JPH08218097A - Automatically aromatizing detergent base - Google Patents

Abstract

PURPOSE: To obtain a detergent base for water-based toilets, excellent in sustained solubilizing effects and capable of sustaining averaged release of a colorant and an aroma and farther detergency without losing the shape even in water for a long period by employing a water-soluble polyurethane resin using a specified amount of a specific polyol as a base. CONSTITUTION: This base comprises (D) a water-soluble solid polyurethane resin derived from (A) a water-soluble polyoxyalkylene polyol (preferably an ethylene oxide homopolymer or a random or a block copolymer of ethylene oxide and propylene oxide), (B) a water-insoluble polyol having 500-2000 number- average molecular weight (preferably a polypropylene ether polyol) and (C) an organic polyisocyanate (preferably 4,4'-diphenylmethane diisocyanate) at (99.9-85.0):(0.1-15.0) weight ratio of the components (A):(B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automatic fragrance cleaner base material for a water storage type flush toilet. More specifically, the present invention relates to a base material having a slow dissolution property, which does not lose its shape even when left in water for a long period of time and sustains the release of colorants and fragrances for a long period of time.

[0002]

2. Description of the Related Art Automatic fragrance cleaners for flush toilets are used to solidify a fragrance substance into a lump and put it into a water tank of the flush toilet to gradually dissolve or disperse the fragrance substance in the water in the water tank. It is a chemical that is used to automatically wash and clean the toilet bowl while causing the fragrance to drift in the toilet along with the running water. Conventionally,
Polyoxyethylene compounds (for example, Japanese Patent Publication No.
No. 3706), a polyurethane resin obtained by reacting a polyoxyalkylene compound with a polyisocyanate (JP-A-55-131098), and the like have been proposed.

[0003]

However, the former one is inherently too soluble in water and therefore has a problem in terms of sustained solubility. In addition, although the latter type has a significantly longer sustainability than the polyoxyethylene type type, it cannot be said that the sustained solubilizing effect is necessarily sufficient, and the dosage form must be changed in order to secure a certain pot life. There were drawbacks such as the need to upsize. An object of the present invention is to provide a base material that solves the above-mentioned drawbacks found in conventional base materials, that is, an automatic fragrance cleaner base material for a flush toilet having excellent slow-dissolving properties.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by using a water-soluble polyurethane resin containing a specific amount of a specific polyol as a base material, The present invention has been accomplished by finding that a cleaning agent having an excellent slow-dissolving property can be obtained. That is, the present invention is derived from a water-soluble polyoxyalkylene ether polyol (A), a water-insoluble polyol (B) having a number average molecular weight of 500 to 2,000 and an organic polyisocyanate (C), and (A) :( The weight ratio of B) is (9
9.9 to 85.0): (0.1 to 15.0), which is a water-soluble solid polyurethane resin (D), which is an automatic fragrance cleaner base material for flush toilets.

In the present invention, examples of the water-soluble polyoxyalkylene compound (A) include ethylene oxide (hereinafter abbreviated as EO) homopolymer; EO / propylene oxide (hereinafter abbreviated as PO) copolymer; hydroxyl group Compound (a) having EO alone or EO and other alkylene oxide [PO, 1,2-butylene oxide, tetrahydrofuran, α-olefin oxide, alkylene oxide substitution product (epichlorohydrin, styrene oxide, etc.)] And a mixture of two or more thereof.

Examples of the above-mentioned (a) include polyhydric alcohols (butylene glycol, hexylene glycol, polypropylene glycol, polyoxytetramethylene glycol, polycaprolactam, dimethylolpropionic acid (salt), glycerin, trimethylolpropane, triethyl alcohol. Methylolethane, pentaerythritol, sorbitol, sucrose, etc.); polyhydric phenols (hydroquinone, catechol, etc.); bisphenols (bisphenol A, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol S, etc.); water; and these Mixtures of two or more may be mentioned. Of these, preferred are ethylene glycol, propylene glycol and water.

