JPH01313600A - Solid detergent for flush toilet - Google Patents

Abstract

PURPOSE:To prevent the separation of a perfume and improve the solubility and persistence of the solubility by incorporating a particular copolymer (derivative) as an active ingredient. CONSTITUTION:A polyoxyalkylene derivative (i) of formula I (wherein B<1> is a residue of a compd. having 2-8 hydroxyl groups; AO is a 3-18C oxyalkylene which may be added to C2H4O in a block or random form; X is a 2-5C unsatd. hydrocarbon group; R<1> is a 1-24C hydrocarbon group or acyl; a1-a3 are each 0-30; b1-b3 are each 0-100, provided that a1-a3 and b1-b3 are not simultaneously 0; l is 1-8 and m and n are each 0-7, provided that l+m+n=2 to 8; a1l+a2m+a3n:b1l+b2m+b3n=0 to 30/100) is reacted with maleic anhydride (ii). The reaction mixture is hydrolyzed (and neutralized) according to need and esterified with a compd. of formula II [wherein B<2> is a residue of a compd. having 1-8 hydroxyl groups; a4 and a5 are each a1; b4 and b5 are each b1; p and q are each 0-8, provided that p+q=1; and a4p+a5q:b4p+b5q=0 to 30/100)], and the esterification product is neutralized according to need, thereby providing a copolymer of component (i) with component (ii), a hydrolyzate of the copolymer (salt) or an ester of the copolymer (salt). At least one of them in an amt. of 5-100wt.% is optionally blended with other water-soluble compds., perfumes, etc.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a solid detergent for flush toilets.

[Conventional technology]

BACKGROUND ART Cleaning agents that elute cleaning components and aromatic components into flushing water are used to clean flush toilets and to increase the sense of cleanliness during or after use. Some of these cleaning agents are liquid and body, but most are solid.
There are two types: a type that is filled in a container that adjusts the dissolution rate, and a type that can be used as is. It is installed at the injection part etc.

Among the above, cleaning agents that are filled into containers are known to have polyethylene glycol as the main ingredient, which gradually dissolves in water, and contain fragrances, colorants, disinfectants, cleaning ingredients, etc. .

[Problem to be solved by the invention]

Adjustment of the rate of dissolution of these detergents into water is done by changing the shape of the container and the composition of the detergent, but on the other hand, the rate of dissolution in the bath is affected by the water temperature, and the rate of dissolution in water is persistent in summer and winter. The problem was that they were significantly different.

Further, when a large amount of fragrance is used to impart aromatic properties, there are problems in that the washing water becomes cloudy and separation of the fragrance occurs because the fragrance is not solubilized.

By using a copolymer of polyoxyalkylene derivatives with a specific structure as a cleaning agent, the present invention has excellent solubility and sustainability, so it can be used without being affected by water temperature, and it can contain a large amount of fragrance. To provide a solid detergent for flush toilets that does not cause turbidity even when used in flush toilets.

[Means to solve the problem]

The present invention relates to a copolymer of a polyoxyalkylene derivative represented by the general formula (1) and maleic anhydride, a hydrolyzate of the copolymer, a salt of the hydrolyzate of the copolymer, a salt of the hydrolyzate of the copolymer, An ester with a compound having at least one hydroxyl group represented by the general formula (2), or a salt of the ester, in an amount of 5 to 100
It is a solid cleaning agent for flush toilets that contains
・(However, B1 is f of a compound having 2 to 8 hydroxyl groups
iX and AO are oxyalkylene groups having 3 to 18 carbon atoms,
AO and C, f (40 may be added in block form or randomly added, X is an unsaturated hydrocarbon group having 2 to 5 carbon atoms, R1 is carbonization of carbon a1 to 24 Hydrogen group or acyl group, al=Q~30.32=Q~3o,
B3=O~30. bt=O~100, b2==
0 to 100.1) 3=Q to al at 100: B2
Rua3=bl=b''=biii, J=1~8, m=θ
~7dn=o~7 and s l + m + n = 2~
B, asl-1-azm+ain:bsll-4
-b2m+bsn=Q: 100~30:10
It is 0. ) (As a friend, B2 is the residue of a compound having 1 to 8 hydroxyl groups, AO is an oxyalkylene group having 3 to 18 carbon atoms, and even if AO and C2H40 are added in a block shape: 5/dumb shape may be added to, R2 is a hydrocarbon group having 1 to 24 carbon atoms or an acyl group, a4 = Q to 30, as = 0 to 3
0, b4=O~100, bs=(1-100, p=o~
8, q=O~8, I)+Q=1~8, atp+asq
: b4p+bsQ=O: 100-30:100. ) Compounds having 2 to 8 hydroxyl groups represented by B1 and B2 in general formulas (1) and (2), teha, catechol, resorcinol, hydroquine, bisphenol A1
Glycols such as phloroglucin, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, styrene glycol, alkylene glycol having 8 to 18 carbon atoms, neopentyl glycol, glycerin, diglycerin, polyglycerin, trimethylolethane, trimethylol Propane, l.

