JP3720420B2 - Laundry paste for textile products - Google Patents

Description

【００２４】
【表２】

【００２５】
【発明の効果】
本発明の繊維製品用洗濯糊剤は，天然繊維のみならず合成繊維製品に対しても糊付着量が高く，またアイロン仕上げ時の着色がなく，アイロンに対する汚れ付着のない点で優れており，極めて有用性が高い。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel laundry paste for textile products. More particularly, the present invention relates to a laundry sizing agent for textiles having a good thermal stability and a good texture made of a specific modified polyvinyl alcohol.
[0002]
[Prior art]
Conventionally, as a laundry sizing agent for textile products, starch, polyvinyl alcohol resin (hereinafter abbreviated as PVA), aqueous solution type such as carboxymethyl cellulose, or polyvinyl acetate emulsion or cationic polymer is used. An emulsion type such as a cationic emulsion obtained by emulsion polymerization of a monomer has been used. However, compared to starch paste, PVA is currently widely used as a water-soluble paste because it can be stored for a long time without being spoiled and the strength of the resulting film is strong, resulting in a crisp texture. . PVA also has better paste removal during washing than emulsion type.
[0003]
[Problems to be solved by the invention]
Conventional PVA-based laundry glue also has the disadvantage that adhesive strength is insufficient with respect to synthetic fiber products such as shirt fabrics, and the adhesive adhesion rate is low because PVA falls off the fibers in the dehydration process during gluing. In addition, the thermal stability is poor, and when white clothes are used for ironing, there are problems such as lowering the whiteness and attaching dirt to the iron.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve such problems, the present inventors have found that a modified PVA containing 1 to 24 mol% of an α-olefin unit having 4 or less carbon atoms in the molecule (the modified PVA further comprises a cationic group). The present invention has been completed by finding a laundry sizing agent for textile products, which may contain 0.1 to 10 mol% of a content unit.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in more detail below. The modified PVA containing 1 to 24 mol% of an α-olefin unit having 4 or less carbon atoms in the molecule used in the laundry paste for textiles of the present invention is a co-polymerization of a vinyl ester and an α-olefin having 4 or less carbon atoms. It is obtained by saponifying the coalescence.
Examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and the like, and vinyl acetate is economically desirable.
The α-olefin used in the present invention has 4 or less carbon atoms, and examples thereof include ethylene, propylene, n-butene, and isobutene. Ethylene is preferable because of easy availability of raw materials.
The α-olefin content is required to be 1 to 24 mol%, preferably 2 to 9 mol%. When the α-olefin content is less than 1 mol%, the effect of the present invention cannot be obtained, and when it exceeds 24 mol%, the water solubility or water dispersibility is lowered and the paste removal property during washing is poor. It becomes.
[0006]
The modified PVA used for the textile product laundry paste of the present invention means a cationic group-containing unit (a chemical structural unit that is dissociated in an aqueous solution and charged to a positive charge) for the purpose of improving water solubility or water dispersibility. ) May be copolymerized.
That is, in the molecule, an α-olefin having 4 or less carbon atoms, a vinyl ester and a cationic group-containing monomer such as trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, 3-acrylamidopropyltrimethyl. Ammonium chloride, 3-methacrylamidopropyltrimethylammonium chloride, quaternary ammonium salt of N- (3-allyloxy-2-hydroxypropyl) dimethylamine, quaternary ammonium salt of N- (4-allyloxy-3-hydroxybutyl) diethylamine Furthermore, acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, N-methylolacrylamide, methacrylamide, N-methylmethacrylate Amide, N- ethyl methacrylamide, N- After methylol by copolymerizing a quaternary ammonium salt such as methacrylamide, an object of the PVA is obtained by saponifying a known manner this.
The content of these cationic group-containing units is preferably from 0.1 to 10 mol%. When the content of the cationic group-containing unit is less than 0.1 mol%, the effect of introducing the cationic group is not observed, and when it exceeds 10 mol%, the performance of the modified PVA of the present invention cannot be obtained. , The production cost is also high, which is not economically preferable.
[0007]
Furthermore, the modified PVA used in the textile product laundry paste of the present invention may be one obtained by copolymerizing other copolymerizable ethylenically unsaturated monomers within a range not impairing the effects of the present invention. Examples of such ethylenically unsaturated monomers include acrylic acid, methacrylic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, acrylonitrile, methacrylonitrile, and acrylamido-2-methylpropane. Examples thereof include sulfonic acid and its sodium salt, sodium vinyl sulfonate, sodium allyl sulfonate, ethyl vinyl ether, butyl vinyl ether, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene and the like.
