KR950006296B1 - Unit packing detergent - Google Patents

Abstract

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Description

Single Package Freshener

The present invention relates to single-package fresheners and films suitable for packaging. As used herein, the term “single packaged detergent” refers to a detergent packaged in a water-soluble polymer film or sheet in a suitable form for single use.

Up to now, detergent powders or granules have usually been packed and sold in boxes or water-insoluble bags, for example polyethylene bags, and the amount of detergent powder or granules has been measured in spoons or measuring cups or otherwise could not be metered into the washing machine. However, this conventional approach is inconvenient to use the cleaning agent in an amount suitable for cleaning, not only wasting it, but also easy to spill for flooring. In addition, unmanned laundry has recently been developed, and there is a desire to develop a single packaged detergent for use therein.

Until now, the use of polyvinyl alcohol (Japanese Patent Publication No. 62-4800) as a single packaging detergent, for example, a packaging film, has been studied and proposed, but the solubility of the film in water is insufficient so that a gel of insoluble polyvinyl alcohol or The jelly adheres to the washed clothing and it takes a long time to wash off the glued ones. Thus, this method was hardly practical.

It is an object of the present invention to provide a single packaged detergent which is readily soluble in water and does not remain in the garment after washing, and a film or sheet suitable for this purpose.

The single packaged detergent of the present invention comprises (1) a tear strength of at least about 50 kg / cm, (2) a dissolution time shorter than about 20 seconds, and (3) an equilibrium of less than about 20% at 20 ° C. and 80% relative humidity. Contains detergent powders or granules packaged in films or sheets made of water-soluble polymers having an equilibrium moisture content.

The present invention has (1) a tear strength of about 50 kg / cm or more, (2) a dissolution time shorter than about 20 seconds, and (3) an equilibrium moisture content of about 20% or less at 20 ° C and 80% relative humidity. A single packaged detergent of the present invention containing a detergent powder or granules packaged in a film or sheet made of a water soluble polymer, and a water soluble polymer film or sheet used for a single packaged detergent.

The water-soluble polymer film or sheet used in the present invention is made of a water-soluble polymer having the properties described above.

The tear strength is determined in accordance with JIS K 6301-1975.

In the present specification, the dissolution time of the polymer is defined as the time required for the polymer film having a thickness of 30 μm and an area of 1 cm 2 to be completely dissolved in water until the surface of the water is increased at 20 ° C.

The equilibrium water content of the polymer is determined as follows: (1) The test film is placed in a petri dish, and the petri dish is placed in a desiccator with an ammonium chloride saturated aqueous solution in an amount of about 5-10% by volume of the lower space. So that the relative humidity in the desiccator is maintained at about 80% at 20 ° C; (2) the desiccator was kept at 20 ° C. for 10 days in a constant temperature chamber; And (3) the film in the desiccator is weighed daily over 10 days to determine the equilibrium moisture content of the polymer.

As a polymer that satisfies the above properties and has film formable properties, polyoxyethylene derivatives such as polyesters of polyether polyols containing polyoxyethylene moieties together with polycarboxylic acids and the like can be exemplified.

Preferred polyether polyols contain polyoxyethylene moieties as main components, which may contain other polyoxyalkylene moieties derived from alkylene oxides such as propylene oxide, butylene oxide and styrene oxide and the like. Such polyether polyols can be derived by reacting alkylene oxides with compounds having a plurality of active hydrogen atoms in the molecule (hereinafter referred to as active hydrogen-containing compounds). Such active hydrogen-containing compounds include alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and the like; Aliphatic polyols such as glycerin, sorbitan pentaerythritol, sugar alcohols, polyglycerols and the like; Aromatic polyols such as hydroquinone, phloroglucinol and the like; Amines such as ethylamine, hexylenediamine, phenylenediamine, cyclohexylamine, benzylamine, aniline, imidazolidine and the like; Amides; Mercaptan etc. are mentioned. Where the active hydrogen-containing compound contains hetero atoms, such as amines, amides or mercaptans, the compounds obtained are also included in the concept of “polyether polyols” although they contain hetero atoms herein.

