JP2700535B2 - Automatic fragrance detergent base - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automatic fragrance detergent base material for flush toilets. More specifically, the present invention relates to a base material which has a slow solubility and maintains the release of a colorant and a fragrance for a long time without losing its shape even when left in water for a long time.

[0002]

2. Description of the Related Art An automatic fragrance cleaning agent for flush toilets hardens fragrance substances in a lump and puts the fragrance substances into a water tank of the flush toilet to gradually dissolve or disperse the fragrance substances in the water in the water tank. It is a chemical that is used to flush the scent in the toilet with the running water and at the same time automatically wash and keep the toilet bowl and the like fresh. Conventionally,
Polyoxyethylene compounds (for example, Japanese Patent Publication No.
No. -3706) and a polyurethane resin obtained by reacting a polyoxyalkylene compound with a polyisocyanate (Japanese Patent Laid-Open No. 55-131098).

[0003]

However, the former is inherently too soluble in water, and thus has a problem in the point of slow solubility. In the latter case, the sustainability is significantly longer than that of the polyoxyethylene type, but the effect of the solubilization is not always sufficient, and the dosage form is required to ensure a certain pot life. There are drawbacks such as the need to increase the size. An object of the present invention is to provide a base material that solves the above-mentioned drawbacks observed in conventional base materials, that is, an automatic fragrance cleaning base material for flush toilets that has excellent slow solubility.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by using a water-soluble polyurethane resin using a specific amount of a specific polyol as a base material, The present inventors have found that a detergent having excellent slow solubility can be obtained, and have reached the present invention. That is, the present invention relates to a water-soluble polyoxyalkylene polyol (A),
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 has a weight ratio of (A) :( B) of (99.9 to 8).
5.0): It is an automatic fragrance detergent base material for flush toilets comprising a water-soluble solid polyurethane resin (D) which is (0.1 to 15.0).

In the present invention, the water-soluble polyoxyalkylene polyol (A) includes, for example, ethylene oxide (hereinafter abbreviated as EO) homopolymer; EO / propylene oxide (hereinafter abbreviated as PO) copolymer; EO alone or EO and another alkylene oxide [PO, 1,2-butylene oxide, tetrahydrofuran, α-olefin oxide, substituted alkylene oxide (epichlorohydrin, styrene oxide, etc.)] And a mixture of two or more of these.

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

[0007] When other alkylene oxide is used together with EO, the addition mode may be random addition or block addition. However, the terminal portion of the polyoxyalkylene chain constituting (A) has a problem in terms of reactivity with polyisocyanate. Those having a hydroxyethyl group are preferred. E
When O and an alkylene oxide other than EO are used in combination, the average oxyethylene unit content in (A) is usually 65%.
% By weight or more, preferably 70% by weight or more.

[0008] Of those exemplified above as (A), particularly preferred are polyethylene glycol and EO /
It is a PO copolymer.

The number average molecular weight of (A) is usually from 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 becomes poorly soluble in water, and when it exceeds 30,000, the reactivity with polyisocyanate (C) becomes poor, and a polyurethane resin having the intended performance is obtained. It becomes difficult.

Examples of the water-insoluble polyol (B) include polyether glycols (polypropylene glycol, polytetramethylene ether glycol, random and / or block copolymers of tetrahydrofuran and propylene oxide, etc.); polyester polyols (poly) Caprolactone polyol, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexylene adipate, polyethylene-butylene adipate, polyethylene terephthalate,
Polyolefin glycols (polybutadiene glycol, polypropylene glycol, hydrides thereof, etc.); Silicone polyols (polymethylsiloxane diol, etc.); Polyether polyester polyols (PO of polybutylene adipate) Adducts, condensates of polypropylene glycol and adipic acid,
Caprolactone polyadduct of polypropylene glycol,
And a condensate of terephthalic acid and a PO adduct of bisphenol A); and a mixture of two or more of these. Among these, preferred are tetramethylene ether glycol, polyalkylene adipate and polycaprolactone polyol.

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

In the present invention, the weight ratio of (A) :( B) is (99.9-85.0) :( 0.1-15.0). When the proportion of (A) exceeds 99.9, the effect of gradually solubilizing decreases, and when the proportion is less than 85.0, the resulting polyurethane resin becomes poor in water solubility and swells in water to cause a shape loss, 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; reactants of tolylene diisocyanate with trimethylolpropane; polyphenylmethane polyisocyanate obtained by phosgenating a polyamine obtained by reacting aniline with formaldehyde in the presence of hydrochloric acid; 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, IDI
PDI and HDI.