Further, a terminal obtained by copolymerizing a vinyl ester monomer such as vinyl acetate with an α-olefin having 4 or less carbon atoms in the presence of a thiol compound such as thiolacetic acid or mercaptopropionic acid, and saponifying it. Modified PVA can also be used.
The content of these ethylenically unsaturated monomer units is preferably less than 2 mol%, more preferably less than 1.0 mol%, and even more preferably less than 0.5 mol%.
[0008]
The average degree of polymerization of the modified PVA used in the textile product laundry paste of the present invention is usually selected from 100 to 5000, preferably 200 to 3000, and the average saponification degree of the vinyl ester portion is not particularly limited. , Usually 60 to 100 mol%, preferably 70 to 99.9 mol%. If the average degree of polymerization is less than 100, the performance as a laundering paste, particularly the strength of the film and the adhesive strength to fibers, is lowered, and if it exceeds 5000, the viscosity of the paste becomes too high, which is not preferable in terms of workability. On the other hand, when the average saponification degree is less than 60 mol%, it is not preferable because water solubility or water dispersibility is deteriorated and paste removal property during washing becomes poor.
[0009]
The laundry paste for textiles made of the modified PVA of the present invention is sufficiently effective in the case of the modified PVA alone, but other known auxiliary agents such as oils, surfactants, softeners, fragrances are used as necessary. , Fluorescent dyes, pigments, preservatives, fungicides, fungicides, etc. may be added. In addition, other known sizing agents such as raw starch, modified starch (cationized starch, carboxymethylated starch, etc.), general PVA, modified PVA (carboxyl group-containing modified PVA, acrylamide modified) without departing from the spirit of the present invention. PVA etc.), carboxymethyl cellulose, water-soluble polyester resin, polyethylene glycol, etc. may be used in combination.
[0010]
When gluing is performed after washing the textile product, the paste of the present invention is preferably used in a range of 0.2 to 5% by weight in solid content with respect to the textile product. Even if the paste of the present invention is diluted with a sufficient amount of water as compared with the conventional PVA-based laundry paste, a good pasting effect can be obtained.
The PVA resin of the present invention can also be effectively used as a spray type finishing agent. Any container of a commercially available spray type can be used, and an aqueous solution prepared by adjusting the solid content concentration of the PVA resin to 1 to 15% by weight is used. This is very practical as a non-solvent finish. Of course, it can be used as a liquefied jet type with a solvent such as dimethyl ether.
[0011]
By ironing the fiber product thus glued at a temperature of about 170 ° C., there is no discoloration due to heat or adhesion of dirt to the iron, and a crisp finished textile product laundry glue is obtained.
As described above, the present invention has been described by taking the textile product laundry paste as an example. The textile product laundry paste of the present invention is a warp paste for textiles, a resin processing, a paste for printing, a felt, It can also be used effectively as a binder for nonwoven fabrics.
[0012]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples. In the following, “part” and “%” mean “part by weight” and “% by weight”, respectively, unless otherwise specified.
[0013]
Example 1
A copolymer of ethylene and vinyl acetate was alkali saponified to obtain an ethylene-modified PVA containing 7.1 mol% of ethylene units, a saponification degree of vinyl acetate units of 95.4 mol%, and a polymerization degree of 1700.
This ethylene-modified PVA was evaluated by the following method. The results are shown in Table 1.
(1) Evaluation of tension Using a small household washing machine, 500 g of the ethylene-modified PVA aqueous solution (solid content 10%) obtained above was added to 10 liters of tap water and dispersed well, and then 500 g Sheets (cotton cloth; broad) were added and stirred for 3 minutes. After that, it was dehydrated, air-dried and ironed for 30 seconds with a dehydrator. A tactile sensation test was carried out by comparing the tension of the cloth subjected to the gluing treatment as described above with a control gluing cloth (starch glue).
Ten people tested and evaluated the performance of the paste with the total of the following evaluation points.
+2: Tightened +1: Slightly tensioned 0: Same as control -1: Slightly tensioned -2: Not tensioned (2) Amount of glue applied Glued by the method of (1) above-Air-dried cotton sheets After finishing by ironing, it was conditioned at 20 ° C. and 65% RH for 24 hours. The amount of glue attached to the glued cloth was determined by weight measurement.
(3) Adhesiveness to iron When the cotton sheet, which had been glued and air-dried by the method of (1) above, was ironed at 170 ° C., the state of adhesion of the residue to the iron was observed.
