JPH04163374A - Silicone-based fiber surface treating agent - Google Patents

Abstract

PURPOSE:To obtain the subject treating agent, composed of an amino-modified silicone, having specified urea groups and a specific molecular weight and excellent in color deepening ability without causing yellowing by reacting an organopolysiloxane having specific amino groups with an aliphatic isocyanate. CONSTITUTION:A textile surface treating agent is composed of a urea- substituted amino-modified silicone, prepared by reacting an organopolysiloxane having at least one primary and/or secondary amino groups in one molecule with a 1-20C aliphatic monoisocyanate (e.g. methyl isocyanate or dodecyl isocyanate) in the form of a straight chain or with a branched chain and having at least one urea group expressed by the formula (R is 1-20C aliphatic hydrocarbon; R<1> is H or alkyl) in one molecule and 1000-500000 molecular weight. The aforementioned treating agent can be, e.g. emulsified and applied to a dyed woven or knit fabric composed of natural, synthetic fiber, etc., to afford excellent color deepening effects without causing yellowing and discoloring.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a urefined organopolysiloxane and a silicone-based fiber surface treatment agent containing the same, and more specifically, it relates to a urefined organopolysiloxane and a silicone fiber surface treatment agent containing the same. and/or 2
A ureated amine-modified silicone obtained by reacting an organopolysiloxane containing a class of amino groups (hereinafter referred to as amino-modified silicone) with an aliphatic monoisocyanate, and a silicone containing the ureated amine-modified silicone, which has excellent color deepening ability and can cause yellowing and discoloration. The present invention relates to a silicone-based fiber surface treatment agent that is free from these problems.

[Prior art and problems to be solved by the invention] Silicone has a polymer skeleton consisting of repeating units of silicon atoms and oxygen atoms, and has a large polarizability (and high ionic bonding, so the atomic bond angle is small). It has a greater degree of freedom than ordinary carbon skeleton polymers, and has a highly flexible main chain.

Traditionally, in the textile processing field, in addition to the flexibility mentioned above,
Various silicone-based processing agents are used that utilize unique properties not found in ordinary carbon skeleton polymers, such as smoothness, water repellency, and color-enhancing ability. In particular, the low refractive index derived from the large polarizability of the silicone main chain is achieved by applying silicone to the fiber surface, which apparently lowers the refractive index of the upper fiber, thereby preventing bulkiness on the surface of the textile product and preventing it from occurring. It has the effect of making dyed fibers appear darker, and is easier and more suitable for mass production than methods such as linearizing the fiber surface, so it has been widely used as a color-deepening treatment for fibers.

However, the color deepening effect of polydimethylsiloxane, which is generally widely used, is not satisfactory, and in recent years, amino-modified silicones in which primary and/or secondary amino groups are introduced into the silicone side chains have been developed to darken the color. It has come to be widely used as a processing agent.

However, as is already known, the amino group is a highly reactive functional group, and has recently become a particular problem in that it changes and becomes colored when exposed to heat and/or oxygen in the air. That is, problems such as yellowing for white products and discoloration for colored products occur, resulting in a decrease in product value.

In order to overcome the drawbacks of such amino-modified silicones, the amino groups are reacted with organic acid anhydrides or organic acid chlorides, and some or all of the amino groups are acylated to contain an organopolysiloxane. A silicone-based fiber surface treatment agent has been proposed (Japanese Patent Publication No. 57-54).
No. 588), its discoloration prevention effect was not said to be sufficient.

[Means to solve the problem]

Therefore, the present inventors conducted extensive research to resolve the drawbacks of the above-mentioned amino-modified silicones, and as a result, developed a ureated organopolysiloxane that has excellent color deepening ability and does not cause yellowing or discoloration. This discovery led to the present invention.

That is, the present invention provides an aliphatic hydrocarbon group having an average of at least one formula% in one molecule (wherein R represents a linear or branched aliphatic hydrocarbon group having 1 to 2 carbon atoms; It has a urea group represented by `` represents H or an alkyl group, and has a molecular weight of 1,000 to 50.
0,000, and an organopolysiloxane containing on average at least one primary and/or secondary amino group per molecule, and an organopolysiloxane having 1 to 1 carbon atoms.
The method for producing the above organopolysiloxane, which is characterized by reacting it with an aliphatic monoisocyanate having a linear or branched chain of 20, and the silicone fiber surface treatment agent, which is further characterized by containing this organopolysiloxane. It provides:

The amino-modified silicone used in the present invention includes 1
Any substance containing at least one primary and/or secondary amino group may be used, and the substitution position thereof may be at the end of the main chain or in the side chain. Furthermore, the ends of the silicone main chain may be blocked with 1-lyorganosiloxane or with other substances.

The aliphatic monoisocyanate used in the present invention is a linear or branched monoisocyanate compound having 1 to 20 carbon atoms, and specifically, methyl isocyanate, ethyl isocyanate, n-propylisocyanate, i -Propyl isocyanate, n-butyl isocyanate, i-butyl isocyanate, t-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, nonyl isocyanate, decyl isocyanate, dodecyl isocyanate, etc., but carbon number 1
Those with a carbon number of ~3 are difficult to handle due to their low boiling points, and those with a carbon number of 9 or more are difficult to purify and have reduced reactivity. Therefore, those having 2 to 12 carbon atoms are preferable, and those having 4 to 8 carbon atoms are preferable.
More preferred is Further, although aromatic isocyanates have high reactivity, they tend to be colored and are therefore unsuitable for the present invention.

