JPS6142027B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel laundry starch compositions. More specifically, the present invention relates to a new laundry finishing glue that eliminates the drawbacks of starch and polyvinyl alcohol that have been conventionally used as laundry glue.

Depending on the type of clothing or other household textile products, dirt is removed by laundry or dry cleaning, and finishes such as starching and softening are applied. The present invention relates to a finishing sizing agent for textile products that are cleaned and finished in the laundry room. It is often used in recycled fiber products or blended products with polyester fibers. However, among them, blends with polyester fibers, such as 35% cotton and 65% polyester fibers, are widely used in white shirt fabrics,
It is used as a blouse fabric, and because it is relatively resistant to wrinkles after washing, it has the advantage that it can be ironed relatively easily compared to products made only of cotton. However, on the other hand, since polyester fiber is a hydrophobic fiber, it easily attracts oil-based stains, generates static electricity, and even when starch-based glue is used as a laundry glue, it has poor adhesion and poor finishing. It has the following disadvantages. In view of this current situation, we have conducted intensive research into washing finishing glues mainly for polyester fiber-cotton blended yarn fabrics, and have found that extremely excellent washing results can be obtained by using a limited amount of water-soluble polyester resin in combination with starch or vinyl alcohol. It has been found that a finishing paste can be obtained. Clothes, blouses, etc. are being washed at home more and more due to the rise in processing fees for specialized laundry shops and the spread of polyester fiber-cotton blended yarn fabrics. There is a growing demand for drugs. From this point of view, the properties required for laundry starches include good adhesion to polyester fibers, excellent antistatic properties, as well as appropriate flexibility and the ability to absorb size liquid. It must meet the required characteristics, such as being stable, able to be used as much as necessary, able to be stored, and easily falling off when rewashed. To meet these required properties, (A) 5 to 40% by weight of polyethylene glycol with an average molecular weight of 600 to 6000, (B) the weight of bis(β-hydroxyethyl) terephthalate and bis(β-hydroxyethyl) isophthalate. Ratio is 95:
5-70:30 mixture of ethylene glycol esters of dibasic acids 40-75% by weight (C) 3-15% by weight of alkali metal salts of 5-sulfoisophthalic acid and (D) 0 ethylene glycol or propylene glycol
By mixing a water-soluble polyester resin obtained by copolycondensation of ~30% by weight with starch and/or polyvinyl alcohol, an extremely excellent laundry paste that satisfies these properties was obtained. Although starch and polyvinyl alcohol are excellent sizing agents for cotton products, they lack adhesion and have poor antistatic properties for polyester fiber-cotton blends, so softeners may be added. It is known to use polyvinyl acetate-based polymers, maleic anhydride-based copolymers, and acrylic ester-based copolymers in combination, but polyvinyl acetate-based polymers themselves are not water-soluble, so they are difficult to wash during washing. It has poor removability and tends to remain with dirt, and it also copolymerizes unsaturated carboxylic acids with maleic anhydride copolymers and acrylic ester copolymers and makes them water-soluble as alkali metal salts and amine salts. At first glance, copolymers have good water solubility and therefore seem to have good washability, but in reality, they selectively adsorb calcium, magnesium ions, or iron in water during washing, making the copolymers themselves insoluble and hydrophobic. It strongly adsorbs to polyester fiber, which is a polyester fiber, and has the disadvantage that it becomes difficult to fall off along with oily stains and gradually yellows when pasting and washing are repeated. On the other hand, the aqueous polyester resin of the present invention can be used in combination with starch or polyvinyl alcohol to increase adhesion, give appropriate flexibility, and not only feel good on the skin, but also have antistatic properties. Unlike ionic copolymers with weak acidic groups copolymerized with saturated carboxylic acids, they do not become insolubilized by calcium salts or magnesium salts in water, so there is no glue residue or accumulation even after repeated use, and stains are removed. It provides an extremely good adhesive. In order to extremely improve this stain removal property, the water-soluble polyester resin used in the present invention must contain 5 to 40% by weight of polyethylene glycol with an average molecular weight of 600 to 6000 as its constituent component (A). Only those with a molecular weight of less than 600, 5% by weight
If it is less than this, the water solubility will be insufficient and the water-soluble polyester resin will be hard and brittle, so the texture of the pasted textile product will be rough and hard, which is not preferable. On the other hand, if the average molecular weight of polyethylene glycol is 6,000 or more or 40% by weight or more, the affinity with fibers will be poor and the sizing effect will be insufficient, which is undesirable. Next, as component (B), bis(β-hydroxyethyl)
Terephthalate and bis(β-hydroxyethyl)
A dibasic acid component having a weight ratio of 95:5 to 70:30 with isophthalate is required in an amount of 40 to 75% by weight. When synthesizing a water-soluble polyester resin, it is necessary to melt and mix each component (A) to (D) at a relatively low temperature to form a homogeneous mixture before the polycondensation reaction proceeds. Bisethylene glycol ester of terephthalic acid or isophthalic acid, i.e. bis(β-hydroxyethyl) terephthalate or bis(β-hydroxyethyl) as acid component.
Isophthalate is necessary, and terephthalic acid or isophthalic acid itself is not preferred because a homogeneous polycondensation reaction product cannot be obtained. When starting from terephthalic acid, isophthalic acid, or their methyl esters, ethyl esters, etc., they are esterified or transesterified with ethylene glycol to form bis(β-hydroxyethyl).
After forming terephthalate or bis(β-hydroxyethyl) isophthalate, a polycondensation reaction can be performed with other components. At the same time, if only bis(β-hydroxyethyl) terephthalate is used as the dibasic acid component, the water-soluble polyester resin and the laundry starch containing it will become coarse and hard, resulting in poor texture of the textile products to which they are pasted, which is the most disliked problem. It is. For this purpose, by mixing bis(β-hydroxyethyl) terephthalate and bis(β-hydroxyethyl) isophthalate in a ratio of 95:5 to 70:30 and polycondensing, only bis(β-hydroxyethyl) terephthalate can be used. This resulted in a resin with an extremely good texture. On the other hand, bis(β-hydroxyethyl)
On the other hand, if the isophthalate ratio exceeds 70:3, the polycondensation reaction will be inhibited and the resin will not only have insufficient adhesion to fibers and shape retention, but will also have poor water solubility, making it difficult to wash when rewashed. The shedding property becomes poor, which causes discoloration during repeated washing and gluing.
Component (C), an alkali metal salt of 5-sulfoisophthalic acid, is necessary in combination with component (A) to increase the water solubility of the polyester resin. If it is less than 3 to 15% by weight, the water solubility will be insufficient, and if it is more than 3% by weight, the hydrophilicity will be excessive and the affinity for fibers, especially hydrophobic fibers, will be insufficient. The alkali metal salt of 5-sulfoisophthalic acid is an alkali metal salt of a sulfonic group, mainly sodium or potassium salt, and isophthalic acid is a free acid. Polyester resins in which no sulfone groups are introduced and carboxyl groups remain can also be made water-soluble by adding an alkali metal to them, but polyester resins made water-soluble by using salts of carboxyl groups can absorb polyvalent metals in water, For example, it is insolubilized by calcium, magnesium, iron, etc., and yellows during repeated washing, which is an extremely undesirable drawback. At the same time, it also has antistatic ability due to the introduction of a sulfone group, and has extremely good properties. next
Ethylene glycol or propylene glycol as component (D) is 30% by weight in order to adjust the degree of polymerization of water-soluble polyester resin and improve affinity with fibers.
Copolycondensate within a range not exceeding . This is 30% by weight
If it is more than that, disadvantages such as insufficient water solubility will appear, which is not preferable. When producing a water-soluble polyester resin from these components (A) to (D), it is preferable to adjust the molar ratio of the acid component to the alcohol component to be around 1:1. Or, since propylene glycol is volatile, it is added in excess and distilled off during the polycondensation reaction.
As a result, the polyester resin can have a ratio of acid component and alcohol component of around 1:1. These components (A) to (D) are mixed and melted by heating, and if necessary, an esterification catalyst such as phosphoric acid, polyphosphoric acid, phosphorous acid, p-toluenesulfonic acid, acetate titanate, etc. is added, and the mixture is heated at normal pressure or Temperature 200-300℃ under reduced pressure
A water-soluble polyester resin is obtained.