Preferred polyether polyols are polyether diols in terms of solubility in water and polymeric ability. Monoalcohols cannot extend the polymer chains, and triols or polyols having three or more hydroxyl groups tend to resemble and become insoluble in water.

Mixtures of polyether polyols such as polyethylene glycol and polypropylene glycol; Polyethylene glycol and polyoxyethylene / polyoxypropylene copolymers; Polyoxyethylene glycerin and polyoxyethylene / polyoxypropylene copolymer; Polyoxyethylene triethanol amine and polyoxyethylene / polyoxypropylene copolymers; These compositions are not limited to the above.

The polyether polyol itself may contain a plurality of residues such as oxyethylene residues and oxypropylene residues, which may be block copolymers or random cyclopolymers.

The polyether polyols are prepared according to the traditional manner, for example, with the desired alkylene oxide or mixture of two or more alkylene oxides with one or more active hydrogen-containing compound (s) and a catalyst, for example alkalis such as calcium hydroxide, sodium carbonate. It can be obtained by reacting at a temperature of, for example, 60 to 160 ° C. under an appropriate pressure such as 0 to 10 atmospheres (gauge pressure) in the presence of a catalyst or an acid catalyst such as boron trifluoride.

Alkali catalysts for the addition polymerization of alkylene oxides are particularly preferred because they can also be used as catalysts for continuous esterification without any removal of the catalyst or additional use of the catalyst.

The content of the polyoxyethylene moiety in the polyether polyol is preferably at least 50% by weight and more preferably 70 to 100% by weight based on the total weight of the polyether polyol. If the content of the polyoxyethylene moiety is less than 50%, the water-solubility is insufficient.

The polyether polyols must be water-soluble and have a weight average molecular weight of preferably about 1,000 or more, more preferably about 2,000 or more, and most preferably about 3,000 to 50,000 in terms of water-solubility and tear strength.

As mentioned above, examples of the most preferred polymers for the present invention are polyesters of polyether polyols and polycarboxylic acids. Such polymers can be prepared according to Japanese Patent Application Laid-open No. 56-226018, which is incorporated in the present specification.

Examples of polycarboxylic acids usable for the production of polyesters include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suveric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, mesaconic acid, malic acid, tartaric acid Aliphatic polycarboxylic acids such as nucleic acid tricarboxylic acid and the like; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimeryl acid, pyromellitic acid, 1,5-naphthalenedicarboxylic acid, dimer acid and the like. The polycarboxylic acid may be part or all ester, which may be reacted by transesterification, or may be an acid anhydride such as maleic anhydride, phthalic anhydride, pyromellitic anhydride and the like.

Lower alkyl esters of polycarboxylic acids can also be used, for example methyl esters, polymethyl esters, mono or polyethyl esters and the like.

Mixtures of polycarboxylic acids can be used.

Most preferred polycarboxylic acids are phthalic acid, terephthalic acid, isophthalic acid, sebacic acid, pyromellitic acid, dimethyl ester, diethyl ester and the like and lower alkyl esters thereof.

Preferred weight average molecular weights of polymers such as polyesters of polyether polyols and polycarboxylic acids are about 10,000 to 500,000. If the molecular weight is less than 10,000, the water-solubility of the obtained polymer film or sheet will be sufficient but the tear strength will be lowered and the average moisture content will exceed the required lower limit, whereas a molecular weight of more than 500,000 will reduce the water-solubility. I will.

The ratio of the polyether polyol and polycarboxylic acid, ester or acid anhydride is not limited as long as the molecular weight of the polyether polyol is not more than 1,000 and the molecular weight of the obtained polymer is not 10,000 or less and 500,000 or less is satisfied.

