JP2003292997A - Solid cleanser base - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid cleanser base which gives solid aromatic cleansers having good sustained release properties and shape retaining properties. <P>SOLUTION: This solid cleanser base contains an alkoxylate type nonionic surfactant having an end-capped specific structure. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid detergent base and a solid fragrance detergent using the same. More specifically, the solid fragrance detergent base prepared using the base of the present invention maintains its characteristic slow-dissolving property even when it is exposed to water for a long time, and swells or loses the shape of the detergent when dissolved. The present invention relates to a solid detergent base and a solid fragrance detergent using the solid detergent base, which achieves effective supply of active ingredients.

[0002]

2. Description of the Related Art Solid cleaning agents are mainly used for toilets, and can be installed in a men's toilet bowl, in the hand-washing part of a water tank of a flush toilet (on-tank type), or put in the interior. By adding (in-tank type), the dye, fragrance, and cleaning agent are appropriately supplied into the wash water to suppress the unpleasant odor generated when using the toilet and to give a clean feeling, and to attach dirt to the toilet bowl. It is a product that has the effect of suppressing cleaning and facilitating cleaning.

Conventionally, solid detergent bases used for solid detergents are polyoxyethylene alkyl (or alkylaryl) ethers described in JP-A-63-147000 and JP-A-59-24797. Polyoxyethylene fatty acid esters, polyoxyethylene-polyoxypropylene copolymers described in JP-A-51-39705 and JP-A-55-131098, and derivatives thereof are known. A common property of these bases is that they are solid at room temperature and slowly dissolve in water or running water to volatilize the active ingredient.

However, in reality, the conventional bases do not have a sufficient balance between the durability and the solubility, and if the composition is highly hydrophilic so as to be easily dissolved uniformly in water, the durability is insufficient. If the composition is highly hydrophobic in order to increase swelling or swelling, the solubility in water will decrease and the water will become cloudy.In severe cases, the dissolved base material will re-aggregate. As a result, they are suspended in the cleaning liquid as particulate matter. In order to overcome these problems, various dissolution modifiers and inorganic components must be added, and there is a problem that the design of the aroma cleaner is limited.

[0005]

The recent fragrance cleaners are:
The on-tank type has been favored over the in-tank type, and the requirements for solubility and shape retention have become higher than ever before.

The object of the present invention is to provide a solid detergent base which has good solubility in water but is durable and does not swell or lose its shape when dissolved, and a solid aroma detergent using the same. To do.

[0007]

As a result of various studies to solve the above problems, a nonionic surfactant having a three-block structure of hydrophilic part-hydrophobic part-hydrophilic part in the molecule was found. It has been found that the solid detergent base has a good balance of solubility and sustainability, that is, good sustained release property, does not cause swelling or deformation during dissolution, that is, has good shape retention property, and completed the present invention. .

The present invention relates to a solid detergent base containing a nonionic surfactant represented by the general formula (1) [hereinafter referred to as nonionic surfactant (1)].

Y ₁ O- (A ₁ O) _n -XO- (A ₂ O) _n'- Y ₂ (1) (In the formula, Y ₁ is an alkyl group or an alkenyl group having 2 to 24 carbon atoms, or An alkylphenyl group having a number of 7 to 18, Y ₂ represents a hydrogen atom, or an acyl group or an alkyl group having a carbon number of _{2 to} 24. A ₁ O and A ₂ O each independently have a carbon number of 2 to 2; It is an alkylene oxide having 4 carbon atoms, and the content of the alkylene oxide having 3 and 4 carbon atoms is 5% by weight or less in each of (A ₁ O) _{n and} (A ₂ O) _{n ′} . Are each independently a number of 20 to 350. X is a polymer chain containing a hydrophobic monomer unit and having a molecular weight of 300 or more.).

