JP2002285192A - Fur-preventing agent for sanitary ceramic and fur- preventing material for sanitary ceramic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agent for preventing the adhesion of the fur generated in sanitary ceramics such as a flushing toilet, and a fur-preventing material for the ceramics. SOLUTION: The fur-preventing agent for the sanitary ceramics is characterized in that it comprises an ester-containing compound (A) having HLB of 1.5-17, or it comprises the compound (A) and a slowly dissolving agent (B) solid at 20 deg.C. The fur-preventing material is made of the fur-preventing agent, and it is used by dipping in a reservoir of a sanitary earthenware-made flushing toilet, by placing at a hand-washing part of the reservoir and/or by placing in the toilet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-scaling agent for sanitary ware, and more particularly to an anti-scaling agent for sanitary ware such as a flush type toilet, a men's toilet, and a hand washing machine.

[0002]

2. Description of the Related Art It has been known that water scale adheres to sanitary ware. For example, in the case of flush toilets, it is known that brown or dark stains (scales) adhere to ball surfaces and draft portions of toilet bowls. The mechanism by which water scale is formed is that the silicic acid contained in tap water first adheres to the ceramic surface as silica scale, and then the iron, calcium, carbon, etc. contained in tap water are mixed with this silica scale to make it brown. It is thought to be a black scale. The scale is a very stubborn dirt, and it is very difficult to remove it using a strong acid such as hydrochloric acid, a strong alkali such as caustic soda, or a bleaching agent.
Therefore, it is important that the scale is not adhered to the sanitary ware. As such an agent, a composition containing a cationic surfactant (JP-A-61-1557591, JP-A-12-198999) is known. ing.

[0003]

However, since each of the above compositions is an aqueous solution, it is very inconvenient, for example, to spray a chemical on the toilet every day in order to protect the toilet bowl from water scale, and the effect of preventing water scale is high. The emergence of drugs that last for more than one month has been desired.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on the above problems, and as a result, have reached the present invention. That is, the present invention relates to an ester group-containing compound (A) having an HLB of 1.5 to 17 or a solid solubilizer (B) which is solid at 20 ° C.
A scalp inhibitor for sanitary ware, characterized by comprising: a immersion type in a water tank of a sanitary ware flush toilet, a sewage tank installation type and / or a stool installation type toilet bowl using the same. It is a prevention material.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, sanitary ware includes a flush toilet such as a porcelain toilet, a water tank, a hand basin and the like, a flush toilet such as a Japanese flush toilet, a men's flush toilet, and a ceramic toilet. Hand basin and wash basin. Examples of (A) constituting the anti-scale agent of the present invention include those having an HLB of 1.5 to 17 and containing at least one carboxylic ester group in the molecule. Of these, preferred are: An ester group-containing compound which is liquid at 20 ° C. and a solid or pasty aliphatic ester at 20 ° C. containing at least one ester group derived from an aliphatic carboxylic acid and / or an alicyclic carboxylic acid in a molecule; And / or at least one selected from the group consisting of alicyclic esters. The HLB of (A) is 1.
If it is less than 5, the anti-scale effect will be poor, and if the HLB exceeds 17, the sustainability of the anti-scale effect will be poor. Where HLB
(Hydrophile-Lipophile Balance) is an index indicating a balance between hydrophilicity and lipophilicity, and is based on the HLB theory of griffin.

The carboxylic acid (a) constituting (A) includes saturated or unsaturated aliphatic, alicyclic and aromatic carboxylic acids, and natural fatty acids. Saturated or unsaturated aliphatic carboxylic acid (2-32 carbon atoms)
As monocarboxylic acids (acetic, propionic, heptanoic, octanoic, lauric, myristic, stearic, montanic, undecylenic, oleic,
Erucic acid, glycolic acid, lactic acid, etc., poly (2-4)
Carboxylic acid [dicarboxylic acid [succinic acid, adipic acid, azelaic acid, fumaric acid, maleic acid, itaconic acid, oxycarboxylic acid (glyceric acid, tartaric acid, malic acid, etc.) etc.], trivalent to tetravalent Or more polycarboxylic acids [1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, oxycarboxylic acid (citric acid) Acid, etc.], etc.], and as the saturated or unsaturated alicyclic carboxylic acid (C6 to C50), monocarboxylic acid (cyclohexanecarboxylic acid, etc.), poly (divalent to tetravalent or more)
Carboxylic acid [dicarboxylic acid (1,2- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-dicarboxymethylcyclohexane, dicyclohexyl-
4,4'-dicarboxylic acid, dimer acid, etc.), trivalent to 4
Polycarboxylic acids (e.g., 1,2,4-cyclohexanetricarboxylic acid) having a valency or higher] and aromatic carboxylic acids (C7 to C16) include monocarboxylic acids (benzoic acid, p-t-butylbenzoic acid). Acid, salicylic acid, 2-naphthalenecarboxylic acid, etc.), poly (divalent to tetravalent or more) carboxylic acid [dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc.), trivalent To 4 or more polycarboxylic acids (e.g., 1,2,4-benzenetricarboxylic acid, pyromellitic acid)], and examples of natural fat fatty acids include coconut oil fatty acids, palm oil fatty acids, and corn oil fatty acids. No. Among these, preferred from the viewpoint of anti-scale characteristics are a saturated or unsaturated aliphatic carboxylic acid having 6 to 32 carbon atoms, an aromatic carboxylic acid having 7 to 16 carbon atoms (particularly, aromatic monocarboxylic acid) and / or It is a natural fat fatty acid.

The hydroxyl group-containing compound (b) constituting (A)
The following alcohols (i) and (ii), and polyoxyalkylene compounds which are alkylene oxide (2 to 4 carbon atoms, the same applies hereinafter) adducts of these alcohols and the following phenol (iii) [number average molecular weight (hereinafter, Mn) (5,000 or less). (I) monool [aliphatic (having 1 to 20 carbon atoms such as methanol, n-, i- and sec-butanol, 2-
Ethylhexanol, lauryl alcohol, stearyl alcohol, oleyl alcohol), alicyclic (C5)
(Ii) polyhydric alcohol (divalent to octavalent) [diol [aliphatic (having 2 to 12 carbon atoms, such as ethylene glycol, propylene glycol, trimethylene glycol, 1 , 4
-Butanediol, 1,6-hexanediol, neopentyl glycol), alicyclic (having 5 to 20 carbon atoms, for example, cyclopentane-1,2- and 1,3-diol, cyclohexane-1,2-, 1,1) 3- and 1,4-diols, cycloheptane-1,2-, 1,3-, 1,4-
And 1,5-diol, hydrogenated bisphenol A)
Etc.] trihydric to octahydric polyhydric alcohol [having 3 to 2 carbon atoms]
0, for example, glycerin, trimethylolethane, trimethylolpropane, hexanetriol, diglycerin, tetraglycerin, hexaglycerin, pentaerythritol, sorbitan, sorbitol, sucrose]] (iii) monovalent phenol [monocyclic (C6-C6) 20, for example, phenol, cresol, butylphenol, octylphenol, nonylphenol), polycyclic (C 1
0-20, for example, phenylphenol and naphthol); divalent phenol [monocyclic (C6-16, for example, hydroquinone, resorcinol), polycyclic (C13-C2)
0, for example, bisphenol F, bisphenol A, bisphenol S)]; trivalent to tetravalent or higher phenol [monocyclic (C6 to C16, for example, 1,3,5-
Trihydroxybenzene), polycyclic (13-20 carbon atoms,
For example, 2,3,4-trihydroxybenzophenone)

Among the above hydroxyl-containing compounds (b), preferred are those having a molecular weight of 62 to 2,000 selected from the group consisting of polyhydric alcohols and polyoxyalkylene compounds.
(Mn) is a hydroxyl-containing compound. (A) in the present invention may be obtained by the dehydration condensation reaction of the above (a) and (b), or may be obtained by directly adding alkylene oxide to (a). Good.
The melting point of (A) is usually 100 ° C. or less, and the melting point of the solid one in (A) is usually 40 to 100 ° C., and preferably 45 to 100 from the viewpoint of the balance between the anti-scale effect and the sustainability of the anti-scale effect. The melting point of the paste is usually 0 to 35 ° C, and preferably 10 to 30 ° C from the viewpoint of the balance between the anti-scale effect and the sustainability of the anti-scale effect.

Specific examples of (A) include (A1) esters of polyhydric alcohols and aliphatic monocarboxylic acids (ethylene glycol-stearic acid monoester, propylene glycol-octanoic acid monoester, propylene glycol-palmitic acid monoester). Esters, propylene glycol-stearic acid monoester, glycerin-lauric acid monoester, tetraglycerin-lauric acid monoester, decaglycerin-lauric acid monoester,
Sorbitan-lauric acid monoester, sorbitan-oleic acid monoester, glycerin-stearic acid monoester, hexaglycerin-stearic acid monoester, sorbitan-palmitic acid monoester, sucrose-oleic acid monoester, pentaerythritol-lactic acid monoester Diglycerin-stearic acid diester, sorbitan-lauric acid diester,
Sorbitan-oleic acid diester, sorbitan-oleic acid triester; (A2) esters of polyhydric alcohol and aliphatic polycarboxylic acid (glycerin-succinic acid diester, tetraglycerin-adipic acid diester;
Trimethylolpropane-azelaic acid diester, pentaerythritol-adipic acid diester, pentaerythritol-fumaric acid diester, trimethylolpropane-itaconic acid diester, glycerin-fumaric acid diester, decaglycerin-itaconic acid diester,
Trimethylolpropane-malic acid diester, etc.);
(A3) Ester of polyhydric alcohol and alicyclic monocarboxylic acid (ethylene glycol-cyclohexane carboxylic acid monoester, propylene glycol-cyclohexane carboxylic acid monoester, glycerin-cyclohexane carboxylic acid monoester, ethylene glycol-cyclohexane carboxylic acid diester (A, propylene glycol-cyclohexanecarboxylic acid diester, glycerin-cyclohexanecarboxylic acid triester, etc.);
4) Ester of polyhydric alcohol and alicyclic polycarboxylic acid (glycerin-1,4-cyclohexanedicarboxylic acid diester, sorbitan-1,4-cyclohexanedicarboxylic acid diester, etc.); (A5) Polyhydric alcohol and aromatic carboxylic acid Esters with acids that are liquid at 20 ° C (glycerin-benzoic acid monoester, diglycerin-
(Salicylic acid monoester, diglycerin-benzoic acid triester, tetraglycerin-benzoic acid pentaester, propylene glycol-phthalic acid diester, diglycerin-phthalic acid diester, etc.) (A6) Ester of polyhydric alcohol and natural fatty acid (glycerin) Coconut oil fatty acid esters, sorbitan-coconut oil fatty acid esters, sucrose-palm oil fatty acid esters, etc.);
(A7) Ester of polyoxyalkylene compound and aliphatic monocarboxylic acid [polyoxyethylene glycol (Mn 200 to 2,000) -lauric acid monoester, polyoxyethylene glycol (Mn 200 to 2,
000) -2-ethylhexanoic acid diester, polyoxyethylene glycol (Mn 200 to 2,000) -lauric acid diester, polyoxyethylene glycol monomethyl ether (Mn 200 to 2,000) -lauric acid monoester, polyoxyethylene glycol monoester Octyl ether (Mn 300-2,000) -lauric acid monoester, polyoxyethylene glycol (M
n200-2,000) monomethyl ether-myristic acid monoester, polyoxyethylene glycol (M
n200-2,000) -Stearic acid monoester,
Polyoxyethylene glycol (Mn 200 to 2,000
0) -Oleic acid monoester, polyoxyethylene glycol (Mn200-2,000) -oleic diester, polyoxyethylene glycol (Mn200-
2,000) monomethyl ether-oleic acid monoester, polyoxyethylene glycol (Mn 200-
2,000) monooctyl ether-oleic acid monoester, polyoxy (ethylene / propylene) [weight ratio of ethylene oxide (hereinafter abbreviated as EO) / propylene oxide (hereinafter abbreviated as PO) = 90/10, random addition] glycol (Mn 200 to 2,000) monooctyl ether-stearic acid monoester, polyoxyethylene glycol (Mn 1,000-2,000) -oleic acid monoester, polyoxyethylene glycol (Mn 800-2,000) -oleic acid diester,
Polyoxy [butylene-ethylene (1,4-butylene oxide / EO weight ratio = 25/75, block addition)] glycol (Mn 1,000-2,000) monomethyl ether-oleic acid monoester, polyoxyethylene glycol (Mn1, 000-2,000) monooctyl ether-oleic acid monoester, polyoxyethylene glycol monohexyl ether (Mn 300-
2,000) -lactic acid monoester, polyoxyethylene (Mn200-2,000) glycerin-lauric acid monoester, polyoxyethylene (Mn200-2.0)
00) pentaerythritol-lauric acid diester,
Polyoxyethylene (Mn 200-2,000) sorbitan-monolaurate, polyoxyethylene (Mn 200-2,000) sorbitan-monooleate, polyoxyethylene (Mn 200-2,000)
00) sorbitan-oleic acid diester, polyoxyethylene (Mn 200-2,000) sorbitan-oleic acid triester, etc.); (A8) polyoxyalkylene compound and aliphatic polycarboxylic acid ester [polyoxyethylene glycol (Mn 200-2) , 000) -succinic acid diester, polyoxyethylene glycol (M
n200-2,000) -Adipic acid monoester, polyoxyethylene glycol (Mn 200-2,000)
0) -Adipic acid diester, polyoxyethylene glycol (Mn 200 to 2,000) -azelaic acid monoester, polyoxyethylene glycol (Mn 200
-2,000) -fumaric acid diester, polyoxyethylene glycol (Mn 200-2,000) -itaconic acid diester, polyoxyethylene glycol (Mn2
00-2,000) glutaric acid diester, polyoxyethylene glycol (Mn 200-2,000) malic acid diester, polyoxy [ethylene-propylene (E
O / PO weight ratio = 90/10), block addition] glycol (Mn 200-2,000) -tartaric acid diester, etc.]; (A9) ester of polyoxyalkylene compound and alicyclic monocarboxylic acid [polyoxyethylene glycol (Mn 800 to 2,000) -cyclohexane monocarboxylic acid monoester, polyoxyethylene glycol (Mn 800 to 2,000) -cyclohexane monocarboxylic acid diester, polyoxyethylene (Mn 200
2,000) glycerin-cyclohexane monocarboxylic acid monoester, polyoxyethylene (Mn 200
(2,000) sorbitan-cyclohexane monocarboxylic acid diester, etc.]; (A10) Ester of polyoxyalkylene compound and alicyclic polycarboxylic acid [polyoxyethylene glycol (Mn 600 to 2,000)-
1,4-cyclohexanedicarboxylic acid diester, etc.]
(A11) Ester of polyoxyalkylene compound and aromatic monocarboxylic acid [polyoxyethylene glycol (Mn 200 to 2,000) -benzoic acid diester, polyoxyethylene glycol (Mn 200 to 2,000)
(A12) esters of polyoxyalkylene compounds and aromatic dicarboxylic acids [polyoxyethylene glycol (Mn 200 to
(2,000) -phthalic acid diester, polyoxyethylene glycol (Mn 200 to 2,000) -isophthalic acid diester, etc.) (A13) Ester of polyoxyalkylene compound and natural fatty acid [polyoxyethylene glycol (Mn 200 to 2, 000) -coconut oil fatty acid ester, polyoxyethylene glycol (Mn20)
0 to 2,000) -palm oil fatty acid ester]. Among these, (A1), (A5), (A6), (A7),
(A11) and (A13).

[0010] The solubilizing agent (B) in the present invention is at 20 ° C.
Is a solid compound that has the property of gradually dissolving when contacted with water. Of these, preferred from the viewpoints of slow solubility and shape retention are aromatic ring-containing esters [esters of aromatic carboxylic acid (B1),
Esters of alcohols containing an aromatic ring excluding (B1) (B
2)] and high molecular weight (Mn 10,000 to 500,0
00) polyoxyalkylene (alkylene having 2 to 2 carbon atoms)
4) Compound (B3). As the aromatic carboxylic acid constituting (B1), a monocarboxylic acid (C 7 to C 1)
6, for example, benzoic acid, pt-butylbenzoic acid, salicylic acid, 2-naphthalenecarboxylic acid, etc., poly (divalent to
(4 or more) carboxylic acid (dicarboxylic acid (C8 to C16, for example, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc.), trivalent to
Tetravalent or higher polycarboxylic acid (C 9 to C 1)
6, for example, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, etc.)]. Examples of alcohols constituting (B1) include aromatic ring-containing alcohols [aromatic aliphatic alcohols [monools having 7 to 16 carbon atoms such as benzyl alcohol and cinnamyl alcohol], diols having 8 to 16 carbon atoms such as dihydroxymethylbenzene. ) Etc.] and alkylene oxide adducts of these alcohols (molecular weight 152 to Mn 2,000),
Alkylene oxide adduct of phenol [molecular weight 138
To Mn 2,000), and those exemplified in the above (b)].

(B1) may be obtained by a dehydration condensation reaction between the aromatic carboxylic acid and an alcohol, or may be obtained by directly adding an alkylene oxide to the aromatic carboxylic acid. Is also good. Specific examples of the aromatic carboxylic acid ester (B1) include: an ester of an aromatic monocarboxylic acid and a monool (such as 2-butoxyethylnaphthalene carboxylic acid ester); and an ester of an aromatic monocarboxylic acid and a diol (or Alkylene oxide adduct of aromatic monocarboxylic acid) [2- (2-
(Hydroxyethyl) naphthalenecarboxylic acid ester, 2
An ester of an aromatic monocarboxylic acid and a polyhydric (3 to 8) alcohol (an esterified product of 2-naphthalenecarboxylic acid and an EO 2 mol adduct of trimethylolpropane, Esterified product of 2-naphthalenecarboxylic acid and sorbitol with EO in 5 moles); ester of aromatic polycarboxylic acid and monool [bis (2-methoxyethyl) isophthalate, bis (2-methoxyethyl) terephthalate, 1,2,4-tris (2-methoxyethyl) benzenetricarboxylate and the like]; an ester of an aromatic polycarboxylic acid and a diol (or an alkylene oxide adduct of an aromatic polycarboxylic acid) [bis (2-hydroxyethyl ) Isophthalate, bis (2-hydroxyethyl) terephthalate 1,2,4-tris (2-hydroxyethyl) benzene tricarboxylate, etc.]; aromatic polycarboxylic acids with polyhydric (3-8 valence) esters with alcohols (terephthalic acid and trimethylolpropane E
Esterified product with an O3 mole adduct, esterified product of isophthalic acid with a EO 5 mole adduct of sorbitol, 1,
Esterified product of 2,4-benzenetricarboxylic acid with an EO 3-mole adduct of trimethylolpropane) and a mixture thereof.

Among these, the ester (or aromatic polycarboxylic acid) of an aromatic polycarboxylic acid and a diol is preferable from the viewpoint of the balance between the anti-scale property, the shape-retaining property of the solubilizer, and the long-lasting effect. Alkylene oxide adduct of carboxylic acid), aromatic polycarboxylic acid and polyvalent (3-8)
Ester with an alcohol, more preferably an ester of an aromatic dicarboxylic acid with a diol (or an alkylene oxide adduct of an aromatic dicarboxylic acid), or an ester of an aromatic dicarboxylic acid with a polyhydric (tri- to octahydric) alcohol Bis (2-hydroxyethyl) is particularly preferred.
Isophthalate and bis (2-hydroxyethyl) terephthalate.

Examples of the aromatic ring-containing alcohol constituting (B2) include araliphatic alcohols [monool (C7 to C16, for example, benzyl alcohol, cinnamyl alcohol), diol (C8 to C16, for example, bishydroxyl) Ethylbenzene) and the like, and the above-mentioned phenol alkylene oxide adducts of 1 to 4 mol. Examples of the carboxylic acid constituting (B2) include monocarboxylic acids [aliphatic (C 12 to C 24, for example, lauric acid, myristic acid, stearic acid, oleic acid), alicyclic (C 7 to C 13, for example, cyclohexane) Carboxylic acid), araliphatic (C8-C16, for example, phenylacetic acid, p-methoxyphenylacetic acid)]; dicarboxylic acid [aliphatic (C2-C12, for example, oxalic acid, fumaric acid, adipic acid, 1,1) 10-decanedicarboxylic acid), alicyclic (8 to 18 carbon atoms, for example, cyclohexanedicarboxylic acid), araliphatic (10 to 18 carbon atoms, for example, benzenediacetic acid) and the like]; trivalent or higher polycarboxylic acid [ Aliphatic (C7-C16, for example, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid), alicyclic (C9-C16, Example, if 1,2,4-cyclohexane tricarboxylic acid), araliphatic (1 carbon atoms
2-18, for example, benzenetriacetic acid).

Esters of alcohols containing aromatic rings (B2)
Specific examples of monoesters of monocyclic phenol EO adducts and monocarboxylic acids (phenoxyethyl myristylate, phenoxyethyl stearate, etc.); diesters of monocyclic phenol EO adducts and dicarboxylic acids [bis (2 -Phenoxyethyl) fumarate, bis (2-phenoxyethyl) adipate, bis (2-phenoxyethyl) fumarate, benzenedi (acetic acid-2-phenoxyethylate) and the like; monocyclic phenol EO adduct and trivalent or higher Polyester with polycarboxylic acid [1,2,4-butanetricarboxylic acid tri (2-phenoxyethylate), 1,2,5-hexanetricarboxylic acid tri (2-phenoxyethylate), etc.]; polycyclic phenol EO addition Diester of a product and a monocarboxylic acid [bis (2-hydroxy Le) naphthalene dilaurate,
Bis (2-hydroxyethyl) naphthalene distearate etc.]; di- and poly-esters of polycyclic phenol EO adduct and dicarboxylic acid [bis (2-hydroxyethyl) naphthalene fumarate, bis (2-hydroxyethyl) Naphthalene adipate, etc.]; polycyclic phenol E
Tri- and poly-esters of O adduct with tri- or higher valent polycarboxylic acid [esterified product of bis (2-hydroxyethyl) naphthalene and 1,2,4-butanetricarboxylic acid, bis (2-hydroxyethyl) Naphthalene and 1,
Esterified product with 2,4-cyclohexanetricarboxylic acid, etc.].

Of these, preferred are diesters of a monocyclic phenol EO adduct and a dicarboxylic acid, polyesters of a monocyclic phenol EO adduct and a trivalent or higher polycarboxylic acid, and more preferably a monocyclic phenol EO adduct. A triester of a phenol EO adduct with a tricarboxylic acid, particularly preferably 1,2,4-butanetricarboxylic acid tri (2-phenoxyethylate).

As (B3), polyethylene glycol, poly [ethylene-propylene (EO / PO weight ratio =
99/1 to 20/80, addition type may be block or random)] glycol, poly [ethylene-butylene (EO / 1,2-, 2,3- and 1,4-butylene oxide weight ratio = 99 / 1 to 20/80, addition type may be block or random)] glycol, and the terminal of these compounds may be a hydrophobic group [for example, a hydrocarbon group (8 to 30 carbon atoms), an alkyloyl group (8 to 3 carbon atoms).
0)], diisocyanate (C 8
-20, for example, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, etc.) and / or dicarboxylic acid (C 2-18,
For example, compounds linked with oxalic acid, fumaric acid, adipic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like can be given.

The above-mentioned (B) can be used alone or in a mixture. Among (B1), (B2) and (B3), (B1) and / or (B3) are preferable from the viewpoint of anti-scaling property, and more preferable is a combination of (B1) and (B3) [(B1 ) / (B3) weight ratio = 5/95
９５95/5], and especially (B1) alone.

The melting point of (B) (measuring method: trace melting point meter) is usually 45 ° C. or higher, and preferably from 50 to 2 from the viewpoint of handling.
00 ° C, more preferably 55 to 150 ° C,
The solubility (g / 100 g H ₂ O) at 0 ° C. is preferably at least 0.01, more preferably 0.02 to 10, particularly preferably 0.02, from the viewpoint of long-term effect.
3 to 3.

In the present invention, the descaling agent comprises (A) or (A) and (B), and when (A) and (B) are used in combination, the weight ratio of (A) and (B) used Is preferably (60/4) from the viewpoint of persistence of the effect of the anti-scale agent.
0) to (5/95), more preferably (40/60)
~ (10/90).

In the present invention, a dissolution rate adjusting component (C) may be used in addition to the above components. As (C), a hydroxyl group-containing compound having low volatility (boiling point of 150 ° C. or more) and a solubility at 20 ° C. (g / 100 g H ₂ O) of 30 or more, for example, (C1) an alkylene glycol having 2 to 6 carbon atoms (Ethylene glycol, propylene glycol, trimethylene glycol, 1,2-, 1,3-, 2,3-
And 1,4-butylene glycol, 1,6-hexylene glycol, etc.), (C2) C3-10 trihydric or higher polyhydric alcohols (glycerin, diglycerin, trimethylolpropane, etc.), (C3 ) Polyoxyalkylene (alkylene having 2 to 4 carbon atoms) glycol having a molecular weight of 100 to less than Mn 10,000 [polyoxypropylene glycol (molecular weight 250 or less), polyoxyethylene glycol (Mn less than 10,000), etc.]
Is mentioned. Of these, preferred are (C2) and (C3) from the viewpoint of compatibility between (A) and (B).
It is. The amount of (C) used is usually 0 to 30% by weight, preferably 0 to 20% by weight, based on the total amount of (A) and (B).
It is.

A surfactant, a coloring agent, a fragrance, a bulking agent and other additives can be added to the solubilizer of the present invention as other components (D).

Examples of the surfactant include a nonionic surfactant (excluding the compounds exemplified as (A) and (B) above), an anionic surfactant, a cationic surfactant,
Examples include an amphoteric surfactant. Examples of the nonionic surfactant include alkylene oxide-added nonionic surfactants [higher alcohols (8 to 18 carbon atoms), alkylphenols (10 to 24 carbon atoms), higher fatty acids (12 to 24 carbon atoms), and higher alkylene oxides. Alkylamine (C8
To 24), etc. (molecular weight: 158 to Mn: 200,000); polyoxyalkylene glycol (molecular weight: 15 to 15) obtained by adding an alkylene oxide to glycol (2 to 12 carbon atoms).
0 to Mn 6,000) and higher fatty acids (C12 to C2).
4) and the like; polyhydric alcohol (having 2 carbon atoms)
To 12, for example, an esterified product obtained by reacting a higher fatty acid (12 to 24 carbon atoms) with a divalent to octavalent or higher polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, and sorbitan. To which an alkylene oxide is added (molecular weight 250 to Mn 30,000), polyhydric alcohol (as described above) alkyl (C3 to 60) ether to which an alkylene oxide is added (molecular weight 120 to
Mn 30,000)], and polyhydric alcohol (as described above) alkyl (3 to 60 carbon atoms) ether.

Examples of the anionic surfactant include carboxylic acids (saturated or unsaturated fatty acids having 8 to 22 carbon atoms).
Or its salts (sodium, potassium, ammonium,
Such as alkanolamines), salts of carboxymethylated compounds [salts of carboxymethylated compounds such as aliphatic alcohols having 8 to 16 carbon atoms and / or EO (1 to 10 mol) adduct thereof], sulfate salts [higher Alcohol sulfates (sulfuric acid esters of aliphatic alcohols having 8 to 16 carbon atoms)], higher alkyl ether sulfates [EO of aliphatic alcohols having 8 to 18 carbon atoms]
(1 to 10 mol) adduct sulfate salt], sulfated oil (natural unsaturated oil or fat, or unsaturated wax which is neutralized by sulfation as it is), sulfated fatty acid ester (lower alcohol of unsaturated fatty acid) Sulfated and neutralized esters; sulfated olefins (sulfurized and neutralized olefins having 12 to 18 carbon atoms); sulfonates [alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinic diesters] Type, α-olefin (12-18 carbon atoms) sulfonate, Igepon T type, etc.) and phosphoric ester salt [higher alcohol (8-60 carbon atoms) EO adduct phosphoric acid ester salt, alkyl (4-6 carbon atoms) 60) Phenol EO adduct phosphate ester salt].

As the cationic surfactant, a quaternary ammonium salt type [tetraalkyl (C4-100) ammonium salt such as lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide] A trialkyl (C3-C80) benzylammonium salt such as lauryl dimethylbenzylammonium chloride (benzalkonium chloride); an alkyl (C2-C60) pyridinium salt such as cetylpyridinium chloride;
Polyoxyalkylene (C2-4) trialkylammonium salt, for example, polyoxyethylene trimethylammonium chloride; sapamine-type quaternary ammonium salt, for example, stearamidoethyldiethylmethylammonium methosulfate], amine salt type [aliphatic higher amine] (C12-C60, such as laurylamine, stearylamine, cetylamine, hardened tallowamine, rosinamine, etc.) Inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salt or organic acid (C2-C22, such as acetic acid, Salts of propionic acid, lauric acid, oleic acid, benzoic acid, succinic acid, adipic acid, azelaic acid); inorganic acid (as described above) such as EO adducts of aliphatic amines (1 to 30 carbon atoms) or organic salts Acid (as described above) salts; tertiary amines (triethanol Emissions monostearate, stearamide ethyl diethyl methylethanolamine) those of inorganic acids (above) salts or organic acids (above one) salts], and others.

Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants [higher alkylamines having 12 to 18 carbon atoms].
Sodium beta-propionate], betaine-type amphoteric surfactant [alkyl (12-18 carbon atoms) dimethyl betaine], sulfate-type amphoteric surfactant [higher alkyl (8-18 carbon atoms) amine sulfate sodium salt , Hydroxyethylimidazoline sulfate sodium salt, etc.], sulfonate type amphoteric surfactants (pentadecylsulfotaurine, imidazoline sulfonic acid, etc.), phosphate ester type amphoteric surfactants [glycerin higher fatty acid (8 to 22) Esterified phosphoric acid ester amine salt].

Among these, a nonionic surfactant is preferred from the viewpoint of compatibility with (A) and (B), and the amount of the nonionic surfactant is preferably (A) or (A) or (B). ) Is usually 30% by weight or less, preferably 0 to 20% by weight, based on the total amount of (1).

As the coloring agent, for example, methylene blue,
Cyanine Blue, Blue No. 1, Blue No. 2 and aluminum lake products thereof, Red No. 1, Red No. 2 and the like. The amount of the colorant used is usually 10% by weight or less, preferably 0 to 5% by weight, based on (A) or the total amount of (A) and (B).
It is.

As the fragrance, vegetable essential oils (lavender oil,
Lemon oil, rose oil, green oil, etc.); animal flavors (musk, civet, etc.); synthetic flavors (aldehydes,
Esters, ketones, etc.); The amount of fragrance used is (A) or
It is usually at most 10% by weight, preferably 0 to 5% by weight, based on the total amount of (A) and (B).

As fillers, inorganic salts (eg, sodium sulfate, anhydrous sodium sulfate, potassium sulfate, sodium carbonate, calcium carbonate,
Calcium phosphate, boric acid, talc, colloidal silica, etc.); and organic compounds (urea, etc.). The amount of the extender used is usually 50% by weight or less, preferably 0 to 20% by weight, based on (A) or the total amount of (A) and (B).

Other additives include builders (sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, etc.), chelating agents (hydroxycarboxylic acids and salts thereof, polyamineacetic acids and salts thereof, water-soluble polycarboxylic acids). And its salts), disinfectants (chitosan, hinokitiol, tea catechin, etc.), disinfectants (chlorine, iodine, quaternary ammonium salts, imidazole, guanidine, etc.), ultraviolet absorbers (salicylic acid, benzophenone) Benzotriazole-based) and the like, and the amount of these other additives used is
It is usually 50% by weight or less, preferably 0 to 20% by weight, based on (A) or the total amount of (A) and (B).

The antiscaling agent of the present invention can be produced by the following method. (1) In a heatable mixing tank, add (A) or (A) and (B), and if necessary, component (C), and add
After melting and mixing at 150 ° C, the temperature is adjusted to 70 to 120 ° C. Next, if necessary, the component (D) is added and further mixed, then poured into a suitable container such as a plastic cup (liquid casting method), and solidified by natural cooling or forced cooling. After at least one hour elapses after casting, the solid is obtained by demolding. (2) Add (A), or (A) and (B), and if necessary, component (C) to a mixer such as a ribbon mixer and mix at 10 to 60 ° C. Next, if necessary, the component (D) is added and mixed, and then mixed with a two-roll mixer. Next, the mixture is extruded at 10 to 60 ° C. using an extruder to obtain a rod-shaped preparation (extrusion molding method). Next, it is cut into a predetermined size by a cutter or the like to obtain a desired solid drug. The solid drug (slowly soluble anti-scale agent) obtained as described above is solid at 20 ° C., and the weight per piece is usually 2 g or more, preferably 15 to 2,000 g. Melting point is usually 40 ° C. or higher, preferably 45 to 12
0 ° C, more preferably 50 to 100 ° C. Also,
The dissolution time of the solid drug of the present invention (defined in (3) Persistence of the test method described later) is usually 10 hours or more,
Preferably, it is 15 to 600 hours. The on-tank drug (duration: 1 month) to be used by installing it in the hand washing section of the water tank of the flush toilet usually has a dissolution time of 10 to 50 hours, preferably 15 to 30 hours, and is put into the water tank of the flush toilet. For in-tank use (1 month duration)
Means that the dissolution time is usually 100 to 250 hours, preferably 1
50-200 hours. Furthermore, the long-lasting drug of 2 months or more of the in-tank drug usually has a dissolution time of 350 hours or more, preferably 400 to 600 hours.

The antiscalp agent (solid chemical) for sanitary ware of the present invention is usually a submerged type in a water tank immersed in a water tank of a sanitary ware flush toilet, and a water tank hand washing part installed in a hand washing part of the water tank. It is used as a scale and / or as a scale preventive material installed in a toilet. Specifically, if the solid medicine is used in a container having an opening, the use time (dissolution time) can be adjusted more widely by adjusting the opening area of the container surface (about 1 to 70%). It is not only advantageous, but also aesthetically pleasing. The solid medicine gradually dissolves by touching the washing water, and every time sanitary ware is used, the pottery surface is washed away with the washing water in which the solid medicine is slightly dissolved and the vitreous pottery surface is protected. Of silica (silicic acid) is deposited on the ceramic surface to prevent water scale. The concentration of the anti-scaling agent [(A) or the sum of (A) and (B)] in the washing water is usually 0.5 to 100 ppm, and preferably 2 to 50 ppm from the viewpoint of anti-scaling properties. As described above, if the anti-descaling agent of the present invention is used, it is possible to perform ordinary maintenance only by rubbing lightly with a brush using water alone or a commercially available household cleaning agent (eg, a neutral liquid detergent) about once a week. Sanitary ware can be kept clean at all times.

[0033]

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples. In the following, parts and% indicate parts by weight and% by weight, respectively. First,
The composition of the raw materials used in the examples is shown below. A1-1: Ethylene glycol monostearate (melting point 50 ° C, HLB 3.7) A1-2: Sorbitan monopalmitate (melting point 46 ° C,
HLB 8.0) A1-3: Sorbitan monolaurate (HLB8.6) A1-4: Tetraglycerin monolaurate (HLB1)
0.3) A1-5: Sorbitan monooleate (HLB4.3) A1-6: Sorbitan trioleate (HLB1.8) A1-7: Decaglycerin monooleate (HLB1)
2.9) A5-1: Glycerin monobenzoate (HLB14.
8) A6-1: Glycerin-coconut oil fatty acid ester (melting point 4
5 ° C., HLB 5.1) A7-1: Polyoxyethylene glycol (molecular weight: 20)
0) Monostearate (melting point 45 ° C., HLB 8.5) A7-2: Polyoxyethylene glycol (Mn 2,0
00) monostearate (melting point 55 ° C, HLB 15.
8) A7-3: Polyoxyethylene glycol (Mn20)
0) Dilaurate (HLB6.6) A7-4: Polyoxyethylene (Mn900) Sorbitan monolaurate (HLB16.7) A7-5: Polyoxyethylene (Mn300) monooctyl ether monolaurate (HLB10.8) A7- 6: polyoxyethylene glycol (Mn40)
0) Monooleate (HLB11.8) A7-7: Polyoxyethylene (Mn300) Sorbitan monooleate (HLB16.7) A11-1: Polyoxyethylene glycol (Mn20)
0) Dibenzoate (HLB9.7) A13-1: EO of sorbitan palm oil fatty acid ester
23 mol adduct (paste, melting point 15 ° C, HLB1
5.5) B1-1: Bis (2-hydroxyethyl) terephthalate (melting point: 110 ° C.) B3-1: Polyoxy [ethylene-propylene (EO /
PO weight ratio = 80/20, block addition)] glycol (Mn 15,000; melting point 57 ° C.) C2-1: trimethylolpropane C3-1: polyoxyethylene glycol (Mn 6,0
00)

The test methods performed in the examples and comparative examples are as follows. (1) Melting point Measured by a micro melting point meter (Yanagimoto Seisakusho). (2) Antifouling property A sanitary ware piece (25 m) that was gently rubbed with a sponge using a commercially available neutral liquid detergent and then thoroughly rinsed with tap water to clean it
(m × 100 mm, thickness 4 mm) was obliquely leaned against a clean 100 ml glass beaker so as not to fall. Next, 200 ml of washing water having a sample concentration of 10 ppm, in which a solid anti-scale agent was dissolved in tap water, was slowly flowed from the top of the pottery piece, and the excess was allowed to overflow.
The operation of flowing the sample washing water was further performed four times every one hour, and then allowed to stand at room temperature (18 to 26 ° C.) for 19 hours. Furthermore,
The same operation as described above in which the sample washing water was allowed to flow five times a day and allowed to stand at room temperature for 19 hours was repeated for 14 consecutive days. After the test, pull the pottery pieces out of the beaker and allow them to air dry,
The presence or absence of water scale on the draft surface and its degree were visually evaluated according to the following criteria. Next, the pottery pieces were lightly rubbed 20 times with a sponge moistened with tap water, rinsed with tap water, dried, and visually evaluated in the same manner as above. <Evaluation Criteria> ：: No dirt at all ○: Slight dirt spots △: Thin linear dirt x: Dark linear dirt (3) Sustained columnar (diameter 30mm, height about 45mm) Of solid medicine (about 50 g) in a cylindrical mesh basket made of stainless steel (40 m in diameter)
m, height 65 mm; opening about 95%) and into a circulating thermostatic water bath (volume: 10 L; water temperature: 25 ° C.)
The relationship between the elapsed time and the residual weight of the solid drug was graphed, and the time at which the residual weight was 5 g was defined as the dissolution time.

Examples 1 to 9 The components shown in Table 1 (component (A) was solid or paste at 20 ° C) were heated to 90 to 110 ° C, uniformly mixed and dissolved, and then cooled to about 80 ° C. After that, 50 g of the mixed solution was
1 into a polypropylene cup. Indoor (about 2
(0 ° C.) for at least 3 hours, cooled, and then demolded to obtain a solid anti-scaling agent. Table 1 shows the evaluation results. Examples 10 to 27 The blending components (A) described in Table 1 were replaced by the blending components (A) described in Table 2.
(Liquid at 20 ° C) was carried out in the same manner as in Examples 1 to 9 to obtain a solid anti-scaling agent. Table 2 shows the evaluation results. Comparative Example 1 The antifouling property was evaluated using only water without using a solid scale inhibitor. Table 1 shows the results. Comparative Example 2 The same evaluation as in Examples 1 to 27 above was performed on a commercially available solid aromatic detergent. Table 1 shows the results.

Example 28 The anti-descaling agent obtained in Example 10 (weight: about 50 g)
Plastic container (opening area: about 30%)
Was placed in a hand washing section of a water tank (low tank) of a new Western-style flush toilet (manufactured by Tohoku Kiki Co., Ltd.), and the test was started as a water tank hand washing section installation type anti-scale material. The toilet was cleaned once a week by rubbing the ball surface and the trap lightly with water only using a nylon brush. Two months later, the bowl surface of the toilet bowl and the draft portion of the trap were visually observed, but no scale was attached. The toilet was used about 1,300 times during the test period, and the residual weight of the solid anti-scale agent after the test was about 15 g.

Example 29 The anti-descaling agent obtained in Example 21 (weight: about 50 g)
A plastic container (opening area: approx. 5%) containing a string is attached, and it is fixed at a place 10 cm below the surface of a new Western-style flush toilet (manufactured by TOTO KOGYO CO., LTD.) Water tank (low tank). The test was started as an immersion type anti-scale material. The toilet was cleaned once a week by rubbing the ball surface and the trap lightly with water only using a nylon brush. Two months later, the bowl surface of the toilet bowl and the draft portion of the trap were visually observed, but no scale was attached. The number of times the toilet was used during the test was about 950 times, and the residual weight of the solid anti-scale agent after the test was about 5 g.

Example 30 A plastic container (opening area: about 30%) containing the anti-descaling agent obtained in Example 3 (weight: about 50 g) was used.
It was placed in the hand washing section of a water tank (low tank) of a new Western-style flush toilet (manufactured by Tohoku Kiki Co., Ltd.), and the test was started as a water tank anti-scale material installed in the hand washing section. The toilet was cleaned once a week by rubbing the ball surface and the trap lightly with water only using a nylon brush. Two months later, the ball surface of the toilet bowl and the draft portion of the trap were visually observed, but no scale was attached. The toilet was used about 1,500 times during the test period, and the residual weight of the solid anti-scale agent after the test was about 20 g.

Example 31 A string was attached to a plastic container (opening area: about 10%) containing the anti-descaling agent (weight about 50 g) obtained in Example 1, and a new Western-style flush toilet (TOTOKIKIKI) The test was started at 10 cm below the water surface in a water tank (a low tank) manufactured as a immersion type anti-scale material in the water tank. The toilet was cleaned once a week by rubbing the ball surface and the trap lightly with water only using a nylon brush. Two months later, the ball surface of the toilet bowl and the draft portion of the trap were visually observed, but no scale was attached. The toilet was used about 1,700 times during the test period, and the residual weight of the anti-scale agent after the test was about 12 g.

Example 32 Example 1 was repeated using 30 parts of A1-5 and 70 parts of B3-1.
To 27 (melting point 7)
(0 ° C.) 50 g in a plastic container (opening area: about 30
%), And placed in a hand washing section of a water tank (low tank) of a new Western-style flush toilet (manufactured by Tohoku Kikai Co., Ltd.), and a test was started as a water tank hand washing section installation type anti-scale material. The toilet was cleaned once a week by rubbing the ball surface and the trap lightly with water only using a nylon brush. Two months later, the ball surface of the toilet bowl and the draft portion of the trap were visually observed, but no scale was attached. The number of times of using the toilet during the test period was about 1,500 times, and the residual weight of the solid anti-scale agent after the test was about 35 g.

Example 33 Example 1 was repeated using 50 parts of A5-1 and 50 parts of B3-1.
To 27 (melting point 6)
(0 ° C.) 50 g in a plastic container (opening area: about 10
%) And stored in a new Western-style flush toilet (manufactured by TOTO Kiki Co., Ltd.)
The container was suspended with a string at a position 10 cm below the water surface in a water tank (low tank) and fixed, and the test was started as an immersion-type anti-scale material in the water tank. The toilet was cleaned once a week by rubbing the ball surface and the trap lightly with water only using a nylon brush. Two months later, the ball surface of the toilet bowl and the draft portion of the trap were visually observed, but no scale was attached. The number of toilets used during the test period was about 1,600
And the residual weight of the solid anti-scaling agent after the test is about 17
g.

Example 34 Example 1 was repeated using 30 parts of A7-7 and 70 parts of B3-1.
To 27 (melting point 6)
50 g in a plastic container (opening area: about 30)
%), Placed in a hand washing section of a water tank (low tank) of a new Western-style flush toilet (manufactured by Tohoku Kikai Co., Ltd.), and the test was started as a water scale hand-washing section installation type anti-scale material. The toilet was cleaned once a week by rubbing the ball surface and the trap lightly with water using a nylon brush. 2
A month later, the bowl surface of the toilet bowl and the draft portion of the trap were visually observed, but no scale was attached. The toilet was used about 1,200 times during the test period, and the residual weight of the anti-scale agent after the test was about 23 g.

Example 35 A plastic container (opening area: 50 g) was prepared using 50 parts of A11-1 and 50 parts of B3-1 in the same manner as in Examples 1-27 using 50 g of a solid anti-scale agent (melting point: 55 ° C.). About 1
0%), and a new Western-type flush toilet (manufactured by Tohoku Kikai Co., Ltd.) suspends the container with a string at a position 10 cm below the water level in the water tank (low tank), and fixes it in the water tank. The test was started. The toilet was cleaned once a week by rubbing the ball surface and the trap lightly with water using a nylon brush. Two months later, the ball surface of the toilet bowl and the draft portion of the trap were visually observed, but no scale was attached. The number of toilets used during the test period is about 1,
The test was performed 200 times, and the residual weight of the solid anti-scaling agent after the test was about 10 g.

[0044]

[Table 1]

[0045]

[Table 2]

As is clear from Tables 1 and 2, the anti-scale agent of the present invention has the ability to prevent the adhesion of the scale to the surface of the sanitary ware even at a very low concentration (10 ppm). Excellent performance for easy removal. In addition, the dissolution time is as wide as 30 to 600 hours. In the field tests with the flush toilets of Examples 28 to 35, it was demonstrated that the anti-scaling agent of the present invention is excellent in anti-scaling properties and excellent in long-term durability of 2 months or more.

[0047]

The anti-scale agent of the present invention is excellent in the performance of gradually releasing a drug (anti-scale component) upon contact with water to prevent the adhesion of scale to the surface of sanitary ware. The use of the anti-descaling agent of the present invention has the merit that maintenance is easy, such as easy cleaning of flush toilets, and that the sanitary ware can be kept in a clean state for a long time, and its practical value is extremely high. .

Claims (8)

[Claims] 1. An anti-scale agent for sanitary ware, comprising an ester group-containing compound (A) having an HLB of 1.5 to 17 or (A) and a solid solubilizer (B) at 20 ° C. 2. The composition according to claim 1, wherein (A) is at least one selected from the group consisting of an ester group-containing compound which is liquid at 20 ° C. and an aliphatic ester and an alicyclic ester which are solid or paste at 20 ° C. Item 1. An anti-scale agent according to Item 1. 3. The method according to claim 1, wherein (B) is an aromatic ring-containing ester and / or
The anti-scale agent according to claim 1 or 2, which is a high molecular weight polyoxyalkylene compound. 4. (A) is selected from the group consisting of an aliphatic carboxylic acid having 6 to 32 carbon atoms and / or an aromatic monocarboxylic acid having 7 to 16 carbon atoms, and a polyhydric alcohol and a polyoxyalkylene compound. Molecular weight 62-2,000
The anti-scale agent according to any one of claims 1 to 3, which is an ester with a hydroxyl group-containing compound. 5. The anti-scale agent according to claim 1, wherein (B) contains an ester of an aromatic carboxylic acid. 6. The anti-scale agent according to claim 1, further comprising a dissolution rate regulator (C). 7. The composition according to claim 1, further comprising an additive selected from the group consisting of a surfactant, a colorant, a fragrance, a bulking agent, a builder, a chelating agent, a disinfectant, a bactericide, and an ultraviolet absorber. The antiscaling agent according to any one of 1 to 6, above. 8. An immersion type in a water tank of a sanitary ware flush toilet using the descaling agent according to any one of claims 1 to 7.
Water scale anti-scale material installed in water tank hand washing section and / or installed in toilet bowl.