Films or sheets obtained from such polymers, in particular polyesters, have excellent water-insolubility and are readily soluble in water, ie can dissolve at a rate of about 2 to 5 times higher than films of water-soluble polyvinyl alcohols of the same thickness. Thus, single-pack detergents packaged with a film or sheet made of the polymer are immediately and completely dissolved in water when thrown into the washing machine, and problems such as adhesion or deposition of polymer insolubles onto washed clothes do not occur. In addition, films or sheets made of such polymers have a tear strength that is high enough not to tear or break when used as packaging films or sheets usable in automatic packaging machines. In addition, the films or sheets obtained from the polymers have a low equilibrium moisture content, which, despite their high water-solubility, can maintain their elevated strength even under high humidity as in the rainy season, which is particularly advantageous for the purposes of the present invention. . Because the polymers described above are chemically stable and heat sealable, as well as the water-solubility of the heat sealed portions remains intact, unlike PVA, they do not adhere and remain on the washed garment after washing, Can be used as a single packaged detergent for home and vending machines.

The esterification of polyether polyols with polycarboxylic acids, esters or acid anhydrides is carried out by conventional methods, for example under reduced pressure of catalysts such as p-toluenesulfonic acid, boron trifluoride, potassium hydroxide, sodium hydroxide, magnesium hydroxide, alkali metals. It can carry out by heating in presence.

Preferred temperatures are about 80-250 ° C., preferred pressures are about 0.001-20 Torr. The reaction is usually completed within 0.5-10 hours. Of course, the reaction may be performed while removing water or lower alcohol generated by venting with nitrogen gas. However, the above esterification is merely a suitable example and should not be taken as limiting.

Molecular weight can be adjusted by adjusting a pressure reduction by the ratio of a polyether polyol and polycarboxylic acid. The latter is more practical and easy. If the reaction pressure is lowered, a polymer having a higher molecular weight can be obtained.

Although the aforementioned polyesters are most suitable for providing detergent packaging films or sheets, other water soluble polymers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, carboxy methyl cellulose, polyvinyl alcohol, Polyvinylpyrrolidone, polyacrylates (e.g., sodium, potassium or ammonium salts) and the like can be mixed with it. However, since the polymer of the present invention is poorly soluble in polyvinyl alcohol and co-use with cellulose derivatives makes the film very water-absorbent, the content of other water-soluble polymers is less than 10% by weight of the polymer of the present invention. desirable.

Films or sheets of polymers suitable for cleaning packaging can be obtained in analgesic ways such as solvent coating and application extrusion.

The films or sheets of the present invention may be prepared from other materials commonly formulated into detergent compositions, such as antioxidants, fluorescent agents, antifoaming agents, chelating agents and the like, and others such as solubility modifiers, for example, relatively low molecular weight polyethylene glycols; Plasticizer; If desired, antifungal agents can be included. The thickness of the film or sheet can be determined in terms of strength or durability of the packaging process, use in vending machines, storage, commercial transport, and the like; Water-soluble in use to facilitate dissolving of detergents and to prevent insoluble materials from re-depositing on washed clothing; Moisture permeability to prevent the cleaning agent from caked, wetting or deteriorating; And from an economic point of view.

Since the conventional thickness of the detergent packaging film is about 10-100 μm, more generally 20-60 μm, it is preferable in the present invention to use a film or sheet having such a thickness, which is generally used for the film or sheet within the above thickness range. This is because it is applicable to the packaging machine used as.

In view of the above, the polymer used for the film or sheet of the present invention should have (1) tear strength, (2) dissolution time and (3) equilibrium moisture content as described above.

The detergent to be packaged in the water-soluble film or sheet of the present invention is not limited, and any conventional one can be used. Detergents typically include surfactants such as alkylbenzene sulfonates, alkyl sulfonates, soaps, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, fatty acid alkylolamides, and the like; Enhancers such as organic enhancers such as polyphosphate zeolites, carbonates, and silicate chelating agents; Fluorescent Whitening Agent; Anti-deposition agents such as sodium silicate, carboxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose and the like; Enzymes such as proteases, lipases, amylases and the like; Emollients such as dimethyldaalkyl quaternary ammonium salts, idazolinium compounds and the like; Bleaches such as sodium percarbonate, sodium perborate and the like; Spices ; Extenders such as sodium sulfate; Antifoaming agent or foam control agent; Thickener; Contains other.

