JPH07258968A - Crease-resistant and shrink-resistant processing agent for cellulose fiber - Google Patents

Abstract

PURPOSE:To obtain a processing agent comprising a polyester produced by adding a specified aliphatic dialdehyde to an esterification product comprising a specific component or that substituted with the esterification product, and capable of crosslinking a cellulose fiber in the presence of a specific catalyst to secure excellent safety and washing durability. CONSTITUTION:A cellulose fiber is dipped in a crease-resistant and shrink-resistant processing agent in the presence of a catalyst comprising magnesium chloride and a phosphate salt selected from sodium biphosphate, ammonium bihosphate, etc., and subsequently thermally treated at 100-170 deg.C for crosslinking the fiber to obtain the cellulose fiber free from the residual unreacted formaldehyde, excellent in safety, not yellowed, superior to washing resistance, and excellent in crease-resistant and shrink-resistant effects. The crease-resistant and shrink-resistant processing agent comprises a polyester produced by adding a 1-4C aliphatic alcohol (preferably methyl alcohol) of one or two aliphatic dialdehyde compounds such as glyoxal to an esterification product of a 3-6C polycarboxylic acid of formula I (R is a 1-3C lower alcohol) or formula II (preferably 1,2,3,4-butanetetracarboxylic acid), or that substituted with the aliphatic alcohol or the aliphatic dialdehyde compounds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wrinkle-proof / shrink-proofing agent for cellulose fibers, a wrinkle-proof / shrink-proof cellulose fiber treated with this agent, and a method for wrinkle-proofing / shrink-proofing of cellulose fibers.

[0002]

2. Description of the Related Art Generally, wrinkle-proofing and shrink-proofing are known as finishing processes for textiles such as woven fabrics. The resin finishing agents used for such processes are known to give cross-linking to cellulose fibers. It provides wrinkle resistance and shrink resistance.

There are various conventional wrinkle / shrinkproofing agents based on resin (initial condensate) which utilize the reactivity of formaldehyde (HCHO). For example, urea formaldehyde precondensate, melamine / urea formaldehyde. There are initial condensates, other uronic resins, propylene urea resins, glyoxal resins, acetal compounds and the like.

Among these, examples of acetal compounds include diethylene glycol acetal which is a reaction product of polyhydric alcohol such as diethylene glycol and pentaerythritol with formaldehyde or dialdehyde.

[0005] These processing agents may cause skin damage and allergies because unreacted formaldehyde is likely to remain, so that it cannot be said that safety is sufficiently ensured.

As a non-formaldehyde resin type processing agent containing no formaldehyde, dimethylol dihydroxyethylene urea which is a derivative of a dimethyl urea type amino resin (aminoplast resin) is known.

[0007]

However, as described above, of the conventional wrinkle-proofing / shrinking-proofing agents for cellulose fibers, formaldehyde-based agents have a problem in safety, and among them, there is no chlorine adsorption property. An excellent acetal compound has shrink resistance against cellulose fibers, but has a problem of poor wrinkle resistance.

Further, the non-formalin resin has a problem that its cross-linking property is insufficient and its washing durability and wrinkle / shrinkproof effect are weak.

Further, such a non-formalin resin is
Crosslinking reaction temperature with cellulose (curing temperature) is 1
There is also a problem in that the cellulose fiber is yellowed when it is in a narrow temperature range of 40 to 150 ° C., that is, at a high temperature exceeding the above temperature range, and an offensive odor (garlic odor) is emitted at a low temperature below the above temperature range.

Therefore, the present invention solves the above-mentioned problems and is capable of safely using the wrinkle-proof / shrink-proofing agent for cellulose fibers, which has washing durability and exhibits wrinkle-proof / shrink-proof effects. Moreover, it is an object to make the allowable temperature range of the crosslinking reaction temperature as wide as possible.

[0011]

In order to solve the above-mentioned problems, in the present invention, a wrinkle-proof / shrink-proofing agent for cellulosic fibers comprises a polycarboxylic acid having 3 to 6 carbon atoms and 1 to 1 carbon atom.
The polyester obtained by adding or substituting 1 to 2 aliphatic dialdehydes to the esterified product of 4 with the aliphatic alcohol was adopted.