3. Polyhydric alcohols such as 5-pentanetriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, nrubitan, sorbite, sorbitol N-glycerin condensate, adonitol, arabitol, xylitol, mannitol, or partially etherified products thereof, or Esterified products, sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gunthianose, melezitose, or partially etherified or esterified products thereof There is. In addition, when B2 is the residue of a compound having one hydroxyl group, the compound includes methanol, ethanol, allyl alcohol, glopanol, inbutanol, butanol, inbutanol,
Pentanol, hexanol, heptatool, 2-ethylhextenol, octatool, nonanol, decanol, undecanol, dodecanol, tridecanol,
Tetradecanol, hexadecanol, octadecanol, inoctadecanol, oleylalcofur, octyldodecanol, eicosanol, decyltetradecanol, benzyl alcohol, cresol, butylphenol, dibutylphenol, octylphenol, nonylphenol, dodecylphenol, di These include octylphenol, dinonylphenol, and styrenated phenol.

The oxyalkylene group represented by AO includes an oxypropylene group, an oxybutylene group, an oxytetramethylene group, an oxystyrene group, an oxystyrene group, an oxytetramethylene group, an oxyhexadecylene group, an octadecylene group, and the like.

Examples of the unsaturated hydrocarbon group having 2 to 5 carbon atoms represented by X include vinyl group, allyl group, methallyl group, 1,1-dimethyl-2-propenyl group, and 3-methyl-3-butenyl group. .

Examples of hydrocarbon groups having 1 to 24 carbon atoms represented by R1 and R2 include methyl group, ethyl group, allyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, and isoamyl group. , hexyl group, hephthyl &, 2-ethylhexyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodenyl group, tridecyl group, tetradecyl group, hexadecyl group, inhexadecyl group, octadecyl group, inoctadecyl group, oleyl group, octyldodecyl group, tocosyl group, decyltetradecyl group, benzyl group, cresyl group , butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dotecylphenyl group, dioctylphenyl group, dinonylphenyl group, styrenated phenyl group, etc., and acyl groups include acetic acid, propionic acid, etc. , butyric acid, isobutyric acid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid, capric acid, undecyl acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid,
Arachic acid, behenic acid, acrylic acid, methacrylic acid, palmitoleic acid, oleic acid, linoleic acid, lylic acid,
There are acyl groups derived from erucic acid, impalmitic acid, isostearic acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, gallic acid, etc.

The copolymer hydrolyzate is obtained by hydrolyzing copolymerized maleic anhydride units to maleic acid units.

Alternatively, similar maleic acid units can be obtained by using maleic acid as a monomer during copolymerization.

Salts of copolymer hydrolysates are salts formed by maleic acid units, and include alkali metal salts and alkaline earth metal salts such as lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts. In addition, there are ammonium salts and organic amine salts. Examples of organic amine salts include methylamine salt, ethylamine salt, propylamine salt, butylamine salt, amylamine salt, hexylamine salt,
Octylamine salt, 2-ethylhexylamine salt, decylamine salt, dodecylamine salt, intridecylamine salt, tetradecylamine salt, hexadecylamine salt, isohexadecylamine salt, octadecylamine salt, inoctadecylamine salt, octyldodecyl Aliphatic and aromatic monoamine salts such as amine salts, tocodylamine salts, decyltetradecylamine salts, oleylamine salts, snolamine salts, dimethylamine salts, trimethylamine salts, aniline salts, ethylenediamine salts, tetramethylenediamine salts, dodecyl-propylene Diamine salt, tetradecyl-propylene diamine salt, hexadecyl-propylene diamine salt, octadecyl-propylene diamine salt,
Polyamine salts such as oleyl-propylene diamine salt, diethylenetriamine group, triethylenetetramine salt, tetraethylenepentamine salt, pentaethylenehexamine salt, monoethanolamine salt, jetanolamine salt,
triethanolamine salts, monoisopropanolamine salts, diimpropanolamine salts, triisoglopanolamine salts, salts of alkylene oxide adducts thereof,
These include salts of alkylene oxide adducts of primary or secondary amines.