The weight of one package (unit) of the single packaged detergent of the present invention preferably contains about 3 g to 100 g, more preferably about 5 g to 50 g of detergent. The term “single pack” means a pack packed in an amount that the detergent is intended to use for a standard one-time wash, but the amount of detergent used is the amount of dirty laundry, the capacity of the washing machine, the hardness of the water, the temperature of the water, the detergent It does not mean to exclude the use of more than one pack of cleaning agents in one wash because it depends on the type of. Also included in the term “single package” is a detergent package intentionally prepared for use in more than one detergent package unit for one wash.

The following examples illustrate the invention but do not limit the invention to their specific details. Throughout the specification as well as in the examples, all parts and percentages are by weight unless otherwise indicated.

Example 1

(1) Preparation of the polymer:

In the presence of 2.2 parts of calcium hydroxide as a catalyst in a degassed autoclave (5 L) containing 4,500 parts of ethylene oxide and 15 parts of propylene glycol, the reaction temperature was about 90 to 130 DEG C and the pressure was about 1 to 2 atmospheric pressures (gauge pressure). Introduced dropwise over about 11 hours while maintaining to prepare a polyether polyol having a weight average molecular weight of 15,000, followed by addition of 68 parts of diethyl isophthalate and heating for about 1 hour to about 180 to 190 DEG C and resulting ethyl alcohol Was removed under reduced pressure of about 0.1 Torr to leave the same catalyst to prepare a polyester having an average molecular weight of about 150,000.

(2) Preparation of the film:

The obtained polyester was dissolved in water to prepare a 20% aqueous solution (viscosity: about 10,000 cps at 25 ° C), the aqueous solution was casted with a coater, and dried at 80 ° C for 0.5 hours to cool a flat film having a thickness of 39 μm. Prepared.

(3) Determination of physical properties:

The physical properties of the obtained film were determined by the following method.

Tear strength is determined according to JIS (Japanese Industrial Standard) K 6301-1975.

In the present specification, the dissolution time of the polymer is defined as the time required for the polymer film having an area of 1 cm 2 to be completely dissolved in water until the surface of the water is significant at 20 ° C.

The equilibrium moisture content of the polymer is determined by (1) placing the test film on a petri dish, and placing the petri dish in a desiccator at the bottom containing an aqueous saturated ammonium chloride solution in an amount of about 5-10% by volume of the lower space. The relative humidity in the desiccator is maintained at about 80% at 20 ° C. The desiccate is held in a constant temperature chamber at 20 ° C. for 10 days, and the film in the desiccator is weighed daily over 10 days to determine the equilibrium water content of the polymer.

The result is as follows:

Tear strength: 105㎏ / ㎝,

Dissolution time (20 ℃): 8 sec, and Equilibrium water content (at 20 ℃ and 80% RH): 10%

(4) Preparation of single packaged detergents:

Powder detergent containing the sodium salt of linear alkylbenzenesulfonic acid as the main surfactant (New Beads: trade name of Kao KK) was obtained in step (2) to contain 20 g of detergent in one package. Packaged film to obtain a single packaged detergent.

(5) Evaluation of single packaged detergents:

Into the water (20 ° C.), the single packaged detergent obtained in step (4) was completely dissolved in water within 10 seconds and the detergent was immediately dissolved in water.

A single packaged detergent was filled in the cardboard case to occupy about 80% volume (about 20% space left) and practical tests (packaging, transport, storage, etc. on a commercial route) were conducted. No breaks or wet packages were observed.