As the polyester, the polyester represented by the following chemical formula 3 or chemical formula 4 can be adopted.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

In addition, an esterified product of a polycarboxylic acid having 3 to 6 carbon atoms and an aliphatic alcohol having 1 to 4 carbon atoms is added to 1
~ Wrinkle-proof with cross-linking between cellulose fibers by polyester with addition or substitution of two aliphatic dialdehydes
It is a shrinkproof cellulose fiber.

Alternatively, in the presence of a catalyst comprising a phosphate selected from sodium hydrogen phosphate and ammonium hydrogen phosphate, and a magnesium salt compound, the cellulose fiber is provided with a polycarboxylic acid having 3 to 6 carbon atoms and a carbon number. 1-4
Wrinkle-proof and shrink-proof processing of cellulosic fiber by impregnating the esterified product with aliphatic alcohol with polyester with 1 to 2 aliphatic dialdehydes added or substituted, and then performing heat treatment to crosslink the fiber I did.

[0017]

The wrinkle-proof and shrink-proofing agent for cellulose fibers according to the present invention is one in which the carboxyl group of the esterified product and the hydroxyl group of cellulose are ester-bonded to crosslink the cellulose fiber, and the ester constituting the crosslink point is formed. Since the chemical structure is strengthened by adding or substituting the aliphatic aldehyde to the (-C00-) portion of the compound, it exhibits wrinkle-proof and shrink-proof effects with washing durability, and the allowable temperature range for the curing temperature is 100. Spreads to about 170 ° C. And since it does not use formaldehyde, it can be used safely.

When the wrinkle-proof and shrink-proofing agent is used to cross-link the cellulose fibers, a catalyst comprising a phosphate selected from sodium hydrogen phosphate and ammonium hydrogen phosphate and a magnesium salt compound is used. When present, the crosslinking reaction proceeds efficiently, so that the tear strength of the cellulose fiber product is improved as compared with the case where the magnesium salt compound is used alone as a catalyst.

[0019]

EXAMPLES First, examples of the cellulose to be subjected to the crosslinking reaction in the present invention include cotton, hemp, rayon and other cellulose blended fibers. These fibers may be textile products such as knitted or woven fabrics.

The polycarboxylic acid used in the present invention is a linear polycarboxylic acid having 3 to 6 carbon atoms or a branched polycarboxylic acid having a side chain which is an isomer thereof, and is a fatty acid having 1 to 4 carbon atoms. When esterified with a group lower alcohol,
Those which can be water-soluble are preferable because of good workability. Specific examples of such a polycarboxylic acid include malonic acid, succinic acid, glutaric acid, saturated dicarboxylic acids such as adipic acid, or their oxycarboxylic acids (such as citric acid), or saturated tricarboxylic acids, 1, 2, 3,4-
Examples thereof include saturated tetracarboxylic acid such as butanetetracarboxylic acid.

The general formula of an ester of 1,2,3,4-butanetetracarboxylic acid and a lower alcohol is shown below.
It was shown to. Among the lower alcohols mentioned above, methyl alcohol is particularly adopted to obtain preferable results.

[0022]

[Chemical 5]

As the dialdehyde used in the present invention, glyoxal represented by OHCCHO, or aliphatic dialdehyde represented by OHC (CH ₂ ) _n CHO (wherein n is an integer of 1 to 4), or these The anhydrous product thereof is mentioned. Among these, more preferable results are obtained when glyoxal or its anhydrous glyoxylic acid is used.

The composition ratio of the polycarboxylic acid, lower alcohol or aliphatic dialcohol constituting the above ester is such that 1 mol of polycarboxylic acid and 4 lower alcohols are used.
-10 mol and 1-2 mol of aliphatic dialdehyde. Esterification reaction of polycarboxylic acid and lower alcohol,
The conditions for the addition or ester substitution reaction of the aliphatic dialdehyde may be either normal pressure or increased pressure, in which case the reaction temperature is 40 to 120 ° C. and the reaction is carried out in the presence of a suitable catalyst. It is preferable in terms of production efficiency.