Starch and polyvinyl alcohol, which are other components of the laundry glue composition of the present invention, do not need to be particularly limited, but may be affected by factors such as ease of handling, stability over time, and the size of aerosol particles when used as an aerosol product. Raw starches such as corn starch and wheat starch can be used as the starch, but soluble starches derived from these by oxidation, roasting, etc., esterified starches, etherified starches, hydroxylated starches, etc. are preferable, and as polyvinyl alcohol, polymerized starches degree 500~2300 degree,
A saponification degree of 80% or more is preferred. These starches and polyvinyl alcohols can be used as a mixture of two or more types, but the mixing ratio of water-soluble polyester resin and starch and/or polyvinyl alcohol is usually 50:50 to 50:50.
It is sufficient to use the water-soluble polyester resin in an amount of about 5:95, that is, 5% by weight or more, which is less than half of the total glue component. In addition, when using such a laundry starch composition, an oil component or a preservative and fungicide may be added to the extent that it does not contradict the idea of the present invention, and it is also suitable for pasting textile products. The entire product may be immersed and squeezed, or it may be applied partially as an aerosol product. In addition, as described in detail, the laundry starch composition of the present invention is particularly effective for polyester fiber blended products, but it is no inferior to other cotton products as well. It can be widely used as long as it is a textile product.