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

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

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

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

The automatic fragrance detergent using the substrate of the present invention is usually formed into an arbitrary shape by melting and mixing a colorant, a fragrance and other additives with the substrate of the present invention. Examples of the colorant include a blue or green dye and a pigment which is a pigment for giving a refreshing feeling of running water.
e G, Green No. 3, Blue No. 1, Brilliant Blue FC
F and the like. As the fragrance, those commonly used may be used, and specific examples thereof include borneol, menthol, camphor, terpineol, and paradichlorobenzol. Further, if necessary, anionic and nonionic surfactants (such as alkylbenzene sulfonates and alkyl sulfates) to enhance detergency, cationic surfactants such as benzalkonium chloride to provide bactericidal properties, and pentachlorophenol and the like. An antibacterial agent component, a higher saturated aliphatic alcohol such as stearyl alcohol, or a solid compound such as sorbitan monostearate may be added to adjust the solubility. Further, a molding may be performed by adding an extender such as water, an organic solvent (such as ethylene glycol, propylene glycol, and glycerin) and a water-soluble resin. Further, if necessary, ion sequestering agents (such as ethylenediaminetetraacetate), deodorants (eg, plant extract components such as lauryl methacrylate, glyoxalic acid, glyrosine, Apolide L (Nippon Kasei), etc.), insect repellents (paradichlorobenzene, naphthalene, Camphor etc.) can be added.

The content of the substrate of the present invention in the automatic fragrance detergent is usually 50 to 95% by weight, based on the weight of the detergent.
Preferably it is 60 to 90% by weight. If it is less than 50% by weight, the durability of the effect is not sufficiently exhibited, and if it exceeds 95% by weight, the effect is hardly further improved.

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In the following, "parts" indicates parts by weight and "%" indicates% by weight.

Example 1 Polyethylene glycol (number average molecular weight 20,000)
92 parts, 8 parts of polybutylene adipate diol (number average molecular weight: 2,000) and 1.3 parts of HDI were reacted at 170 ° C. for 5 hours to obtain a substrate [1] of the present invention comprising a water-soluble polyurethane resin. The weight average molecular weight (hereinafter the same) of the [1] determined 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), 2 parts of polycaprolactone diol (number average molecular weight 980) and 5 parts of MDI at 180 ° C.
The reaction was carried out for a time to obtain a substrate [2] of the present invention comprising a water-soluble polyurethane resin. The weight average molecular weight of [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, 3 parts of polyoxytetramethyl ether glycol (number average molecular weight 1,000) and TDI 1.4
The parts were reacted at 160 ° C. for 5 hours to obtain a substrate [3] of the present invention comprising a water-soluble polyurethane resin. The weight average molecular weight of [3] was 89,000.

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

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

Comparative Example 2 Polyoxyethyleneoxypropylene glycol [polypropylene glycol (number average molecular weight 1,700)
O-added; number average molecular weight 8,500] was used as a comparative substrate [6].

Performance Test Example 1 Each of the substrates [1] to [6] was melt-mixed at a ratio of 90% for the substrate, 3% for the fragrance (borneol), and 7% for the colorant (Blue No. 1), and then mixed with the diameter. 3 in each 3.5cm cylindrical mold
0 g was poured and solidified to prepare an automatic fragrance cleaner.
Each cleaning agent was put into a tank containing 10 L of water, and was flowed 10 times per day at a rate of 10 L / time of water, the state of dissolution in water was observed, and the number of days until the completion of dissolution was measured. Table 1 shows the results.

[0028]

[Table 1]

[0029]

The automatic fragrance cleaner for flush toilets using the base material of the present invention has an excellent solubilizing effect as compared with the conventional base material, and does not lose its shape in water for a long time. Maintains colorant and fragrance release and detergency averaged over time.

Continuation of the front page Examiner Ichiyoshi Karaki (56) References JP-A-55-131098 (JP, A) JP-A-6-322392 (JP, A) JP-A-7-53712 (JP, A)

Claims (6)

(57) [Claims] 1. A water-soluble polyoxyalkylene polyol (A), derived from a water-insoluble polyol (B) having a number average molecular weight of 500 to 2,000 and an organic polyisocyanate (C), wherein (A): (B) ) Is (9)
(9.9 to 85.0): an automatic fragrance detergent base material for flush toilets comprising a water-soluble solid polyurethane resin (D) which is (0.1 to 15.0). 2. The method according to claim 1, wherein (D) is obtained by dividing the total hydroxyl group of (A) and (B) and the isocyanate group of (C) by 1: (0.5 to 1.0).
2. The base material according to claim 1, wherein the base material is a water-soluble solid polyurethane resin reacted 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 substrate 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. The method according to claim 1, wherein (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 the above. 6. The method according to claim 1, wherein (C) is at least one member selected from the group consisting of 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate. Base material.