Example 2

(1) Preparation of the polymer:

4,500 parts of ethylene oxide in a degassed autoclave (5 L) containing 400 parts of polyetherylene glycol (MW = 3,000) in 20 hours under a pressure of 1.1 atmosphere (gauge) at about 115 ° C. in the presence of 2.4 parts of sodium hydroxide. Polyethylene glycol having a weight average molecular weight of about 32,000 was prepared by introducing over polymerization of ethylene oxide to polystyrene glycol, to which 32 parts of dimethyl terephthalate was added, and methanol produced for 1 hour at about 200 ° C. The reaction was carried out under the reduced pressure of about 0.05 Torr to prepare a polyester having a weight average molecular weight of about 250,000.

(2) Preparation of the film:

From the polyester obtained in the process (1) of Example 2 of the film of 50 micrometers in thickness, it manufactured using the calendar roll.

The film has the following properties:

Tear strength: 150㎏ / ㎝,

Dissolution time (20 ° C.): 15 seconds at 50 μm thickness, 8 seconds at 30 μm thickness, and

Equilibrium water content (at 20 ℃ and relative humidity 80%): 7%

(3) Preparation and evaluation of single packaged detergents:

A single packaged detergent was prepared and evaluated in the same manner as in Example 1 except that the polyester film of Example 2 was used instead of the film of Example 1. The same result as in Example 1 was obtained.

Comparative Example 1

Powder detergent (new beads) was packaged using a 30 μm thick film made of polyvinyl alcohol soluble in cold water in the same manner as in Example 1. The film has the following physical properties:

Tear strength: 180 ㎏ / ㎝, and

Equilibrium moisture content (at 20 ℃ and 80% relative humidity): 13%

However, the dissolution time (20 ° C.) is 35 seconds. A single packaged detergent was prepared and evaluated in the same manner as in Example 1 except that the above polyvinyl alcohol film was used instead of the polyester film of Example 1.

Although the body of the film was completely dissolved in water within a relatively short time, the fused or overlapping parts solidified in water to form a gelled mass, which adhered to the washed garment.

[Examples 3-5]

Three kinds of water-soluble films were obtained and physical properties were determined in the same manner as in Example 1. The types and properties of the polyether polyols and polycarboxylic acids used are listed in Table 1 below.

TABLE 1

EO: polyoxyalkylene moiety

(1) tear strength

(2) Dissolution time of the polymer (seconds / 30 ㎛ thickness)

(3) equilibrium moisture content

Claims (12)

(1) tear strength of about 50 kg / cm or more, (2) dissolution time shorter than about 20 seconds, and (3) equilibrium moisture content of less than about 20% at 20 ° C and 80% relative humidity. A single packaged detergent containing a detergent blade or granule packed in a water-soluble film or sheet made of a polymer having properties. The single packaged detergent of claim 1, wherein the water soluble film has a thickness of about 10 to 100 micrometers. The unpacking detergent of claim 1, wherein the polymer comprises a polyester having a polyoxyethylene moiety. 4. The single packaged detergent of claim 3, wherein the polyester has a weight average molecular weight of about 10,000 to 500,000. 4. The single packaged detergent of claim 3, wherein the polyester has a polyether polyol moiety of about 1,000 or more weight average molecular weight. 4. The single pack detergent of claim 3 wherein the polymer additionally comprises a water soluble polymer other than polyester. (1) a tear strength of at least about 50 kg / cm, (2) a dissolution time shorter than about 20 seconds, and (3) an equilibrium moisture content of less than about 20% at 20 ° C and 80% relative humidity. A water-soluble film or sheet suitable as the packaging material for a single packaged detergent. The film or sheet of claim 7 having a thickness of about 10-100 micrometers. 8. The film or sheet of claim 7, wherein the polymer comprises a polyester having a polyoxyethylene moiety. 10. The film or sheet of claim 9 wherein the polyester has a weight average molecular weight of about 10,000 to 500,000. 10. The film or sheet of claim 9, wherein the polymer additionally comprises a water soluble polymer other than polyester. 10. The film or sheet of claim 9, wherein the polymer additionally comprises a water soluble polymer other than polyester.