The present invention also provides a nonionic surfactant represented by the general formula (2) [hereinafter referred to as nonionic surfactant (2)
]] Is included in the solid detergent base. _{[Y 3 -O- (A 1 O} ) n - (B 1 O) m] l -Z - [(B 2 O) m '- (A 2 O) n' -Y 4] l '(2) ( In the formula, Y ₃ and Y ₄ are each independently a hydrogen atom or an acyl group having 2 to 24 carbon atoms, and 1 Y ₃ and 1 ′
The Y _4's may be the same or different, but Y ₃ and Y ₄
Not all of which become hydrogen atoms at the same time. A ₁ O and A ₂ O are each independently an alkylene oxide having 2 to 4 carbon atoms, and the content of the alkylene oxide having 3 or 4 carbon atoms is (A ₁ O) _n or (A ₂ O). It is 5% by weight or less in each of _{n '} . Also, n and n ′ are
Each is independently a number from 20 to 350. B ₁ O and B ₂ O are each independently an alkylene oxide having 2 or more carbon atoms, and contain 50% by weight or more of an alkylene oxide having 3 or more carbon atoms. m and m'are
Each is independently a number from 2 to 300. Z is a group derived from a compound having three or more active hydrogen groups. l and l ′ are each independently a number of 1 or more, and l + l ′ is equal to the total number of active hydrogen groups of the compound from which Z is derived. ).

The present invention also relates to a solid detergent base containing a water-soluble solid urethane compound obtained by reacting a compound represented by the following general formula (3) with an organic isocyanate compound. _{[Y 5 -O- (A 1 O} ) n - (B 1 O) m] l -Z - [(B 2 O) m '- (A 2 O) n' -Y 6] l '(3) ( In the formula, Y ₅ and Y ₆ are each independently a hydrogen atom or an acyl group having 2 to 24 carbon atoms, and 1 Y ₅ and 1 ′
The Y _6's may be the same or different, but all Y _5's
And at least one of Y ₆ is a hydrogen atom. A ₁ O and A ₂ O are each independently an alkylene oxide having 2 to 4 carbon atoms, and the content of the alkylene oxide having 3 or 4 carbon atoms is (A ₁ O) _n or (A ₂ O). It is 5% by weight or less in each of _{n '} . Also, n and n '
Are each independently a number from 20 to 350. B ₁
O and B ₂ O are each independently an alkylene oxide having 2 or more carbon atoms and contain 50% by weight or more of an alkylene oxide having 3 or more carbon atoms. m and m '
Are each independently a number from 2 to 300. Z is 3
A group derived from a compound having one or more active hydrogen groups. l and l ′ are each independently a number of 1 or more, and l + l ′ is equal to the total number of active hydrogen groups of the compound from which Z is derived. ).

The present invention also relates to a solid fragrance detergent containing the above-mentioned solid detergent base of the present invention.

The molecular weight described in this specification means the number average molecular weight, and the value can be calculated by determining the polymerization number of alkylene oxide by a general analysis method such as H ¹ -NMR. it can.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION <Nonionic Surfactant (1)> The nonionic surfactant (1) is obtained by reacting a monomer having a compound having an alkyl group, an alkenyl group or an alkylphenol group with a hydrophilic part [(A ₁ O) _n ] -hydrophobic part [XO]-
A polymer having a polymer (hereinafter referred to as a "3-block structure polymer") formed in a block in the order of hydrophilic part [(A ₂ O) _{n '} ], and further esterified or etherified if necessary. It is an end cap type.

The nonionic surfactant (1) is specifically a hydrophilic alkylene oxide (hereinafter referred to as AO), such as ethylene oxide (for example, in the hydrophobic group portion having an active hydrogen group, that is, alcohol or alkylphenol). Hereafter, EO) and the like are polymerized, and then a hydrophobic AO such as propylene oxide (hereinafter, P) is polymerized.
O), butylene oxide (hereinafter referred to as BO), tetrahydrofuran, and the like, and further hydrophilic AO, such as EO, is obtained by further polymerizing the terminal having an active hydrogen group. Obtained by esterification or etherification.

The hydrophobic portion X of the three-block structure polymer is a polymer chain containing a hydrophobic monomer unit and having a molecular weight of 300 or more, and X is an alkylene oxide having 3 or more carbon atoms.
It is preferably a polymer chain of AO containing at least 80% by weight, more preferably at least 90% by weight, particularly preferably at least 90% by weight, and having 3 carbon atoms.
And / or a polymer chain of only 4 AO is preferred. The hydrophobic portion is 50 as long as the hydrophobicity is not impaired.
It may contain less than wt% EO units. The polymerization number of hydrophobic monomers such as alkylene oxide is H ¹ -NMR.
Can be found at.

