonate (Ct~Ce) ester, alkyl (or alkenyl, 08~c2φ) isphonic acid, alkyl (or alkenyl, line 01~C) ester and its salt (Na
SK, Ca, alkanol (C2-G3) amine]
Phosphonic acids such as dialkyl (C1-c3 or allyl)-N,N-bis(2-hydroxyethyl)aminomethanephosphonate, 0.0-bisalkyl Cct~
C/8) Phosphonates such as (3,5-di-t-butyl-4-hydroxybenzene)phosphonate; phosphonium salts such as tetrakis-hydroxymethylphosphonium, tetraphenylphosphonium; nitrilotrismethylenephosphonic acid and its sodium salt; 2,4.
6-) Nitrogen-containing phosphorus compounds such as alkyl phosphazenes with the general formula % (formula %); alkyl (alkylphenyl, Cs NC yl) polyoxy Ethylene phosphate ester, phosphorus-containing polyether polyol urethane resin, guanidine phosphate/formalin condensate, poly(n=2-5) phosphoric acid/urea condensate, alkanol (CIλ~C74)/4,4'- There are polymer compounds such as isopropylidene diphenol triphenyl phosphite polycondensate and polymethyl phosphate, and these compounds alone or in combination are usually applied to textile products as an aqueous solution or emulsion. Preferred are nitrogen atom-containing phosphorus compounds.

Adhesion methods include coating, dipping, spraying, and punting, which are commonly used in textile processing.
The valent phosphorus compound may be handled in the same bath, or the pentavalent phosphorus compound or organopolysiloxane may be applied to the cloth in advance, dried if necessary, and then the organopolysiloxane and the pentavalent phosphorus compound may be applied. The processing may be performed in two steps.

In that case, it is preferable to process the phosphorus compound and the organopolysiloxane in this order. In any case, the amount of adhesion to textile products is the amount of organopolysiloxane (a) and pentavalent phosphorus compound (
It is appropriate to adjust the ratio (b) to (b) to be 0.1 or more, preferably 0.1 to 2, particularly preferably 0.4 to 1.2.

At this time, the phosphorus compound is 10%
%, no significant improvement in melt resistance is observed compared to organopolysiloxane alone. (B)/(
If the weight ratio of (a) exceeds 2, no significant improvement in melt resistance is observed despite the large amount of the pentavalent phosphorus compound (b) added, and in this case, the organopolysiloxane milk dispersion and the phosphorus Preparing the compounds in the same bath may have an adverse effect on the stability of the mixed bath, which is not preferred. The amount of the agent according to the present invention deposited on the synthetic fibers, which are preferably impregnated or coated separately, is preferably 2 to 20% by weight (based on the weight of the fabric) of the organopolysiloxane (a).
Particularly preferably from 3 to 10 in terms of melt resistance, cost, and texture.
Weight % is appropriate.

In addition, other processing chemicals such as polyethylene,
Softeners such as wax emulsions, acrylic emulsions,
A stiffening agent such as melamine resin, a hand control agent, etc. may be used in combination as long as the melt-proofing effect is not impaired.

In this way, textile products to which organopolysiloxane (a) and pentavalent phosphide @ff (b) are attached generally have an 80 to 2
It is finished by heat treatment at a temperature of 00°C for 20 seconds to 30 minutes.

The fiber products processed in this manner have extremely excellent melting and heat resistance, and have a satisfactory feel.

The reason for the excellent melt-proofing effect of the present invention has not been elucidated in detail, but it is likely that the phosphorus compound has the property of promoting dehydration during heat, which promotes carbonization and dehydration of synthetic fibers, and It is presumed that the melt-proofing and heat-resistant effect of polysiloxane is greatly improved. However, it is thought that various factors are at play, not just for these reasons.

The present invention is mainly applied to cloth, knitted fabrics, or non-woven fabrics made of synthetic fibers, particularly polyamide or polyester fibers, but it is also possible to mix or blend some of these knitted fabrics or non-woven fabrics with other natural or recycled fibers. Needless to say, almost the same effect can be obtained even if

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these in any way. "Parts" and "%" in the text are based on weight.

Each measured value in the examples was measured and evaluated based on the following test method.

(11) Hold the melt-proof heat-resistant test piece horizontally so that there is no sagging, place a lit cigarette vertically on top of it, support it from the side so that it does not fall over, and place a melt hole in the test piece. The time taken for the cigarette to fall under its own weight was measured and evaluated.

<21 i match Judgments were made by touch as follows.

○: No slimy feeling △: Slightly slimy feeling ×: Significant slimy feeling Example 1 Methylphenyl polysiloxane diol (viscosity 1000
cst), 10 parts of methylhydrodiene polysiloxane (viscosity: 25 cst), 2 parts of polyoxyethylene nonylphenol ether (HLB13), and 48 parts of water were emulsified using a homogenizer (pressure: 280 kg/csl). This emulsion is referred to as composition (A).

Dimethylpolysiloxane methylhydrogenpolysiloxane cocondensate (viscosity 50 cst, cocondensation molar ratio 9
/1) 50 parts of polyoxyethylene tridecyl ether (HL B 12.5) and 47 parts of water were emulsified using a homogenizer. This emulsion is referred to as composition (B).

5 parts of dibutyltin dilaurate, 1 part of polyoxyethylene tridecyl ether (HLBIo, 5), and 94 parts of water were emulsified using a homomixer. This emulsion is referred to as composition (C).

25 parts of dimethylpolysiloxane (viscosity 100,000 cst) and polyoxyethylene oleyl ether (HLB 13.5)
) 3M and 72 parts of water were emulsified using a homomixer. This emulsion is referred to as composition (D).