Next, a more detailed explanation will be given with reference to examples.

Example 1 A water-soluble polyester resin (A) was synthesized using the following raw material composition.

Bis(β-hydroxyethyl) terephthalate
1000g (41.7% by weight) Bis(β-hydroxyethyl)isophthalate
400〃(16.7〃) Polyethylene glycol (molecular weight 2000)
300〃(12.5〃) Sodium 5-sulfoisophthalate
300〃(12.5〃) Ethylene glycol 400〃(16.7〃) Calcium acetate 1〃 A glue having the following composition was prepared using the above water-soluble polyester resin (A).

Modified starch 7% Water-soluble polyester glue (A) 3 Methyl paraoxybenzoate 0.5 When this glue solution was further diluted 20 times and glued to a cotton blouse, it had a firm yet supple finish. It completely fell off after washing, and stain removal was also good.

Example 2 A water-soluble polyester resin (B) was synthesized using the following raw material composition.

Bis(β-hydroxyethyl) terephthalate
1000g (48.8% by weight) Bis(β-hydroxyethyl)isophthalate
200〃(14.4〃) Polyethylene glycol (molecular weight 4000)
400〃(19.5〃) Sodium 5-sulfoisophthalate
200〃(9.8〃) Propylene glycol 250〃(12.2〃) Titanium potassium oxalate 1〃 A glue having the following composition was prepared using the above water-soluble polyester resin (B).

Polyvinyl alcohol (degree of polymerization 1700) 3% Water-soluble polyester glue (B) 0.6 This glue solution was further diluted 10 times with water and glued onto a polyester/cotton (65/35) mixed dress shirt. It has a firm yet smooth finish. Furthermore, no static electricity was observed even during the dry winter season. In addition, washing - starching - wearing 20
After repeated use several times, stains were removed well and there was almost no decrease in whiteness.

Example 3 A water-soluble polyester resin (C) was synthesized using the following raw material composition.

Bis(β-hydroxyethyl) terephthalate
1000g (57.1% by weight) Bis(β-hydroxyethyl)isophthalate
300〃(17.1〃) Polyethylene glycol (molecular weight 1000)
300〃(17.1〃) Sodium 5-sulfoisophthalate
150〃(8.6〃) Calcium acetate 1〃 Prepare an aerosol type glue having the following composition using the water-soluble polyester resin (C) above.

Polyvinyl alcohol (degree of polymerization 500) 4g Water-soluble polyester glue (C) 1〃 Water 95〃 Dimethyl ether 150〃 Spray this aerosol type glue on the collar and cuffs of a dress shirt made of polyester/cotton (65/35) blend. As a result, the finish had a suitable hardness and stain removal was also extremely good.

Claims (1)

[Claims] 1 (A) 5 to 40% by weight of polyethylene glycol with an average molecular weight of 600 to 6000 (B) The weight ratio of bis(β-hydroxyethyl) terephthalate to bis(β-hydroxyethyl) isophthalate is 95:5 to 70:
30 to 75% by weight of a mixture of ethylene glycol esters of dibasic acids (C) 3 to 15% by weight of alkali metal salts of 5-sulfoisophthalic acid and (D) 0 to 30% by weight of ethylene glycol or propylene glycol. A laundry paste composition comprising a water-soluble polyester resin obtained by copolycondensation in combination with starch and/or polyvinyl alcohol.