The addition mode when other alkylene oxide is used together with EO may be random addition or block addition, but the terminal portion of the polyoxyalkylene chain constituting (A) is in view of reactivity with polyisocyanate. Those having a hydroxyethyl group are preferred. E
When O and alkylene oxide other than EO are used in combination, the average oxyethylene unit content in (A) is usually 65.
It is at least wt%, preferably at least 70 wt%.

Particularly preferable ones exemplified above as (A) are polyethylene glycol and EO /
It is a PO copolymer.

The number average molecular weight of (A) is usually 1,000 to
It is 30,000, preferably 2,000 to 25,000. When the number average molecular weight of (A) is less than 1,000, the polyurethane resin is poorly soluble in water, and when it exceeds 30,000, the reactivity with the polyisocyanate (C) becomes poor and a polyurethane resin having the desired performance is obtained. Becomes difficult.

As the water-insoluble polyol (B), for example, polyether glycols (polypropylene glycol, polytetramethylene ether glycol, random and / or block copolymer of tetrahydrofuran and propylene oxide, etc.); polyester polyols (polyether glycols Caprolactone polyol, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexylene adipate, polyethylene-butylene adipate, polyethylene terephthalate,
Polypropylene isophthalate, polybutylene terephthalate, etc.); Polyolefin glycols (polybutadiene glycol, polypropylene glycol, hydrides thereof, etc.); Silicon-based polyols (polymethylsiloxane diol, etc.); Polyether polyester polyols (PO of polybutylene adipate) Addition product, condensation product of polypropylene glycol and adipic acid,
Caprolactone polyaddition product of polypropylene glycol,
Bisphenol A PO adduct and terephthalic acid condensate); and mixtures of two or more thereof. Among these, preferred are tetramethylene ether glycol, polyalkylene adipate and polycaprolactone polyol.

The number average molecular weight of (B) is usually 500 to 2,
000. If the number average molecular weight is less than 500, the slow solubility of the polyurethane resin decreases, and if it exceeds 2,000, it becomes poorly soluble in water, which is not preferable.

In the present invention, the weight ratio of (A) :( B) is (99.9-85.0) :( 0.1-15.0). If the ratio of (A) exceeds 99.9, the solubilizing effect is reduced, and if it is less than 85.0, the water solubility of the resulting polyurethane resin is poor and the polyurethane resin swells in water and loses its shape, which is not preferable.

As the organic polyisocyanate (C),
For example, 4,4′-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPD)
I), ethylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-
Diisocyanates such as phenylene diisocyanate and xylylene diisocyanate; reaction products of tolylene diisocyanate and trimethylolpropane; polyphenylmethane polyisocyanates obtained by phosgenating polyamines obtained by reacting aniline with formaldehyde in the presence of hydrochloric acid; Mention may be made of crude polyisocyanates obtained in these production steps; and mixtures of two or more thereof. Among these, preferred are diisocyanates and crude diphenylmethane diisocyanate, and particularly preferred are MDI, TDI and I.
PDI and HDI.

In the present invention, the equivalent ratio of the total hydroxyl groups of (A) and (B) to the isocyanate group of (C) (hereinafter referred to as NCO group) is usually 1: (0.8 to 1.0), preferably Is 1: (0.9-0.98). NCO group is 0.
If it is less than 8 equivalents, the molecular weight of (C) will be low and the water retention will be insufficient, and if it exceeds 1.0 equivalent, the residual NCO groups will react with water in the aqueous solution to crosslink and reduce the water solubility of the polyurethane resin, which is not preferable. .

The weight average molecular weight of the water-soluble solid polyurethane resin (D) in the present invention is usually 5,000 to 50.
50,000, preferably 10,000 to 400,000
Is. When the weight average molecular weight is less than 5,000, the dissolution rate in water is fast and a sufficient sustained solution effect cannot be obtained.
If it exceeds 50,000, the melt viscosity will increase and the melt molding will be difficult.

The content of oxyethylene units in (D) is usually at least 60% by weight, preferably at least 80%.
% By weight. If the content of oxyethylene units in (D) is less than 60% by weight, the water solubility will be insufficient.