The hydrophilic part of the three-block structure polymer is mainly a polymerized product of hydrophilic EO, but contains 5% by weight or less of PO units, BO units and the like within a range in which the properties of the hydrophilic part are not changed. But good. N and n ′ in the general formula (1) are each 20 to 350, more preferably 50 to 350, and most preferably 70 to 350.

As described above, by adjusting the ratio of the hydrophilic and hydrophobic constituent units in the hydrophilic part and the hydrophobic part in the three-block structure polymer, it is possible to improve the sustained solubility and shape retention of the solid detergent base. The balance can be adjusted. The triblock structure polymer is not limited to one kind, and good performance can be obtained even if two or more kinds having different structural units of the hydrophilic part and the hydrophobic part are mixed and used.

The molecular weight of the three-block structure polymer is 100.
It is preferably 0 or more, more preferably 3800 or more, and most preferably 5000 or more.

In the general formula (1), the alkyl or alkenyl group having 2 to 24 carbon atoms represented by Y ₁ may be linear or branched, and is derived from any of primary, secondary and tertiary alcohols. It can be one. Regarding the alkylphenol group having 7 to 18 carbon atoms, the degree of branching of the alkyl group portion also differs, but it may be linear or multibranched. When the acyl group, alkyl group, or alkenyl group represented by Y ₂ has 16 to 24 carbon atoms, unreacted raw material remains in the solid detergent base depending on the production conditions, and it precipitates as an insoluble matter. Since it may reduce performance,
It is preferable to use a raw material having a branched chain or an unsaturated bond.

The number average molecular weight of the nonionic surfactant (1) is preferably 2000 or more, more preferably 4000 or more, and particularly preferably 6000 or more.

The nonionic surfactant (1) has a melting point of 25.
It is preferably at least ° C, more preferably at least 40 ° C.

Next, a method for producing the nonionic surfactant (1) will be described. The nonionic surfactant (1) is a polymer having a three-block structure of hydrophilic part-hydrophobic part-hydrophilic part, which is obtained by adding AO to alcohol or alkylphenol in the presence of a suitable catalyst, if necessary. It can be obtained by reacting with an appropriate fatty acid or alcohol after it is obtained.

More specifically, both acid and base catalysts can be used for the synthesis of the polymer portion having a triblock structure, and those synthesized using an acid catalyst such as boron trifluoride diethyl ether complex are Polymers with a narrower polymerization distribution than those with base catalysts are obtained. In addition, Mg-Z
nO, Mg-SnO, Mg- TiO 2, Mg-SbO,
A polymer having a narrower polymerization distribution can also be obtained by using a catalyst such as MgO which gives a narrow AO addition distribution (narrow range).
Even if these polymers having different polymerization distributions are used, if the end-cap type nonionic surfactant of the general formula (1) has a three-block structure of hydrophilic part-hydrophobic part-hydrophilic part inside, it is equivalent. Exhibits excellent properties.

The fatty acids used in the end cap reaction are
Those having 2 to 24 carbon atoms, preferably 8 to 2 carbon atoms
4 of them. The fatty acid may be linear or branched and may have an unsaturated bond. When the number of carbon atoms is 16 or more, a small amount of unreacted fatty acid may remain depending on the reaction conditions and it may precipitate as an insoluble matter. Therefore, it is preferable to use a liquid fatty acid such as one having a branched chain or an unsaturated bond. preferable. In a general esterification reaction, the composition is determined by the reaction conditions, so the reaction product is several%
It is composed of a mixture of 10% or more of unreacted raw material and ester, and depending on the reaction conditions, it may contain a small amount of catalyst, neutralizing agent and the like. If the amount of unreacted raw material is small, even if it is contained in the solid detergent base or the solid detergent, the performance is not significantly affected.

