JP2009029973A - Slow-solubilizing agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a slow-solubilizing agent having miscibility, moldability, quality stability, long-term persistency, temperature dependence of slow-solubilizing speed and the like. <P>SOLUTION: The slow-solubilizing agent contains a compound (A) expressed by formula (1) and a compound (B) expressed by formula (3), wherein the sum total of (A) and (B) is ≥70 wt.% and the weight ratio (A)/(B) is 0.1-0.5. The formula (1) is Q[-(OA<SP>1</SP>)<SB>m</SB>-Z]<SB>n</SB>, wherein Q represents a residue of a 3-6 valent aliphatic polyhydric alcohol or a specific 4 valent group; Z represents OH, a 12-22C acyloxy or acylamino, at least one Z out of n Zs is OH; OA<SP>1</SP>represents a 2-4C oxyalkylene; m is an integer of 0-2; n is an integer of 3-6; m×n is a number of 0-6. The formula (3) is R<SP>2</SP>-(OA<SP>2</SP>)<SB>k</SB>-OH, wherein R<SP>2</SP>represents H, a 1-25C alkyl or a 2-25C alkenyl; OA<SP>2</SP>represents a 2-4C oxyalkylene; k is a number of 70-700. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a slow solubilizing agent. More specifically, the present invention relates to a slow-dissolving agent that can be used for a slow-dissolving preparation such as a solid aroma cleaner for flush toilets and a kitchen sink drainage slime inhibitor.

A slow-dissolving agent is a drug that can be adjusted so that it gradually dissolves in water by gradually dissolving itself in water so that a drug that should be gradually released, such as a fragrance, a coloring agent, and a surfactant, is gradually dissolved in water. .
Conventionally, as a solubilizer, an oxyethylene group-containing aromatic compound, or a combined system of the oxyethylene group-containing aromatic compound and a water-soluble aliphatic compound (Patent Document 1), at least a carboxylic acid ester having an aromatic group and a fatty acid Combination system of alkanolamide and / or high molecular weight polyoxyalkylene compound (Patent Document-2), urethane compound of polyoxyalkylene glycol and organic polyisocyanate compound (Patent Document-3), end-capped alkoxylate type non An ionic surfactant (Patent Document-4), a polyester polyol (Patent Document-5) containing at least 2 units of a specific polyalkylene glycol, and the like are known.
The performance required for a slow-dissolving agent includes miscibility with fragrances and coloring agents, moldability during formulation molding, quality stability during long-term storage of the formulation, long-term sustainability of the slow-solubility effect, and slowness depending on the temperature of the water used. The dependence of the solubilization rate is small and the shape retention stability during use is such that conventional slow-dissolving agents have insufficient at least one of these required performances. A satisfactory slow-dissolving agent has not been obtained. For example, Patent Document-1 and Patent Document-2 have insufficient moldability during formulation molding, and Patent Document-3 has insufficient shape retention stability.
JP-A-8-319472 JP 2002-114965 A JP-A-55-1331098 JP 2003-292997 A JP 2005-298830 A

  The problems of the present invention include miscibility with fragrances and coloring agents, moldability at the time of formulation molding, quality stability during long-term storage of the formulation, long-term sustainability of the slow-solubility effect, and slow dissolution rate depending on the temperature of the water used. It is to provide a slow-dissolving agent having little dependence and a shape-retaining stability during use, and a slow-dissolving preparation containing the slow-dissolving agent and various additives.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention provides a slow solubilizing agent comprising the compound (A) represented by the general formula (1) and the compound (B) having a number average molecular weight of 3,000 to 30,000 represented by the general formula (3). The total weight of (A) and (B) based on the weight of the slow solubilizer is 70% by weight or more, and the weight ratio (A) / (B) is 0.1 to 0.5. It is a characteristic slow-dissolving agent.
[Wherein, Q is a residue of a trivalent to hexavalent aliphatic polyhydric alcohol or a tetravalent group represented by the general formula (2); Z is a hydroxyl group, an acyloxy group having 12 to 22 carbon atoms, or 12 to 12 carbon atoms; 22 is an acylamino group, wherein at least one of n Z is a hydroxyl group; OA ¹ is an oxyalkylene group having 2 to 4 carbon atoms; m is a number from 0 to 2, and n is an integer from 3 to 6. M × n representing the average number of moles of (OA ¹ ) per molecule is a number from 0 to 6. ]
[Wherein, R ¹ represents an alkylene group having 2 to 6 carbon atoms. ]
[Wherein, R ² is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an alkenyl group having 2 to 25 carbon atoms; OA ² is an oxyalkylene group having 2 to 4 carbon atoms; k is a number from 70 to 700. . )

  The slow-dissolving agent of the present invention is excellent in miscibility with fragrances and coloring agents, excellent in moldability during formulation molding, quality stability during long-term storage of the formulation, long-term sustainability of the slow-solubility effect, water used Less dependent on the slow solubilization rate due to temperature, and excellent shape retention stability during use.

  Q in the general formula (1) representing the compound (A) is a residue of a trivalent to hexavalent aliphatic polyhydric alcohol, or a group represented by the general formula (2), preferably from the viewpoint of miscibility. It is a residue of a 3-6 valent aliphatic polyhydric alcohol.

  The following are mentioned as a 3-6 valent aliphatic polyhydric alcohol. Examples of the trihydric alcohol include glycerin and trimethylolpropane. Examples of the tetrahydric alcohol include physitol, pentaerythritol, diglycerin and sorbitan. Examples of the pentahydric alcohol include xylit and triglycerin. Examples of the hexavalent alcohol include sorbitol, mannitol, dipentaerythritol and the like.

R ¹ in the tetravalent group represented by the general formula (2) is an alkylene group having 2 to 6 carbon atoms, and examples thereof include an ethylene group, a propylene group, a trimethylene group, a butylene group, a pentamethylene group, and a hexamethylene group. . From the viewpoint of temperature dependency of water, an ethylene group or a propyl group is preferable, and an ethylene group is more preferable.

  Among Z in the general formula (1), as the acyloxy group having 12 to 22 carbon atoms (RCOO-), for example, lauroyloxy group, myristoyloxy group, palmitoyloxy group and stearoyl derived from saturated aliphatic monocarboxylic acid Oxy group, etc., and lauroreyloxy group, myristoloxy group, palmitoleyloxy group, oleyloxy group, linoleyloxy group, linoleyloxy group, linolenyloxy group, and vacenyloxy derived from aliphatic unsaturated monocarboxylic acid Groups and the like.

  Among the acyloxy groups, preferred are a lauroyloxy group, a myristoyloxy group, a palmitoyloxy group derived from a saturated aliphatic monocarboxylic acid from the viewpoints of shape retention, stability of a slow solubilization rate and quality stability during storage. A stearoyloxy group and a combination thereof.

  Among Z in the general formula (1), examples of the acylamino group having 12 to 22 carbon atoms (RCONH-) include, for example, lauroylamino group, myristoylamino group, palmitoylamino group and stearoyl derived from saturated aliphatic monocarboxylic acid Amino groups and the like, and lauroreylamino groups derived from aliphatic unsaturated monocarboxylic acids, myristolylmonomono groups, palmitoleylamino groups, oleylamino groups, linoleylylamino groups, linoleylamino groups, linolenylamino groups, and Examples include a vacenyl amino group.

  Of the acyloxy group and acylamino group, an acyloxy group is preferred from the viewpoint of miscibility.

  In the compound (A), a residue of the trivalent or hexavalent aliphatic polyhydric alcohol or a part of the tetravalent group represented by the general formula (2) is esterified or amidated, and the remainder is a hydroxyl group. A compound. Among the 3 to 6 hydroxyl groups or tetravalent groups of the polyhydric alcohol, there is an average of at least one group that is not esterified or amidated, that is, an average of at least one of n Z is a hydroxyl group. .

OA ¹ in the general formula (1) is an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, a trimethylene group, and a butylene group. From the viewpoint of shape retention, preferred are an ethylene group and a 1,2-propylene group, and more preferred is an ethylene group.

In general formula (1), m is a number from 0 to 2, n is an integer from 3 to 6, and m × n representing the average number of moles of (OA ¹ ) per molecule is 0 to 6. In addition, when mxn is not 0, the compound (A) is usually produced through a process of adding alkylene oxide, and thus is a mixture of different addition mole numbers, and mxn is an average addition. Represents the number of moles. m is preferably 0 to 1 and more preferably 0 from the viewpoint of shape retention. M × n is preferably 0 to 4, more preferably 0 to 3, particularly 0 from the viewpoint of storage stability.

  The hydroxyl value (JIS K0070-1992) of (A) is preferably 90 to 400 mgKOH / g from the viewpoint of sustainability of the slow solubility effect. More preferably, it is 100-300 mgKOH / g.

  (A) preferably has a melting point of 50 to 80 ° C. If it is 50 degreeC or more, it is excellent in the long-term storage property in the normal temperature warehouse etc. of summer, and if it is 80 degreeC or less, it is excellent in the moldability at the time of manufacture.

  In (A), a compound in which Q is a residue of an aliphatic polyhydric alcohol and a part of Z is an acyloxy group is an esterification of an aliphatic polyhydric alcohol with a fatty acid represented by RCOOH or a halide thereof. Obtained by reaction. Examples of fatty acids represented by RCOOH include saturated aliphatic monocarboxylic acids such as lauric acid, myristic acid, palmitic acid and stearic acid, and lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, and linolenic acid. And aliphatic unsaturated monocarboxylic acids.

  The molar ratio in the esterification reaction is x mole of fatty acid per mole of aliphatic polyhydric alcohol. As the catalyst for the esterification reaction, either an acid catalyst or a base catalyst can be used. Examples of the acid catalyst include hydrogen halides (such as hydrogen chloride), carboxylic acids (such as acetic acid and oxalic acid), phosphoric acid, and sulfonic acids (such as methanesulfonic acid). Examples of the base catalyst include alkali metal hydroxide salts (sodium hydroxide, potassium hydroxide, etc.), triethylamine, pyridine, 2,4,6-trimethylpyridine, 1,8-diazabicyclo [5,4,0] undec-7- En, 1,4-diazabicyclo [2,2,2] octane and the like. From the viewpoint of preventing coloring, an alkali metal hydroxide salt is preferred. The temperature is preferably 150 to 250 ° C. and the time is preferably 2 to 20 hours.

Specific examples of the compound in which Q is a residue of an aliphatic polyhydric alcohol and a part of Z is an acyloxy group in (A) include the following.
(A1): Lauric acid ester of 1,2-propylene oxide 2.5 mol adduct of sorbitol [average of 1.8 Z is lauroyloxy group and average of 4.2 is hydroxyl group, hydroxyl value = 358 mgKOH / g]
(A2): Myristic acid ester of sorbitan ethylene oxide 2.5 mol adduct [
An average of 2.6 of 4 Zs is a myristoyloxy group and an average of 1.4 is a hydroxyl group, hydroxyl value = 95 mgKOH / g]
(A3): Palmitic acid ester of 0.5 mol adduct of physitol ethylene oxide [average of 4 Z is palmitoyloxy group and average of 2.0 is hydroxyl group, hydroxyl value = 179 mgKOH / g ]
(A4): Glycerin stearate [average 1.3 of 3 Z is stearoyloxy group and average 1.7 is hydroxyl group, hydroxyl value = 216 mgKOH / g]

  Among (A), a compound in which Q is a tetravalent group represented by the general formula (2) is represented by the general formula (4) by an amidation reaction between an amino compound represented by the general formula (4) and a fatty acid or a halide thereof. The amidated product represented by 5) is produced, and two molecules of the amidated product are condensed with urea to obtain a condensate represented by the general formula (6).

In formulas (4) to (6), R ³ represents an alkylene group having 2 to 4 carbon atoms, and examples thereof include the aforementioned alkylene groups. R ⁴ represents a residue of a fatty acid having 12 to 22 carbon atoms, and examples of the fatty acid include fatty acids represented by RCOOH.

  Examples of the amino compound represented by the general formula (4) include 2- (2-aminoethylamino) ethanol and 3- (3-aminopropylamino) propanol.

  It is preferable that the preparation molar ratio in amidation reaction is 0.95-1.05 mol of fatty acid or its halide with respect to 1 mol of amino compounds shown by General formula (4). The temperature is preferably 160 to 200 ° C., and the time is preferably 1 to 10 hours. The charging molar ratio in the condensation reaction with urea is preferably 0.5 to 0.8 mol of urea with respect to 1 mol of the amidated compound represented by the general formula (5). The temperature is preferably 160 to 200 ° C., and the time is preferably 1 to 10 hours.

As a specific example of the compound in which Q is a tetravalent group represented by the general formula (2) in (A),
(A5): Compound obtained by condensing 2-molecule-stearamide of 2-aminoethyl-2-aminoethanol with urea [Q is a group represented by the general formula (2); The average of 2.0 is a stearoylamino group, the average of 2.0 is a hydroxyl group, and the hydroxyl value is 292 mgKOH / g].

The compound (B) in the present invention is represented by the general formula (3). R ² in the general formula (3) is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an alkenyl group having 2 to 25 carbon atoms, and is preferably a hydrogen atom from the viewpoint of sustainability of the slow solubility effect. OA ² is an oxyalkylene group having 2 to 4 carbon atoms. From the viewpoint of moldability, OA ² is preferably 90% by weight or more, more preferably all oxyethylene groups.
Moreover, since (B) is normally manufactured by the manufacturing method including the addition reaction process of the alkylene oxide to a hydroxyl group, the addition mole number in these addition products has distribution. Therefore, k in General formula (3) is represented by an average value, is a number of 70-700, and preferably 200-500 from the viewpoint of the sustainability of the slow solubility effect.

The number average molecular weight of (B) is 3,000 to 30,000, preferably 10,000 to 20,000. If it is less than 3,000, long-term sustainability is insufficient, and if it exceeds 30,000, the shape retention stability is lowered. The number average molecular weight (hereinafter abbreviated as Mn) of (B) is measured by polyethylene permeation chromatography (GPC) using polyethylene glycol as a standard substance.
The melting point of (B) is preferably 35 to 80 ° C. When the melting point is within this range, the effect of formability is more easily exhibited.

Specific examples of (B) include the following.
(B1): Polyethylene glycol (Mn 10,000)
(B2): Polyethylene glycol (Mn 3,000) ethylene oxide block adduct (Mn 25,000)
(B3): Ethylene oxide adduct of hexyl alcohol (Mn 6,000)
(B4): Ethylene oxide adduct of oleyl alcohol (Mn 20,000),
Etc.

(B) can be produced by the usual addition reaction of alkylene oxide. When two or more types of alkylene oxide are used in combination, block addition (chip type, balance type, active secondary type, etc.), random addition, or a mixed system of both may be used.

  The content of (A) and (B) in the solubilizing agent is generally 70% by weight or more (70 to 100% by weight) based on the weight of the solubilizing agent. From the viewpoint of shape retention and sustainability of the slow solubility effect, the content is preferably 75 to 100%. Further, the weight ratio (A) / (B) of (A) and (B) is usually 0.1 to 0.5, and 0.2 to 0.4 from the viewpoint of moldability and shape retention. preferable.

  The slow solubilizer of the present invention may further contain a surfactant (C) of 30% or less, preferably 15% or less, particularly preferably 10% or less, if necessary, based on the weight of the slow solubilizer. By containing the surfactant (C), the effects of miscibility and moldability are more easily exhibited.

  Examples of the surfactant (C) include nonionic surfactants (excluding (A) and (B)), anionic surfactants, cationic surfactants, and amphoteric surfactants.

  Nonionic surfactants include, for example, alkylene oxide adducts such as alkylphenols, higher fatty acids or higher alkylamines; trihydric or higher polyhydric alcohols (trivalent to 7-valent such as propylene glycol, glycerin, pentaerythritol, sorbitan, or An alkylene oxide adduct of a polyhydric alcohol (higher polyhydric alcohol); an alkylene oxide adduct of a polyhydric (divalent to octahydric or higher) alcohol alkyl ether, and these compounds and polyalkylene glycol are reacted with an organic polyisocyanate. The urethane compound (modified polyether) which does not have an isocyanate group at the terminal obtained is mentioned.

  Examples of the anionic surfactant include carboxylic acid (saturated or unsaturated fatty acid having 8 to 22 carbon atoms) salt (salt such as sodium, potassium, ammonium, alkanolamine), aliphatic alcohol having 8 to 16 carbon atoms, or the like. Carboxymethylated salt of ethylene oxide adduct, higher alcohol sulfate, higher alkyl ether sulfate, sulfated oil, sulfated fatty acid ester, sulfated olefin, alkylbenzenesulfonate, alkylnaphthalenesulfonate, sulfosuccinic acid Examples include diester type, α-olefin (C12-18) sulfonate, Igepon T type, and higher alcohol or alkylphenol ethylene oxide adduct phosphate ester salt.

Examples of the cationic surfactant include a quaternary ammonium salt type and an amine salt type.
Examples of the amphoteric surfactant include amino acid type amphoteric surfactants, betaine type amphoteric surfactants, and surfactants described in JP-B-57-39678.

The slow solubilizing agent of the present invention is added with optional components such as (A), (B) and if necessary (C) in a heatable mixing tank, heated, melted and mixed, taken out, and left at room temperature. Then, it can be solidified and, if necessary, can be produced by pulverizing to an appropriate size (block or powder).
The heating temperature is usually 70 to 100 ° C. The slow solubilizer of the present invention is usually solid at 35 ° C. or lower, and its melting point is usually 40 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 to 80 ° C.

  The gradually soluble preparation of the present invention is a gradually soluble preparation containing the above-mentioned slowly dissolving agent and a fragrance and / or a colorant (D) and molded.

Examples of the colorant include 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 coloring agent used is preferably 15% or less (15 parts by weight or less out of 100 parts by weight of the slowly soluble preparation), more preferably 10% or less based on the weight of the slowly dissolving preparation. Examples of the fragrances include plant essential oils such as lavender, lemon oil, rose oil and green oil; animal fragrances such as musk and civet; synthetic fragrances such as aldehydes, esters and ketones, and blended fragrances thereof. . The amount of the fragrance used is preferably 15% or less (15 parts by weight or less out of 100 parts by weight of the slowly soluble preparation), more preferably 10% or less based on the weight of the slowly dissolving preparation.

  The slow-dissolving preparation is optionally added with at least one selected from the group consisting of deodorants, bleaches, extenders, builders, disinfectants, fungicides, insecticides, chemical pesticides, chemical fertilizers and UV absorbers. An agent (E) may be contained. Examples of the deodorant include aldehyde compounds such as glyoxal; metal compounds such as zinc sulfate and zinc lactate; and known deodorants such as plant extract oil. The amount of the deodorant used is preferably 25% or less, more preferably 15% or less, based on the weight of the slowly soluble preparation. Examples of the bleaching agent include oxygen bleaching agents such as sodium perborate and sodium persulfate; and chlorine bleaching agents such as chlorinated isocyanuric acid. The amount of bleach used is preferably 25% or less, more preferably 15% or less, based on the weight of the slowly soluble preparation. Examples of the bulking agent include inorganic salts such as sodium sulfate, anhydrous sodium sulfate, potassium sulfate, sodium carbonate, calcium carbonate, calcium phosphate, boric acid, talc, colloidal silica; and organic compounds such as urea. The use amount of the extender is preferably 65% or less, more preferably 50% or less, based on the weight of the slowly soluble preparation. Others, builders (sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, etc.), disinfectants (chitosan, hinokitiol, tea catechin, etc.), bactericides (chlorine, iodine, quaternary ammonium salt, imidazole, Guanidines), insecticides (pipetrin, aldrin, etc.), chemical pesticides (3-allyloxy-1,2-benzisothiazole, etc.), chemical fertilizers (calcium phosphate, urea, etc.), UV absorbers (salicylic acid, benzophenone, The amount of each of these additives used is preferably 30% or less, more preferably 15% or less, based on the weight of the slowly soluble preparation.

  The total amount of the additive (E) is preferably 65% or less, more preferably 50% or less, based on the weight of the slowly soluble preparation.

  In the slow-dissolving preparation of the present invention, the temperature of the slow-dissolving agent is adjusted to a temperature equal to or higher than its melting point, for example, 70 to 100 ° C., and then necessary components selected from (D) and (E) are added. Further, after mixing, it can be produced by molding into a desired shape by a liquid casting method, an extrusion molding method, a compression molding method or a tableting molding method. In addition, the method of molding after the components (A), (B) and (C), and (D) and / or (E), which are components of the slow-dissolving agent, are melted and mixed together as necessary. The slowly soluble preparation of the invention can be produced.

Examples of the mold of the liquid casting method include a plastic cup. In the case of the extrusion molding method, a rod-shaped preparation is obtained by molding at 20 to 60 ° C. with an extrusion molding machine, and then is made into a predetermined size with a cutter. The desired solid preparation can be obtained by cutting. In the case of the compression molding method or tableting method, the mixed powder is compression molded at room temperature (pressure: 0.1 to 1 ton / cm ² ) using a rotary type tableting molding machine and then demolded. Thus, a disc-shaped solid preparation can be obtained.

  The gradually soluble preparation obtained as described above is usually solid at 35 ° C. or lower, and its melting point is usually 40 ° C. or higher, preferably 40 to 120 ° C., more preferably 50 to 80 ° C.

  As described above, in the present invention, various known molding methods such as a liquid casting method, an extrusion molding method, a compression molding method (tablet molding method) can be applied, so a solid aroma cleaner for flush toilets, a kitchen sink Sustained-release preparations (solid) such as anti-swelling agents for drains, sustained-release fungicides for pools, sustained-release agrochemicals and sustained-release fertilizers can be easily produced.

<Example>
The following examples further illustrate the invention, but the invention is not limited thereto. Parts and% mean parts by weight and% by weight unless otherwise specified. First, the composition of the raw materials used in the examples is shown below.
(A1): Lauric acid ester of 1,2-propylene oxide 2.5 mol adduct of sorbitol [average of 1.8 Z is lauroyloxy group and average of 4.2 is hydrogen atom, hydroxyl group Value = 358 mgKOH / g]
(A2): Myristic acid ester of sorbitan ethylene oxide 2.5 mol adduct [
An average of 2.6 of 4 Zs is a myristoyloxy group and an average of 1.4 is a hydrogen atom, hydroxyl value = 95 mgKOH / g]
(A3): Palmitic acid ester of an adduct of 0.5 mol of physitol ethylene oxide [average of 2.0 Z is palmitoyloxy group, average of 2.0 is hydrogen atom, hydroxyl value = 179 mgKOH / g]
(A4): Stearate ester of glycerin [average 1.3 of 3 Z is stearoyloxy group, average 1.7 is hydrogen atom, hydroxyl value = 216 mgKOH / g]
(A5): Compound obtained by condensing 2-molecule-stearamide of 2-aminoethyl-2-aminoethanol with urea [Q is a group represented by the general formula (2); The average of 2.0 is stearoylamino group and the average of 2.0 is hydrogen atom, hydroxyl value = 292 mgKOH / g]

B1: Polyethylene glycol (Mn 10,000, melting point 62 ° C.)
B2: Polyethylene glycol (Mn 3,000) ethylene oxide block adduct (Mn 25,000, melting point 57 ° C.)
B3: Ethylene oxide adduct of hexyl alcohol (Mn 6,000, melting point 64 ° C.)
B4: Ethylene oxide adduct of oleyl alcohol (Mn 20,000, melting point 59 ° C.)
B5: Polyethylene glycol (Mn 2,500, melting point 51 ° C.)

C1: Modified polyether compound obtained from the reaction of polyalkylene glycol and organic polyisocyanate (“New Pole T-240U” manufactured by Sanyo Chemical Co., Ltd.)
D1: Blue No. 1 aluminum lake (colorant)
D2: Rose oil (fragrance)

Examples 1-12 and Comparative Examples 1-6
Among the blending components listed in Tables 1 and 2, (A), (B) and (C) were heated to 120 ° C. and uniformly melted, then cooled and adjusted to about 80 ° C., and (D ) And stirring and mixing, 20 g of the mixed slurry is poured into a 30 ml polypropylene cup, left to cool at room temperature for 24 hours, cooled, and demolded to form a columnar slow-dissolving preparation (diameter 35 mm, height 20 mm) Got.

  Tables 3 and 4 show the performance evaluation results of the miscibility, moldability, storage stability, sustainability, temperature dependency and shape retention of the slowly soluble preparation. The test method is as follows.

(1) Miscibility: Miscibility (A) and (B) with fragrances and colorants, and if necessary, miscibility when (C) and / or (D) is stirred and mixed at 80 ° C visually. It was evaluated and judged according to the following criteria. However, since Example 11 did not add any of (C) and (D), miscibility was not evaluated.
◎: Good compatibility, easy to mix evenly ○: Good compatibility, mix evenly △: Hard to mix ×: Poor compatibility, difficult to mix

(2) Moldability: Moldability at the time of slowly dissolving preparation molding 30.0 ml of polypropylene cup made of polypropylene was weighed 20.0 g each of the blended solution adjusted to 80 ° C. and allowed to stand for 24 hours to cool to room temperature. Thereafter, the molding container was turned upside down, and free fall was repeated about several tens of times vertically from a height of 5 cm to remove the mold from the mold. The weight of the preparation obtained by demolding was weighed. Since the moldability is better as the amount lost due to vibration during demolding is smaller, it was evaluated according to the following criteria.
A: The weight of the demolded preparation is 19.9 g or more. ○: The weight of the demolded preparation is 19.8 g or more and less than 19.9 g. Δ: The weight of the demolded preparation is 19.6 g or more and less than 19.8 g. Molded formulation weighs less than 19.6g

(3) Storage stability: Storage stability over time of the slowly soluble preparation The appearance after storage of the slowly soluble preparation at 45 ° C. for 3 months was visually evaluated and judged according to the following criteria.
◎: No change in mold ○: No change in mold, but tend to soften △: Some shape loss ×: Dissolution

(4) Persistence and temperature dependence: Sustained effect of sustained-release preparation and temperature dependence of water used The slow-release preparation was placed in a 1 L plastic container (diameter 100 mm), and the temperature was adjusted to 30 ° C and 15 ° C. Water (100 ml) was added, the preparation was completely immersed in water, and left in a temperature-controlled room. The water was changed every day, and the weight of the preparation was measured at the time of replacement, and the number of days that would be 50% by weight compared to before evaluation was obtained. The longer the value, the better the sustainability of the effect, and the smaller the difference between the values of 30 ° C. and 15 ° C., the less the temperature dependency, the better.

(5) Shape retention: shape retention property against swelling of slow-dissolving preparations The slow-dissolving preparation is placed in a 1 L plastic container (diameter 100 mm), water (50 ml) adjusted to 25 ° C is added thereto, and the preparation is submerged in water. And was immersed in a temperature-controlled room at 25 ° C. About swelling property after 24 hours, swelling rate (%) was calculated | required from {(diameter of the formulation upper part) / (diameter of the formulation after shaping | molding)} * 100. Smaller values mean better shape retention.

  As is apparent from Table 3, the slow-dissolving agent of the present invention, and the slow-dissolving preparations (Examples 1 to 12) containing the slow-dissolving agent and various additives are miscible with perfumes and coloring agents, Moldability during formulation molding, quality stability during long-term storage of the formulation, low dependence on slow dissolution rate depending on the temperature of water used, shape retention stability during use, stability of slow dissolution rate, and slow dissolution Has long-lasting effects and satisfies all of these performances. On the other hand, as is clear from Table 4, none of Comparative Examples 1 to 6 satisfies all the performance items.

  The slow-dissolving agent of the present invention and the slow-dissolving preparation containing the slow-dissolving agent and various additives are miscible with fragrances and coloring agents, formability during preparation molding, and stable quality during long-term storage of the preparation. Properties, the dependence of the slow solubilization rate on the temperature of the water used is small, the shape retention stability during use, the stability of the slow solubilization rate, and the long-term sustainability of the slow solubilization effect. Therefore, it can be used for slow-dissolving preparations such as solid fragrance cleaners for flush toilets and kitchen sink drainage slime prevention agents.

Claims (4)

A slow solubilizer comprising a compound (A) represented by the general formula (1) and a compound (B) having a number average molecular weight of 3,000 to 30,000 represented by the general formula (3). The total weight of (A) and (B) based on the weight of the agent is 70% by weight or more, and the weight ratio (A) / (B) is 0.1 to 0.5. .
[Wherein, Q is a residue of a trivalent to hexavalent aliphatic polyhydric alcohol or a tetravalent group represented by the general formula (2); Z is a hydroxyl group, an acyloxy group having 12 to 22 carbon atoms, or 12 to 12 carbon atoms; 22 is an acylamino group, wherein at least one of n Z is a hydroxyl group; OA ¹ is an oxyalkylene group having 2 to 4 carbon atoms; m is a number from 0 to 2, and n is an integer from 3 to 6. M × n representing the average number of moles of (OA ¹ ) per molecule is a number from 0 to 6. ]
[Wherein, R ¹ represents an alkylene group having 2 to 6 carbon atoms. ]
[Wherein, R ² is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, or an alkenyl group having 2 to 25 carbon atoms; OA ² is an oxyalkylene group having 2 to 4 carbon atoms; k is a number from 70 to 700. . ] The hydroxyl value of the compound (A) is 90 to 400 mgKOH / g, and 90% by weight or more of (OA ² ) k in the general formula (3) is composed of units of (CH ₂ CH ₂ O). 2. The slow solubilizer according to claim 1.   The slow solubilizer according to claim 1 or 2, further comprising 30% by weight or less of the surfactant (C) based on the weight of the slow solubilizer.   A slow-dissolving preparation comprising the slow-dissolving agent according to any one of claims 1 to 3 and a fragrance and / or a coloring agent, which is molded.