In the present invention, the reaction between the amino-modified silicone and the aliphatic monoisocyanate may be carried out in a conventional manner. For example, the amino-modified silicone is mixed with the aliphatic monoisocyanate-1 in a toluene solvent at room temperature, and then The reaction is carried out at a temperature of about 50 to 110"C by heating under a gas flow. The remaining aliphatic monoisocyanate and solvent can be easily removed by topping under reduced pressure.

If you want to convert all the amino groups in the amino-modified silicone to urea groups, you can react the amino groups with an equal or slightly excess amount of aliphatic monoisocyanate, or convert some of the amino groups in the amine-modified silicone to urea groups. When it is desired to convert it into a group, it is sufficient to react with aliphatic monoisocyane-1. in an amount equivalent to or slightly in excess of the desired conversion rate.

II? of the ureated amino-modified silicone obtained in this reaction? By performing spectral analysis, 1650c
m-'("A characteristic absorption of urea was observed near J, and 2
The characteristic absorption of isocyanate observed around 250 cm-' disappears, confirming that the reaction is proceeding and completing.

The ureated amine-modified silicone thus obtained was 1
It has an average of at least one urea group represented by the formula % (in the formula, R and R' have the same meanings as above) in the molecule, and has a molecular weight of 1,000 to 500,0.
00.

When the ureated amino-modified silicone of the present invention is used as a fiber treatment agent, it is applied after being dissolved in an organic solvent, or it is applied in the form of an emulsion using an emulsifier.

In the present invention, fiber refers to natural fibers; synthetic fibers such as polyester, nylon, and acrylic; semi-synthetic fibers such as acetate; and blended, knitted, and knitted fabrics thereof.

To apply the treatment agent of the present invention to the fibers, any of the dipping method, spraying method, and banding method may be used. The fibers treated with the ureated amine-modified silicone of the present invention are darkened and have a descendant-like color, and are heat resistant.
Because it does not yellow or discolor due to light, high-quality processing is possible.

(Examples) The present invention will be specifically explained below using synthesis examples and examples, but the present invention is not limited to these examples.

Synthesis Example 1 An amino-modified silicone Log having an average molecular weight of 100,000 and an amine equivalent of 4,000 was dissolved in approximately 30 g of pre-dried toluene, and further dissolved in 0.3 g of n-butyl isocyanate.
g was added thereto, and the reaction was carried out at about 60°C for 3 hours under a nitrogen stream. After the reaction, the solvent toluene and excess n-butyl isocyanate were removed by topping under reduced pressure.
A ureated amino-modified silicone represented by the following formula was obtained.

CIl, CH.

(CIl3) 3S io −(−SiO+rrg”r
--<-5io -)r"-Si (Cll a) 3
CIl3 (Cth) JIICONHC4
11q As a result of IR spectrum analysis of this compound,
A characteristic absorption of urea was observed near 1650 cm-',
Also, isocyanium-1 observed near 2250 cm-'
The characteristic absorption of ~ had disappeared. From this fact, it was confirmed that the urea-forming reaction with n-butyl isocyane-1 was completed.

Example 1 2 parts by weight of various organoborisiloxanes shown in Table 1 were mixed with 49 parts by weight of ethanol and 49 parts by weight of LPG (2,5) to prepare a uniform and transparent injection liquid.

Next, a color deepening effect evaluation test and a yellowing resistance evaluation test were conducted using this solution. The results are shown in Table-2.

The darkening effect evaluation test and the yellowing resistance evaluation test were conducted as follows.

<Pretreatment of test fabric> Commercially available wool, polyester/wool blend fabric (80/2
Black school uniforms (hereinafter referred to as blends) and cotton broadcloth were cut into a size of approximately 20 x 20 (cm) and dry cleaned using perchlorethylene to remove deposits.

<Preparation of samples for evaluation of darkening effect> Each organopolysiloxane was sprayed onto various base fabrics so that the base amount was 0.4% owf. The degree of darkening of this sample was measured by reflectance (-ΔB).

-The larger the value of ΔL, the higher (better) the color deepening ability is.
.

<Preparation of samples for evaluation of yellowing resistance> Each organopolysiloxane was sprayed onto various base fabrics so that the base amount was 4.0% owf. Afterwards, it was ironed for 2 minutes using an iron at 180°C, washed and dried with New Beads (powdered laundry detergent made by Kao ■), and then ironed again for 2 minutes using an iron at 180"C.The color of this sample The index was measured (ΔB).

The smaller the value of ΔB, the better the yellowing resistance (harder to change color).

Table-1 CH3CH.

(CL) asio + 5iO−)T(−3iO什S
i (C)13) 3CH,R Table-2 [Effect of the invention] Comparing and contrasting products 1 to 4 of the present invention and comparison products 5 to 8, ureated amino-modified silicone is darker than acetylated amino-modified silicone. It can be seen that it is superior in both coloring effect and yellowing resistance.

Furthermore, when compared with ordinary amino-modified silicone (comparative product 9) and polydimethylsiloxane (comparative product 10),
It is clear that ureated amino-modified silicone is superior in both color deepening effect and yellowing resistance.

Claims (1)

[Claims] 1. On average, at least one compound of the formula -NR'CONHR per molecule (wherein R represents a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, R' represents H or an alkyl group), and has a molecular weight of 1,000 to 50
0,000 organopolysiloxane. 2. Reacting an organopolysiloxane containing on average at least one primary and/or secondary amino group per molecule with a linear or branched aliphatic monoisocyanate having 1 to 20 carbon atoms. 2. The method for producing an organopolysiloxane according to claim 1, further comprising the step of: 3. A silicone fiber surface treatment agent containing the organopolysiloxane according to claim 1.