Since the ester obtained by the above esterification reaction contains an excess of alcohol, it is usually concentrated under reduced pressure and then concentrated to a concentration not corresponding to a dangerous substance to remove the alcohol content before use. However, even if the concentration step is omitted and used as it is, the effect of the present invention is not impaired, and when the concentration is performed, water can be appropriately added to adjust the concentration.

In the present invention, in the reaction of impregnating the fiber with the ester and heating to crosslink between the cellulose,
It is preferably carried out in the presence of a catalyst in which a phosphate selected from sodium hydrogen phosphate and ammonium hydrogen phosphate and a magnesium salt compound are used in combination.

As the above-mentioned sodium hydrogen phosphate,
There are sodium dihydrogen phosphate (NaH ₂ PO ₄ ) or disodium hydrogen phosphate (Na ₂ HPO ₄ ), and ammonium hydrogen phosphate includes ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ) and hydrogen phosphate. There is diammonium ((NH ₄ ) ₂ HPO ₄ ).

Examples of the above-mentioned catalyst magnesium salt compound include magnesium chloride and other salts. Such magnesium salts, when used alone as a catalyst, deteriorate the strength of cellulose such as cotton and hemp and reduce the tear strength thereof, but are selected from the above-mentioned sodium hydrogen phosphate and ammonium hydrogen phosphate. By using such a phosphate together, it is possible to prevent the strength of the cellulose from decreasing.

[Production of wrinkle-proof / shrinkproofing agent] [Example 1] Methyl alcohol 128 g was added to 234 g (1 mol) of 1,2,3,4-butanetetracarboxylic acid in the presence of caustic alkali as a catalyst. (4 mol), water 2
00 g and 145 g (1 mol) of 40% glyoxal were placed in a reactor and reacted with stirring at 85 ° C. and 2 atm for 2 hours to obtain a liquid represented by the formula ( ₃ ) (wherein R = CH ₃ OH). A wrinkle-proof and shrink-proofing agent comprising the ester of

Example 2 To 234 g (1 mol) of 1,2,3,4-butanetetracarboxylic acid, 320 g (1 mol) of methyl alcohol was added in the presence of caustic alkali as a catalyst.
0 mol) and 290 g (2 mol) of 40% glyoxal
Was stored in a reactor and reacted with stirring at 80 ° C. and 2 atm for 2 hours to obtain a wrinkle-proofing and shrink-proofing agent consisting of an ester represented by the formula (4) (R = CH ₃ OH). It was

[Wrinkle-proof / shrink-proof processing of cellulosic fiber] [Examples 3 to 8] Using the wrinkle-proof / shrink-proof processing agent of Example 1 or Example 2, catalyst A (magnesium chloride), catalyst B
(Composite magnesium salt system of magnesium chloride + zinc borofluoride) or catalyst C (magnesium chloride + sodium dihydrogen phosphate) in the presence of the ratio (% by weight) shown in Table 1 cotton broad 40S or rayon taffeta (W / 108).
Book, F / 74), squeezing ratio 80%, predrying 1
Wrinkle-proof / shrink-proof treatment was performed under the conditions of 00 ° C. for 3 minutes, curing conditions of 140 ° C. for 3 minutes, and pre-drying for the width-extending.

Wrinkle resistance (JIS L-1004 B method for cotton broad; JIS L-1003 B method for rayon taffeta) and shrinkage resistance for cotton broad or rayon taffeta that has undergone such prescribed processing. (JIS L-1042 F-1 method), tear strength (JIS L-1004 C method for cotton broad, JIS L-1003 C method for rayon taffeta), wash and wear property (hereinafter abbreviated as W / W property). (AATCC method), flexural wear test (JISL-1)
An evaluation test of physical properties was performed according to the method (003b). The results are shown in Tables 2 and 3.

Further, regarding the cotton broad cloth and rayon taffeta which have been subjected to the wrinkle-proof and shrink-proof treatment in Example 8, the household electric washing method of JIS L-0271-103 method (H
Repeated washing test (1, 5, 10,
20 times) and the results are shown in Table 4 or Table 5.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

[Table 5]

[Comparative Examples 1 and 2] The cotton broad 40S which was not subjected to any wrinkle-proof / shrink-proof treatment was designated as Comparative Example 1, and rayon taffeta (W /
108 pieces, F / 74 pieces) was used as Comparative Example 2 and the evaluation test of the physical properties was performed, and the results are shown in Table 2 or Table 3 together.