As the salt of the esterified product of the copolymer of the polyoxyalkylene derivative represented by the general formula (1) and maleic anhydride and the compound represented by the general formula (2), the same salts as above can be used.

a1%a5 and bI-b5 indicate the average number of added moles of alkylene oxide and ethylene oxide of carbon a3 to 18 in each chain bonded to B1 or 82, and the addition polymerization mode may be random, block, or a combination of both. In the case of a block shape or a combination of the two, the order of addition is arbitrary.

The copolymer of the present invention may contain other copolymerizable unsaturated monomers for the purpose of adjusting water solubility or melting point, such as EVA, styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester. Also included are multi-component copolymers made by copolymerizing.

The copolymer used in the present invention consists of a polyoxyalkylene derivative represented by the general formula (1), maleic anhydride, a maleate salt, a maleic acid ester, and the above-mentioned copolymerizable unsaturated monomers. Copolymerization is carried out by heating in the presence of a polymerization initiator such as peroxide or azobisisobutyronitrile, copolymerization is carried out using a redox initiator such as potassium persulfate-ascorbic acid, or copolymerization is carried out using the general formula (
It can be obtained by copolymerizing the compound of 1) with maleic anhydride and a copolymerizable unsaturation rate, followed by hydrolysis, neutralization of the hydrolyzate, or esterification, neutralization of the esterified product, etc. .

, in general formula (1), j may be 1 to 8, but it is desirable that the cleaning agent is completely washed away after a certain period of time, approximately one month.
It is preferable that the content of A', :2 in the polyoxyalkylene derivative represented by the formula is about 5% by weight or less. If the period of use is to be kept longer than one month, it is possible to use 1c even if the content of the 142 composition exceeds 5 weight.

In addition, in the polyoxyalkylene derivative represented by the general formula (1), m may be O to 7, but if it exceeds this range, an intramolecular esterification reaction will occur in the obtained copolymer,
As a result, the solubility in water becomes poor. In order to obtain a copolymer that washes away in about one month, the general formula (
In 1), the content of the polyoxyalkylene derivative composition with m≧1 is preferably 5% by weight or less.

In general formulas (1) and (2), the average addition amount of 7 oxyalkylene groups having 3 to 18 carbon atoms is limited by al to a5 because if it exceeds 30, the solid state of the copolymer is maintained. On the other hand, the water solubility is poor. Regarding the ratio of the average addition amount to ethylene oxide, the molar ratio of AO represented by an oxyalkylene group having 3 to 18 carbon atoms to ethylene oxide is preferably in the range of 0:100 to 30:100.

, in general formulas (1) and (2), the average amount of ethylene oxide added is limited by b and ~b5.
If it exceeds 0, the viscosity of the copolymer becomes extremely high during molding, making it difficult to handle.

The content of the copolymer in the cleaning agent is 5 to 100% wax, and includes a copolymer of the compound of general formula (1) and maleic anhydride, and other copolymerizable unsaturated monomers. When using a multi-component copolymer alone, or when using a multi-component copolymer in combination with other water-soluble compounds such as polyethylene glycol, polyvinyl alcohol, starch, cellulose derivatives, etc. It is limited to this range because it is necessary to keep the dissolution rate constant.

The amount of other copolymerizable unsaturated monomers contained in the multi-component copolymer needs to be 50% by weight or less, since if a large amount of these compounds is contained, it becomes water-insoluble, and the preferred range is The weight range is 0 to 30.

The copolymer used in the present invention has an appropriate dissolution rate,
It not only functions as a detergent, but also supports perfumes and other ingredients.

In the solid detergent of the present invention, the copolymer may be used as it is or mixed with other water-soluble compounds. If necessary, commonly used fragrances and blended fragrances, water-soluble dyes as coloring agents, alkylaminoethylglycine as bactericidal agents, quaternary ammonium salts, etc. can be blended and used.