(4) Thermal coloring property After the cotton sheets dried and air-dried by the method of (1) were heat-treated at 170 ° C. for 10 minutes, the degree of coloring was observed in comparison with the original fabric (no pasting).
Further, the polyester-cotton blended fabric (polyester / cotton = 65/35; cloth for shirts) was subjected to gluing-finishing in the same manner and evaluated.
[0014]
Example 2
A test was conducted in the same manner as in Example 1 except that ethylene-modified PVA containing 2.3 mol% of ethylene units, having a saponification degree of 88.0 mol% of the vinyl acetate portion and a polymerization degree of 1000 was used. The results are shown in Table 1.
[0015]
Example 3
It contains 5.5 mol% of ethylene units, 1.0 mol% of cationic group-containing units (3-acrylamidopropyltrimethylammonium chloride units), has a saponification degree of vinyl acetate part of 88.0 mol% and a polymerization degree of 1700. The same test as in Example 1 was performed except that ethylene-cationic group-modified PVA was used. The results are shown in Table 1.
[0016]
Comparative Example 1
The same test as in Example 1 was performed except that commercially available unmodified PVA (Kuraray Poval PVA-CST) was used. The results are shown in Table 1.
[0017]
Comparative Example 2
The same test as in Example 1 was performed except that commercially available unmodified PVA (Kuraray Poval PVA-210) was used. The results are shown in Table 1.
[0018]
Example 4
A copolymer of ethylene and vinyl acetate was alkali saponified to obtain an ethylene-modified PVA containing 5.5 mol% of ethylene units, a saponification degree of vinyl acetate units of 95.0 mol%, and a polymerization degree of 500.
This ethylene-modified PVA was evaluated by the following method. The results are shown in Table 2.
(1) Evaluation of tension A 5% aqueous solution of ethylene-modified PVA thus obtained was prepared, glued to a sheet (cotton cloth; broad) using a commercial sprayer, and finished by ironing. A tactile sensation test was performed by comparing the tension of the glued cloth with a control glued cloth (starch glue).
Ten people tested and evaluated the performance of the paste with the total of the following evaluation points.
+2: Tension +1: Slight tension 0: Same as control -1: Slight tension-2: No tension (2) Clogging test Using a commercial sprayer, temperature 20 ° C, humidity 65% RH environment Under spraying 10 times / day for one month, the presence or absence of clogging was examined.
(3) Adhesiveness to iron When the cotton sheet glued by the method of (1) was ironed at 170 ° C., the adhesion state of the residue to the iron was observed.
(4) Thermal coloring property After the cotton sheets glued by the method of (1) were heat-treated at 170 ° C. for 10 minutes, the degree of coloring was observed in comparison with the original fabric (no gluing).
Further, the polyester-cotton blended fabric (polyester / cotton = 65/35; cloth for shirts) was subjected to gluing-finishing in the same manner and evaluated.
[0019]
Example 5
It contains 5.5 mol% of ethylene units, 1.0 mol% of cationic group-containing units (3-acrylamidopropyltrimethylammonium chloride units), has a saponification degree of vinyl acetate portion of 81.9 mol% and a polymerization degree of 500. The same test as in Example 4 was performed except that ethylene-cationic group-modified PVA was used. The results are shown in Table 2.
[0020]
Example 6
It contains 7.1 mol% of ethylene units, 2.0 mol% of cationic group-containing units (3-acrylamidopropyltrimethylammonium chloride units), has a saponification degree of 73.1 mol% of the vinyl acetate moiety and a polymerization degree of 500. The same test as in Example 4 was performed except that ethylene-cationic group-modified PVA was used. The results are shown in Table 2.
[0021]
Comparative Example 3
The test was conducted in the same manner as in Example 4 except that a commercially available unmodified PVA (Kuraray Poval 205) was used instead of the ethylene-modified PVA used in Example 4. The results are shown in Table 2.
[0022]
Comparative Example 4
The test was conducted in the same manner as in Example 4 except that a commercially available unmodified PVA (Kuraray Poval 405) was used instead of the ethylene-modified PVA used in Example 4. The results are shown in Table 2.
[0023]
[Table 1]

[0024]
[Table 2]

[0025]
【The invention's effect】
The laundry paste for textiles of the present invention is excellent in that it has a high amount of glue applied not only to natural fibers but also to synthetic fiber products, has no coloring during ironing, and does not adhere to the iron. Very useful.

Claims (2)

For fiber products comprising 1 to 24 mol% of α-olefin units having 4 or less carbon atoms in the molecule, an aqueous solution of modified polyvinyl alcohol having an average degree of polymerization of 500 to 5000 and an average degree of saponification of 60 to 100 mol% Laundry paste.   The laundry paste for textiles according to claim 1, wherein the modified polyvinyl alcohol contains 0.1 to 10 mol% of a cationic group-containing unit.