In the etherification reaction for the end cap, it can be synthesized by, for example, the method described in JP-A-11-116522 or the Williamson method. The alcohol used for the etherification reaction has 2 to 24 carbon atoms, preferably 8 to 24 carbon atoms. The alcohol may be linear or branched and may have unsaturation. When the carbon number is long, a small amount of unreacted alcohol may remain depending on the reaction conditions, and it may be precipitated as an insoluble matter. Therefore, it is preferable to use one having a branched chain or an unsaturated bond. Even in the etherification reaction, a substance containing a small amount of unreacted raw material is produced depending on the conditions, but if the amount of unreacted raw material is small, even if it is contained in the solid detergent base or the solid detergent, Does not significantly affect performance.

Further, as a catalyst used in carrying out the etherification reaction or the esterification reaction, basic hydroxides such as potassium hydroxide, sodium hydroxide and barium hydroxide, tin oxide, tin hydroxide and the like are used. Metals forming metal soap, metal oxides and organic metal salts such as titanium isopropoxide, and acetic acid as a neutralizing agent, fatty acids such as acetic acid and propionic acid, lactic acid, glycolic acid, malic acid, citric acid, and glyceric acid. , Oxycarboxylic acids such as glyoxylic acid, and mineral acids such as phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid. Salts produced from these catalysts and neutralizing agents may be contained in the base material, but if the content is several% or less, the solubility,
It has almost no effect on the balance of durability and shape retention, the odor of products, and compatibility with fragrances, and does not affect essential performance.

The hydrophilic base portion of the polymer having a triblock structure of hydrophilic portion-hydrophobic portion-hydrophilic portion is mainly a polymer of hydrophilic EO, but is 5% by weight within the range where the hydrophilic property is not changed. The following hydrophobic PO and BO may be added for polymerization. By adding these, the physical properties of the intended solid detergent base can be finely adjusted. Similarly, with respect to the hydrophobic group portion, EO in an amount of less than 50% by weight can be added and polymerized within a range not impairing the hydrophobicity.

<Nonionic Surfactant (2)> The nonionic surfactant (2) is specifically a compound having three or more active hydrogen groups (compound to be Z), for example, glycerin,
To a polyhydric alcohol such as trimethylolpropane, pentaerythritol or sorbitol, or a polyamine such as ethylenediamine, in the presence of a suitable catalyst, a hydrophobic group moiety, that is, hydrophobic AO such as PO, BO or tetrahydrofuran is added, and then hydrophilic. It can be obtained by reacting a fatty acid with an intermediate polymer obtained by polymerizing AO, such as EO.

This intermediate polymer is used in the total amount of AO, that is, n × l A ₁ O, m × l B ₁ O and n ′ ×.
EO in the total of l ′ A ₂ O and m ′ × l ′ B ₂ O
Is less than 50% by weight. The ratio of the hydrophilic part to the hydrophobic part, that is, n × l A ₁ O and m ×
In the total of l B ₁ O, n ′ × l ′ A ₂ O, and m ′ × l ′ B ₂ O, m × l B ₁ O and m ′ × l ′ B
The total proportion of ₂ O is preferably 55% by weight or more, more preferably 70% by weight or more.

The molecular weight of this intermediate polymer is 100.
It is preferably 0 or more, more preferably 3800 or more, and most preferably 5000 or more.

The nonionic surfactant (2) is obtained by reacting this intermediate polymer with an acylating raw material such as a suitable fatty acid in the presence or absence of a catalyst. The fatty acid used in this reaction has 2 to 24 carbon atoms, preferably 8 to 24 carbon atoms. The fatty acid may be linear or branched and may have an unsaturated bond. When the carbon number is long, if a large amount of unreacted fatty acid is present, it may be precipitated as an insoluble substance and the performance may be deteriorated. Therefore, it is preferable to use a fatty acid having a branched chain or an unsaturated bond.

The solid detergent base in the present invention is used mainly as a solid product. Therefore, the melting point of the nonionic surfactant (2) is preferably 25 ° C or higher, and more preferably 40 ° C or higher.

The method for producing the nonionic surfactant (2) will be described in more detail. The nonionic surfactant (2) is
By reacting an intermediate polymer which is a triblock structure polymer with a fatty acid having 2 to 24 carbon atoms, preferably a fatty acid having 8 to 24 carbon atoms in the presence of a catalyst such as sodium hydroxide, tin oxide or titanium tetraisopropoxide. Obtained by esterification.