The manufacturing method of (D) is not particularly limited,
It can be obtained by reacting (A), (B) and (C) by an ordinary method for producing a polyurethane resin (one-shot method or multi-step method). The reaction temperature for urethanization is usually 30 to 200 ° C, preferably 50 to 180 ° C.
The reaction time is usually 0.1 to 30 hours, preferably 0.1 to
8 hours. The urethanization reaction is usually carried out in a solventless system, but if necessary, it may be carried out in an organic solvent inert to isocyanate. Examples of the organic solvent include acetone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, toluene, dioxane and the like. When a solvent is used, the solvent is usually distilled off after the reaction to obtain the water-soluble polyurethane resin (D).

The automatic fragrance cleaner using the base material of the present invention is usually formed by mixing the base material of the present invention with a colorant, a fragrance and other additives in an arbitrary shape. Examples of the colorant include blue and green dyes and pigments which are pigments for producing a refreshing feeling of running water, and specifically, Turg Blu.
e G, Green No. 3, Blue No. 1, Brilliant Blue FC
F etc. are mentioned. As the fragrance, those usually used may be used, and specific examples thereof include borneol, menthol, camphor, terpineol, paradichlorobenzol and the like. In addition, anionic and nonionic surfactants (alkylbenzenesulfonate, alkylsulfate, etc.) to enhance detergency as needed, cationic surfactants such as benzalkonium chloride for imparting bactericidal properties, and pentachlorophenol A solid compound such as an antibacterial agent component, a higher saturated aliphatic alcohol such as stearyl alcohol, or sorbitan monostearate may be added to adjust the solubility. Further, water, an organic solvent (ethylene glycol, propylene glycol, glycerin, etc.), a water-soluble resin, or another extender may be added for molding. If necessary, an ion sequestering agent (such as ethylenediamine tetraacetate), a deodorant [plant extract components such as lauryl methacrylate, glyoxalic acid, glyrosin, and Apollide L (Nippon Kasei)], insect repellent (paradichlorobenzene, naphthalene, Camphor etc.) can be added.

The content of the base material of the present invention in the automatic fragrance cleaner is usually 50 to 95% by weight, based on the weight of the cleaner.
It is preferably 60 to 90% by weight. If it is less than 50% by weight, the sustainability of the effect is not sufficiently exhibited, and if it exceeds 95% by weight, the effect is hardly further improved.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following, "part" means part by weight and "%" means% by weight.

Example 1 Polyethylene glycol (number average molecular weight 20,000)
92 parts, 8 parts of polybutylene adipate diol (number average molecular weight of 2,000) and 1.3 parts of HDI were reacted at 170 ° C. for 5 hours to obtain a base material [1] of the present invention composed of a water-soluble polyurethane resin. The weight average molecular weight (hereinafter, the same) of the [1] by gel permeation chromatography was 100,000.

Example 2 Polyethylene glycol (number average molecular weight 20,000)
100 parts, polyethylene glycol (number average molecular weight 8,
000) 100 parts, polycaprolactone diol (number average molecular weight 980) 2 parts and MDI 5 parts at 180 ° C.
After reacting for a time, a base material [2] of the present invention made of a water-soluble polyurethane resin was obtained. The weight average molecular weight of the [2] is 7
It was 9,000.

Example 3 Polyethylene glycol (number average molecular weight 20,000)
90 parts, polyoxyethylene oxypropylene glycol [polypropylene glycol (number average molecular weight 3,50
0) with EO added; number average molecular weight 15,000
0] 10 parts, polyoxytetramethyl ether glycol (number average molecular weight 1,000) 3 parts and TDI 1.4.
Parts were reacted at 160 ° C. for 5 hours to obtain a base material [3] of the present invention composed of a water-soluble polyurethane resin. The weight average molecular weight of the [3] was 89,000.

Example 4 Polyoxyethylene oxypropylene glycol [polypropylene glycol (number average molecular weight 1,700) E
O added; number average molecular weight 8,500] 98 parts,
17 parts of polyoxytetramethyl ether glycol (number average molecular weight 1,500) 2 parts and IPDI 12.6 parts
The reaction was carried out at 0 ° C. for 5 hours to obtain a base material [4] of the present invention composed of a water-soluble polyurethane resin. The weight average molecular weight of the [4] was 75,000.