The solid detergent for flush toilets of the present invention is filled into a container or used as is. When filling a container, use it as is, or mold it to an appropriate size and fill it into a water-permeable plastic container. If it is not filled into a container, it is molded into an appropriate size and shape. Generally used methods can be used, such as immersing it in the flushing water tank of a flush toilet and bringing it into contact with the flushing water in the tank, or installing it at the flushing water inflow part (hand washing part) or the spraying part. There is a method of elution by contact with washing water flowing in or jetting out.

By bringing the solid detergent for flushing toilets into contact with the flushing water as described above, its components are eluted into the flushing water, imparting detergency to the flushing water.

Further, when a fragrance is used, the fragrance component is gradually released, and a feeling of cleanliness can be obtained during or after using the flush toilet.

〔Effect of the invention〕

The solid detergent of the present invention may contain a copolymer of an alkylene oxide derivative with a specific structure and maleic anhydride, a salt of a hydrolyzate of the copolymer, an ester of the copolymer, or a salt thereof. As a result, it has excellent solubility and sustainability, maintains an appropriate rate of dissolution without being affected by water temperature, and does not cause separation of fragrances even when fragrances are blended.
Furthermore, it has the effect of not making the discharged water noticeably cloudy.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 Composition 507 consisting of 90 parts by weight of the copolymer shown in Table 1 and 10 parts by weight of fragrance (floral compound fragrance) was placed in a cylindrical shape with a diameter of 5-1 and length lo(7) with an open top. Fill a plastic container with an inner diameter of 15 cm and a length of 60 cm.
cm in an automatic pipette washer, the inflow of 20°C tap water 51 at a rate of once every 2 minutes, the time taken for the entire amount of the composition to be dissolved was measured, and the drained water was The turbidity was measured. A similar test was conducted on tap water at 5°C. Further, the comparative products shown in Table 1 were also tested in the same manner. The results are shown in Table 2.

From the results in Table 2, it can be seen that the product of the present invention has excellent persistence and fragrance solubility without being affected by water temperature.

(The following is a blank space) Example 2 After filling containers with the products of the present invention and comparative products shown in Table 3 in the same manner as in Example 1, the openings were covered with a wire mesh having a mesh size of about 1 mesh. Using the same automatic pipette washer as in Example 1, place this solid detergent onto a funnel with a diameter of 15 c1n set 10 crn below the outlet, with the wire mesh part facing down, and pipet the detergent once every 5 minutes. Then, tap water at 20°C was discharged, the solid detergent came into contact with the water through the wire mesh, and the time until the entire amount of the composition was dissolved was measured, as well as the turbidity of the water flowing from the funnel. did. 5
A similar test was conducted on tap water at ℃. The results are shown in Table 3.

The results in Table 3 show that the product p1 of the present invention has excellent persistence and solubility without being affected by water temperature.

Claims (1)

[Claims] 1. A copolymer of a polyoxyalkylene derivative represented by the general formula (1) and maleic anhydride, a hydrolyzate of the copolymer, a salt of the hydrolyzate of the copolymer, A solid cleaning agent for flush toilets containing 5 to 100% by weight of an ester of the copolymer and a compound having at least one hydroxyl group represented by general formula (2), or a salt of the ester. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1) (However, B^1 is the residue of a compound with 2 to 8 hydroxyl groups, and AO is an oxyalkylene group with 3 to 18 carbon atoms. So, A
O and C_2H_4O may be added in blocks or randomly, X is an unsaturated hydrocarbon group having 2 to 5 carbon atoms, and R^1 is a hydrocarbon group having 1 to 24 carbon atoms. group or acyl group, a_1=0-30, a_2=0-3
0, a_3=0-30, b_1=0-100, b_2=
0-100, b_3=0-100 and a_1=a_2=a
l=1 to 8, except _3=b_1=b_2=b_3=0
, m=0-7, n=0-7, l+m+n=2-8, a
_1l+a_2m+a_3n:b_1l+b_2m+b
_3n=0:100 to 30:100. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(2) (However, B^2 is the residue of a compound having 1 to 8 hydroxyl groups, and AO is an oxyalkylene having 3 to 18 carbon atoms.) Based on AO
and C_2H_4O may be added in blocks or randomly, and R^2 has 1 to 24 carbon atoms.
hydrocarbon group or acyl group, a_4=0-30, a_
5=0-30, b_4=0-100, b_5=0-10
0, p=0-8, q=0-8, p+q=1-8, a_
4p+a_5q:b_4p+b_5q=0:100~3
It is 0:100. )