[Comparative Example 3] In the presence of the catalyst B, a non-formalin base resin (manufactured by Union Chemical Co., Ltd .: Unicale Resin)
NF-116) was impregnated into cotton broad 40S at the ratio (% by weight) shown in Table 1, squeezing ratio of 80%, predrying at 100 ° C. for 3 minutes, curing conditions at 140 ° C. for 3 minutes, and pre-drying width. Was subjected to wrinkle-proof and shrink-proof processing under the conditions of the original width finish.

After the processing, the cotton broad after the above-mentioned processing was subjected to the above-mentioned physical property evaluation tests, and the results are shown in Table 2 or Table 3.
Also described in.

[Comparative Example 4] In the presence of the catalyst B, a non-formalin base resin (manufactured by Union Chemical Co., Ltd .: Unicale Resin)
NF-116) was impregnated in rayon taffeta (W / 108 pieces, F / 74 pieces) at the ratio (% by weight) shown in Table 1, and the squeezing ratio was 80%, predrying was performed at 100 ° C. for 3 minutes, and curing condition 1 was used.
At 40 ° C. for 3 minutes, the preliminary drier was subjected to wrinkle-proof / shrink-proof processing under the conditions of original width finishing.

After the processing, rayon taffeta was subjected to the evaluation test of each physical property described above, and the results are shown in Table 2 or Table 3.

As is clear from the results of Tables 2 to 4, in the treatment method using the wrinkle-proof and shrink-proofing agent of Example 1 or 2 (Examples 3 to 8), cotton broad or rayon made of cellulose fiber was used. The wrinkle resistance, shrink resistance, and W / W property of taffeta were significantly improved as compared with Comparative Examples 1 to 4. In particular, in Example 5 or Example 8 in which a predetermined catalyst was used at the time of fiber processing, it was found that the tear strength and bending wear resistance were improved.

[0045]

[Effect] As described above, according to the present invention, the wrinkle-proof / shrink-proofing agent for cellulosic fibers is composed of an esterification product of a predetermined polycarboxylic acid and an aliphatic alcohol. Demonstrates a wrinkle-proof and shrink-proof effect that can be secured and has washing durability against cellulose fibers,
Moreover, there is an advantage that the allowable temperature range of the curing temperature is widened and the cellulose fibers are less likely to yellow.

In the processing method of crosslinking the wrinkle-proof / shrink-proofing agent for cellulose fibers to the cellulose fibers in the presence of a catalyst in which a predetermined phosphate and magnesium salt compound are used in combination, the tear strength of the cellulose fiber product is improved. There is also an advantage.

Claims (5)

[Claims] 1. An esterified product of a polycarboxylic acid having 3 to 6 carbon atoms and an aliphatic alcohol having 1 to 4 carbon atoms, and 1 to 2
A wrinkle-proofing / shrinking-proofing agent for cellulose fibers, which is made of polyester in which aliphatic dialdehydes have been added or substituted. 2. The wrinkle-proof and shrink-proofing agent for cellulose fibers according to claim 1, wherein the polyester is a polyester represented by the following chemical formula 1. [Chemical 1] 3. The wrinkle-proof and shrink-proofing agent for cellulose fibers according to claim 1, wherein the polyester is a polyester represented by the following chemical formula 2. [Chemical 2] 4. An esterified product of a polycarboxylic acid having 3 to 6 carbon atoms and an aliphatic alcohol having 1 to 4 carbon atoms, in which 1 to 2 is added.
A wrinkle-proof and shrink-proof cellulose fiber obtained by cross-linking cellulose fibers with a polyester in which aliphatic dialdehydes have been added or substituted. 5. A polycarboxylic acid having 3 to 6 carbon atoms and a carbon number in a cellulose fiber in the presence of a catalyst comprising a phosphate selected from sodium hydrogen phosphate and ammonium hydrogen phosphate, and a magnesium salt compound. An esterification product of 1 to 4 aliphatic alcohols is impregnated with a polyester in which 1 to 2 aliphatic dialdehydes are added or substituted, and then heat-treated to give cross-links to the fibers to prevent cellulosic fibers. Wrinkle / shrinkproof processing method.