Mixtures shown in Table 1 were prepared by combining various compositions (A), (B), (C), and (D) with pentavalent phosphorus compounds, and a polyester-treated fabric (fabric weight: 120 g) was added to this as a sample.
/rd) and then passed through a squeezing roll to a squeezing rate of 5.
It was set to 0%.

Subsequently, this sample was dried at 120°C for 1 minute and further dried at 17°C.
Heat treatment was performed at 0°C for 30 seconds.

As shown in Table 1, the method of the present invention provides extremely superior heat and melt resistance and hand feel compared to the single treatment of silicone and the combined treatment of silicone and a trivalent phosphorus compound shown in the comparative example. It is recognized that

Example 2 A dyed polyamide jersey (fabric weight: 280 g/rrr) was immersed in a mixed solution of 2 parts of dimethylphosphonopropionamide and 98 parts of trichlene, passed through a squeezing roll to a squeezing rate of 100%, and heated at 100°C for 4 minutes. Dry.

Next, an organopolysiloxane solution consisting of 50 parts of methylphenylpolysiloxane (viscosity: 10,000 cst) and 50 parts of xylene was applied to the sample at a coating amount of 30 g/rrr.
(net) using a gravure roll coater and dried at 80°C for 3 minutes.

In addition, this example, the following Example 3, and Comparative Example 2.3.4
The heat and melt resistance test results are shown in Table 2.

Example 3 Using the same polyamide jersey as used in Example 2, it was immersed in a mixture of 4 parts of diethyl-N,N-bis(2-hydroxyethyl)aminomethanephosphonate and 96 parts of toluene, and squeezed through a squeeze roll. The drying rate was set to 100%, and the mixture was dried at 100° C. for 3 minutes. Next, 2 parts of polyoxyethylene oleyl ether (HLB20) and 1 part of polyoxyethylene tridecyl ether (HL B13) were added to 40 parts of epoxy-modified dimethylpolysiloxane (viscosity 5200 cst, epoxy equivalent 2000), and 56 parts of water was added. After stirring and emulsifying with a homomixer, add Metrose 9
0SH15000 (manufactured by Shin-Etsu Chemical, methyl cellulose) 1
110 g of the viscous liquid was added to the sample and dissolved and mixed.
/nr (net) using a roll coater, and heat-treated at 80°C for 3 minutes and then at 140°C for 1 minute.

Comparative Example 2 Using the same polyamide jersey as that used in Example 2, it was immersed in a mixed solution of 2 parts of dimethylphosphonopropionamide and 98 parts of trichlene, then passed through a squeezing roll to a squeezing rate of 100%, and heated at 100°C for 4 hours. Dry for a minute.

Comparative Example 3 Using the same polyamide jersey as that used in Example 2, a viscous liquid of the epoxy-modified dimethylpolysiloxane emulsion prepared in Example 3 was mixed at 110 g/rrr (net
) with a roll coater and coated at 80°C with 3
minutes, followed by heat treatment at 140° C. for 1 minute.

Comparative Example 4 Using the same polyamide jersey as that used in Example 2, a mixture was prepared consisting of 5 parts of tris(1-bromo-3-chloropropyl) phosphate, 6 parts of methylphenylpolysiloxane (viscosity 10,000 cst), and 91 parts of toluene. Immerse it in the blended solution, then pass it through a squeezing roll to make the squeezing rate 100%, and
It was dried at 00°C for 4 minutes.

Table 2 As shown in Table 2, halogen-free pentavalent phosphorus compound alone (Comparative Example 2) and silicone alone (Comparative Example 3)
) has drawbacks in heat resistance and melt resistance and texture, and the combination of silicone and halogen-containing pentavalent phosphorus compound (Comparative Example 4) does not provide sufficient effects in both heat resistance and melt resistance and texture. . On the other hand, the method according to the present invention (Example 2.3) was found to be extremely excellent in terms of both heat and melt resistance and texture.

Agent Patent Attorney Katsutoshi Takahashi Procedural Amendment Date Yuzuki 7, 1985 Manabu Shiga, Commissioner of the Patent Office 16 Display of Case 1982 Patent Application No. 143373 2 Title of Invention Method for anti-melting processing of synthetic fiber products 3. Relationship with the case of the person making the amendment Patent applicant: 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (2)
8B> Dainippon Ink & Chemicals Co., Ltd. Representative: Shigeru Mura Kuni 4, Agent Address: 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Dainippon Ink & Chemicals Co., Ltd. Phone: Tokyo (03) 272-4511 (Dainippon Ink & Chemicals Co., Ltd.) Representative) -
・(8876) Patent attorney Katsutoshi Takahashi 5, subject to amendment
.

Detailed explanation of the invention in the specification column 6, content of amendment +2> r+PN (CORf) in the third line from the bottom of page 6
fi) ÷ n'' is corrected as Toten N P (OR)t3 禮, J.

(3) Correct "batting" in line 10 of page 7 to "puffde□ingj".

(4) "Polysiloxane and pentavalent" on page 7, line 14 is corrected to r-polysiloxane or pentavalent J.

(5) "Processed textiles" in line 6 of page 11 is corrected to r-processed textiles j.

(that's all)

Claims (1)

[Claims] Synthetic fiber products are treated with (a) organopolysiloxane and (b) a halogen-free pentavalent phosphorus compound so that the weight ratio of (b)/(a) is 0.1 or more, and heat treated. A method for melt-proofing synthetic fiber products, characterized by: