JPS62289674A - Hydrophilic treatment agent - 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 3. Detailed Description of the Invention (Field of Industrial Application) The present invention provides hydrophilic properties to synthetic fibers used as raw materials in applications that directly contact the skin, particularly synthetic fibers for sanitary materials. The present invention relates to a hydrophilic treatment agent suitable for application.

(Conventional technology) Synthetic fibers such as polyester fibers and polyamide fibers are
Since they are generally highly hydrophobic, they do not absorb sweat, and they have drawbacks such as electrostatic charge that can cause electric shocks if they are wrapped around them, which has been an obstacle in their use in clothing.

In order to overcome this drawback, various hydrophilic treatment agents have been proposed. For example, Special Publication No. 53-46960
According to the publication, (al-fi formula R.

RO(CHCHt O) n A M (wherein R: alkyl group, alkenyl group, or alkylaryl group, R1: hydrogen atom or methyl group, A
:SO2 group, (CHz)mso:+ group or PO3
group, M: hydrogen atom, ammonium group, alkyl group, or alkali metal, n: an integer of 4 to 20, m: a surfactant represented by 2 or 3), and (b) adding an acid and/or a water-soluble salt. Hydrophilic treatment agents have been proposed.

(Problem to be solved by the invention) Textile products treated with this hydrophilic treatment agent have initial hydrophilicity,
Although it has excellent antistatic properties and stain resistance, its durability against washing with water is not necessarily satisfactory, and it is also highly irritating to the skin, so it is used in underwear that is used in direct contact with the skin, especially diapers, sanitary napkins, etc. When this hydrophilic treatment agent is used for sanitary materials such as, there is a risk that the problem of skin irritation may occur.

The purpose of the present invention is to improve the washing durability and skin irritation of such conventional hydrophilic treatment agents, and to develop a hydrophilic treatment agent that is mild to the skin and is particularly suitable for sanitary materials such as diapers and sanitary napkins. It is about providing.

(Means for Solving the Problems) As a result of extensive studies to achieve the above object, the present inventors have found that in conventional hydrophilic treatment agents, the surfactant component does not adhere to the fibers of the hydrophilic agent polymer. We investigated that the durability changes due to the condition and that it irritates the skin, and by using alkanolamine salt as the surfactant component, we improved the washing durability with less skin irritation. We have discovered that this can be significantly improved and have arrived at the present invention.

That is, the present invention provides a polyester polyether block comprising terephthalic acid and/or isophthalic acid and/or 5-sodium sulfoisophthalic acid or a lower alkyl ester thereof, lower alkylene glycol, and polyalkylene glycol and/or polyalkylene glycol monoether. This is a hydrophilic treatment agent characterized by containing a copolymer and an alkyl sulfate alkanolamine salt represented by the following general formula.

R-0 +
", R'" is an alkyl group, alkenyl group, or alkylaryl group having 1 to 18 carbon atoms, or ÷X-0? kH,
X is an alkylene group having 2 to 4 carbon atoms with or without a side chain, n is an integer of 0 to 2o, and k is an integer of 1 to 20.

Polyester polyether blocks comprising terephthalic acid and/or isophthalic acid and/or 5-sodium sulfoisophthalic acid or lower alkyl esters thereof, lower alkylene glycols, and polyalkylene glycols and/or polyalkylene glycol monoethers used in the present invention. Examples of the polymer include terephthalic acid-alkylene glycol-polyalkylene glycol, terephthalic acid-isophthalic acid-alkylene glycol-polyalkylene glycol,
Block copolymers of terephthalic acid-alkylene glycol-polyalkylene glycol monoether, terephthalic acid-isophthalic acid-alkylene glycol-polyalkylene glycol monoether, terephthalic acid-5-sodium sulfoisofucric acid-alkylene glycol-polyalkylene glycol, etc. However, the block copolymer usually has terephthalate units: isophthalate units (5-sodium sulfoisophthalate units) = l
OO: 0 to 50:50 (molar ratio) is preferable from the viewpoint of durability of the effect, and when considering ease of dispersion, terephthalate unit: isophthalate unit (5-sodium sulfoisophthalate unit) = 90:10 to 50: 50
(molar ratio) is particularly preferred. In addition, the block copolymer usually has a terephthalate unit, isophthalate unit (5-sodium sulfoisophthalate unit): polyalkylene glycol 41-position-2 to 15:1 (molar ratio).
When considering the durability of the effect, dispersibility, exhaustion into fibers, etc., a molar ratio of 3 to 8:l is particularly preferable.

The alkylene glycols used in the production of the block copolymer include alkylene glycols having 2 to 10 carbon atoms, such as ethylene glycol, propylene glycol, tetramethylene glycol, and decamethylene glycol. Average molecular weight is 6
00-12.000, preferably average molecular weight 1.00
0 to 5,000 polyethylene glycol, polyethylene glycol/polypropylene glycol copolymer, polyethylene glycol/polytetramethylene glycol copolymer, polypropylene glycol, etc., as well as monomethyl ether, monoethyl ether, mono of polyethylene glycol, polypropylene glycol, etc. Includes phenyl ether, etc. However, monoethers of polyethylene glycol are particularly preferred from the viewpoint of hydrophilic effect.

The average molecular weight of the block copolymer depends on the molecular weight of the polyalkylene glycol used, but is usually 2.0
00-20,000, preferably 3.000-13°0
It is 00. If the average molecular weight is less than 2.000, both the modifying effect and durability will be insufficient, and if it is more than 20.000, the dispersibility and hydrophilic effect will decrease, which is not preferable. The polyalkylene glycol used to control the molecular weight of the block copolymer during polycondensation is particularly preferably one in which one end group is blocked, such as monomethyl ether, monoethyl ether, or monophenyl ether. Further, the aggregation initiation temperature of a block copolymer dispersion dispersed without using a surfactant is usually 30 to 100°C, preferably 60 to 90°C. The amount of the block copolymer used is usually 0.02 to 5.0% by weight based on the treated fiber product.
, preferably 0.1 to 3.0% by weight.

Preferred specific examples of the alkyl sulfate alkanolamine salt represented by the above general formula used in the present invention include the following compounds.

C+5Hst C+5H3t O+CHz CHz O7-+5SO
s H-NR'R"R1Cm H+, O+CH's
CHz CHz CHz O 廿+eS Os H・NR
'R"R' CH3 C, 2H!S-0+CHCHI O?+6303
H-NR'R"R#H3 C+5Hst 3Oa H-NR'R"R' Here, as preferred specific examples of NR'R"R#, the following can be mentioned.

N +CHz CHt OH) s CH2S +CHt CHz OH) ! <Ct Hs
fz N CHz CHz OHCmH+t-N+
CHz CHt 0H)2C+zHzs N++CH
z CH2O nago. H) 2C+@Hzt N -H-
CHZ CHO? -s H) t■ CH.

(C+5Hst)z -N+CH! CHO? -tCH
, CHt On HCH3 (C+sHs, dez N +c Hz CII Hake-s
HC+ s Hjs N -+-+c Hz CH
z Osu+5H)zCs Ht N-+CHz CH
z 0H) z In the alkyl sulfate alkanolamine salt used in the present invention, in order to improve washing durability and skin irritation, R' of -i2 is +X-〇? IIH
, but R" or R#R# must also be +X
-0iH is preferable because washing durability and skin irritation are further improved. In this case, R', R", R
'' may be different or the same.

The amount of these alkyl sulfate alkanolamine salts to be used varies depending on the composition and molecular weight of the block copolymer used, the pH of the treatment solution, the amount of salt added, the treatment temperature, etc.
0 for normal processing liquid. O1-50g/l, preferably 0
．． 3 to 20 g/l. 0゜01g/j! If the temperature is lower than that, sufficient stability of the treatment solution cannot be obtained, and when heated above the agglomeration start temperature, the block copolymer aggregates into very large particles, which not only causes adhesion spots (but also prevents diffusion into the fibers). At 50 g/i! or higher, the desired agglomeration initiation temperature cannot be obtained unless a large amount of salt is added, and the block copolymer fibers This is undesirable because it prevents adsorption to.

The alkyl sulfate alkanolamine salt may be added to the aqueous solution in which the block copolymer is dispersed, or the molten block copolymer may be directly added and dispersed in the aqueous alkanolamine salt solution.

The synthetic fibers to be treated are immersed in the treatment agent of the present invention thus prepared and treated. Processing temperature is usually 66℃~180℃
, preferably 80 to 160°C, more preferably 1
00-140°C. The time is usually 5 to 120 minutes, preferably 30 to 60 minutes.

The synthetic fibers treated with the treatment agent of the present invention include:
Examples include hydrophobic synthetic fibers such as polyester fibers, polyamide fibers, and polyolefin fibers, and among them, remarkable effects can be achieved when applied to polyester fibers. Furthermore, synthetic fibers can be processed into any form such as filaments, stable fibers, sliver fabrics, knitted fabrics, and nonwoven fabrics.

To the treatment agent of the present invention, a hinged phenol compound having a melting point of 70°C or higher, such as pentaerythrityl-tetrakis (3-(3,5-di-t-butyl-4-hydroquinphenyl)propionate) is added. This is preferable because it does not irritate the skin (and improves weather resistance and heat resistance).

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

The conditions and methods for measuring various properties of the treated synthetic fiber web in Examples are as follows.

(1) Hydrophilicity (seconds): Web I from the height of 10 cranes above the water surface
A cotton sample rolled into a circle with a diameter of approximately 301 g was freely dropped onto the water surface, and the time (seconds) from immediately after the fall until the cotton sample was submerged in water was measured.

The shorter this time, the better the hydrophilicity.

(2) Washing conditions: 1 g/i aqueous solution of commercially available detergent Sub (product name: Kao Corporation) at 40°C for 10 minutes (1)
The sample was placed in a case bag, washed in a washing machine, and washed with water.

(3) Reflective irritation: Judgment was made according to the Kawa method, which is a pasting test judgment method based on microscopic observation. That is, along with a control (blank), a web made of fibers to which a treatment agent had been applied was applied to the inner side of the upper arm, and the applied piece was removed 24 hours later.

Thereafter, a Sumpu plate coated with Sumpu liquid was applied to the skin surface on which the patch test was performed, and after a while, the Sumpu plate was removed and evaluated by observing it under a microscope. The judgment criteria are as follows. However, stimulation A was excluded from the evaluation because the skin returned to normal skin about 24 hours after the test substance was removed and reacted even to slight stimulation.

(This page, the following margins) In addition, in the example, both C and D stimuli were positive and there were no problems, so only the judgment value of B stimulus is shown.

Examples 1 to 6, Comparative Examples 1 to 8 As the block copolymer, terephthalic acid/isophthalic acid/ethylene glycol/polyethine glycol block copolymer (terephthalate unit: isophthalate unit +
70: 30, terephthalate units 10 isophthalate units: polyethylene glycol units = 5:1, polyethylene glycol molecule! = 2,000, average molecular weight of the block copolymer = 10.000) and various surfactants at a ratio of 80:20 to create an aqueous dispersion containing 10% of the active ingredient. In the manufacturing process, the stretched polyester tow was treated with the aqueous dispersion, and then the aqueous dispersion was squeezed and crimped using a push crimper, followed by heat treatment at a temperature of 130°C for 30 minutes and cutting. . The obtained fiber had a fineness of 1.5 d and a fiber length of 44 tsuru. threading the fibers through a card to create a web;
Hydrophilicity and skin irritation were evaluated. The results are shown in Table 1.

(This page, blank space below) As is clear from Table 1, Examples 1 to 6 all have an alkanolamine structure as a surfactant, and have excellent initial hydrophilicity and washing durability. At the same time, it has low skin irritation and is good. In particular, those containing many alkanol groups are better.

On the other hand, Comparative Examples 1 to 6 were all inferior in hydrophilic washing durability and showed a strong tendency to cause skin irritation. Comparative Example 7 shows an example in which cetyl phosphate potassium salt, which is usually used as an oil agent for spinning, is used, but although the skin irritation is weak, the hydrophilic washing durability is poor.

Moreover, Comparative Example 8 shows an example in which no treatment was performed with a treatment agent, and the hydrophilicity was extremely poor.

Examples 7 to 9, Comparative Example 9.10 As a block copolymer, terephthalic acid/15-sodium isophthalate sulfoisophthalic acid/ethylene glycol/polyethylene glycol block copolymer (terephthalate unit: isophthalate unit: 5-sodium sulfonate) Isophthalate units = 70:25: 5 (terephthalate units 10 isophthalate units + 5-sodium sulfoisophthalate units: polyethylene glycol units = 5 = 1, polyethylene glycol molecular weight = 2.OO
Average molecular weight of O,7' lock copolymer = 10,000)
and various surfactants in a ratio of 90:10,
Hereinafter, the same treatment as in Example 1 was performed, and the results are shown in Table 2.

(This page, blank space below) As is clear from Table 2, Examples 7 to 9 all have an alkanolamine structure as a surfactant, and have excellent initial hydrophilicity, durability, and skin irritation. ing.

In particular, those with a large number of alkanol groups are better.

On the other hand, Comparative Examples 9 and 10 have poor hydrophilic washing durability and are highly irritating to the skin, which is not preferred.

Example 10 In Example 3, during the polymerization reaction of the block copolymer,
Pentaerythrityl with a melting point of 113℃ as an antioxidant
Tetrakis (3-(3,5-di-t-butyl-4hydroxyphenyl)propionate) was added in an amount of 0.5% by weight based on the block copolymer. The hydrophilicity of the fiber web is initially
Skin irritation (B irritation) is 0/B after washing 5 times for 2 seconds each.
Both were good.

When this web was heat treated in a hot air dryer at a temperature of 160° C. for 120 minutes, no yellowing was observed. On the other hand, when the web of Example 3 was similarly heat-treated, it turned slightly yellow.

(Effects of the Invention) According to the hydrophilic treatment agent of the present invention, it is possible to not only impart excellent and durable hydrophilicity to textile products, but also cause almost no irritation to the skin, so it can be used in diapers, sanitary napkins, etc. It can be applied to textile products that are used in direct contact with the skin, such as sanitary materials or underwear.

Claims (1)

[Claims] 1. Polyester polyester comprising terephthalic acid and/or isophthalic acid and/or 5-sodium sulfoisophthalic acid or lower alkyl ester thereof, lower alkylene glycol, and polyalkylene glycol and/or polyalkylene glycol monoether A hydrophilic treatment agent characterized by containing an ether block copolymer and an alkyl sulfate alkanolamine salt represented by the following general formula. R-O-(X-O)-_nSO_3H・NR'R″R'
``Here, R is an alkyl group, alkenyl group, or alkylaryl group having 1 to 18 carbon atoms, and R' is -(X-O)-_
kH, R″, R′″ are alkyl groups, alkenyl groups, or alkylaryl groups having 1 to 18 carbon atoms, or (X-O)
_kH, X has 2 to 4 carbon atoms with or without a side chain
alkylene group, n is an integer of 0 to 20, and k is an integer of 1 to 20.