Comparative Example 1 Polyoxyethylene oxypropylene glycol [Polypropylene glycol (number average molecular weight 1,700) E
O addition: 100 parts of number average molecular weight 8,500] and 2.3 parts of MDI were reacted at 170 ° C. for 3 hours to obtain a comparative base material [5] made of a water-soluble polyurethane resin. The weight average molecular weight of the [5] was 56,000.

Comparative Example 2 Polyoxyethylene oxypropylene glycol [Polypropylene glycol (number average molecular weight 1,700) E
O was added; a number average molecular weight of 8,500] was used as a comparative substrate [6].

Performance Test Example 1 Using each of the base materials [1] to [6], the base material 90%, the fragrance (borneol) 3%, and the colorant (blue No. 1) 7% were melt mixed, and then the diameter was obtained. 3 in each 3.5 cm cylinder
An automatic fragrance cleaner was prepared by pouring and solidifying 0 g.
Each cleaning agent was placed in a tank containing 10 L of water, and the amount of 10 L / water was flown 10 times a day to observe the state of dissolution in water, and the number of days until the completion of dissolution was measured. Table 1 shows the results.

[0028]

[Table 1]

[0029]

EFFECT OF THE INVENTION The automatic fragrance cleaner for flush toilets using the base material of the present invention is superior in the effect of gradually dissolving compared to the one using the conventional base material, and does not lose its shape in water for a long period of time. Maintains average color and fragrance release and detergency throughout.

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[Procedure amendment]

[Submission date] November 21, 1995

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[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by using a water-soluble polyurethane resin containing a specific amount of a specific polyol as a base material, The present invention has been accomplished by finding that a cleaning agent having an excellent slow-dissolving property can be obtained. That is, the present invention provides a water-soluble polyoxyalkylene polyol (A), 5
It is derived from a water-insoluble polyol (B) having a number average molecular weight of 00 to 2,000 and an organic polyisocyanate (C), and the weight ratio of (A) :( B) is (99.9 to 8).
5.0): An automatic fragrance cleaner base material for a flush toilet comprising a water-soluble solid polyurethane resin (D) of (0.1 to 15.0).

[Procedure 3]

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In the present invention, examples of the water-soluble polyoxyalkylene polyol (A) include ethylene oxide (hereinafter abbreviated as EO) homopolymer; EO / propylene oxide (hereinafter abbreviated as PO) copolymer; hydroxyl group Compound (a) having EO alone or EO and another alkylene oxide [PO, 1,2-butylene oxide, tetrahydrofuran, α-olefin oxide, alkylene oxide substitution product (epichlorohydrin, styrene oxide, etc.)] And a mixture of two or more thereof.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Tanaka 1 1-11, Hitotsubashi-honcho, Higashiyama-ku, Kyoto Sanyo Chemical Industry Co., Ltd.

Claims (6)

[Claims] 1. A water-soluble polyoxyalkylene ether polyol (A), a water-insoluble polyol (B) having a number average molecular weight of 500 to 2,000, and an organic polyisocyanate (C), wherein (A) :( An automatic fragrance cleaner base material for a flush toilet comprising a water-soluble solid polyurethane resin (D) having a weight ratio of B) of (99.9 to 85.0) :( 0.1 to 15.0). 2. (D) has a total hydroxyl group of (A) and (B) and an isocyanate group of (C) of 1: (0.5 to 1.0).
The base material according to claim 1, which is a water-soluble solid polyurethane resin obtained by reacting at an equivalent ratio of. 3. The substrate according to claim 1, wherein the oxyethylene group content in (D) is at least 60% by weight. 4. The base material according to claim 1, wherein (A) is an ethylene oxide homopolymer and / or a random or block copolymer of ethylene oxide and propylene oxide. 5. (B) is at least one selected from the group consisting of polypropylene ether polyol, polytetramethylene ether polyol, polyester polyol and polyolefin polyol.
The substrate according to any one of 1. 6. The method according to claim 1, wherein (C) is at least one selected from the group consisting of 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate. Base material.