When synthesizing the nonionic surfactant (2),
By adjusting the ratio of the intermediate polymer and the fatty acid according to the required physical properties, compositions having different degrees of esterification can be obtained, and solid detergent bases suitable for various purposes can be obtained. In a general esterification reaction, the composition is determined by the reaction conditions, and therefore the reaction product is several% to several 1 in consideration of equilibrium.
It becomes a mixture of 0% of unreacted raw material and monoester / diester / triester, and depending on the conditions, a small amount of a catalyst, a neutralizing agent and the like may be contained. The inclusion of unreacted raw materials, catalysts, neutralizing agents, and salts that are produced has almost no effect on the balance of solubility, sustainability, shape retention, odor of products, and compatibility with fragrances, and contributes to essential performance. Does not affect.

The intermediate polymer used for producing the nonionic surfactant (2) has three blocks of hydrophilic group-hydrophobic group-hydrophilic group from the end having any active hydrogen group to the end having another active hydrogen group. It has the following structure. The hydrophilic base portion is mainly a polymerized product of hydrophilic EO, but may be polymerized by adding 5% by weight or less of hydrophobic PO and butylene oxide within a range not changing the hydrophilic property. By adding these, the physical properties of the intended solid detergent base can be finely adjusted. Similarly, with respect to the hydrophobic group portion, EO in an amount of less than 50% by weight can be added and polymerized within a range not impairing the hydrophobicity.

<Water-Soluble Solid Urethane Compound> The water-soluble solid urethane compound of the present invention is obtained by reacting the compound represented by the general formula (3) with an organic isocyanate compound. As the compound of the general formula (3), preferred compounds represented by the nonionic surfactant (2) can be used, except that at least one of Y ₃ and Y ₄ is a hydrogen atom.

The water-soluble solid urethane compound of the present invention is
Specifically, the compound of the general formula (3) obtained according to the method for producing the nonionic surfactant (2) and an organic isocyanate compound, for example, 4,4′-diphenylmenthocyanate, 2,4- / 2,6-tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc., the ratio of the number of hydroxyl groups of the compound of the general formula (3) and the number of isocyanate groups of the organic isocyanate compound is preferably 0.2 to 1.0, More preferably, it is used so as to be 0.5 to 0.8, and can be synthesized by reacting it according to a usual method for producing a urethane compound.

<Solid fragrance cleaner> In the solid fragrance cleaner using the solid detergent base of the present invention, various fragrances, food blue No. 1, food blue No. 2, food yellow No. 4 are used as necessary. ,
Dyes such as edible yellow No. 5, carboxymethyl cellulose, carboxymethyl cellulose alkali metal salts, thickening substances such as hydroxypropyl cellulose, dissolution rate regulators for hydrophobic substances such as alcohols, fatty acids and silicones, alkylbenzene sulfonic acid, alcohol ethoxylates, fluorine Surfactants such as surfactants, chelating agents such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, specific gravity adjusting agents such as inorganic salts such as sodium sulfate, sodium chloride and sodium silicate, triclosan, sodium hypochlorite, benzalco chloride A sterilizing agent such as nickel and a pH adjusting agent such as sodium hydrogen carbonate, citric acid and oxalic acid are mixed.

The solid detergent base in the present invention is mainly intended to be compounded and used as a solid product.
The melting point is preferably 25 ° C or higher, more preferably 40 ° C or higher.

The ratio of the solid detergent base of the present invention to the solid aroma detergent is preferably 20 to 90% by weight, and 50
-80% by weight is more preferred. When the content of the base is 20% by weight or more, the sustained-dissolving property and the shape-retaining property of the base are sufficiently exhibited, and when the content is 90% by weight or less, the fragrance and the characteristic of the aroma cleaner The color effect is exhibited well.

[0042]

Examples Production Example 1 300 g of Kao Corporation's Calcol 6850 (cetyl / stearyl mixed alcohol) was hydrated in a 10-liter stirring rotary autoclave equipped with two measuring tanks for EO and PO. 11.6 potassium
g, charged with nitrogen, heated to 110 ° C., and
Dehydration was performed at 3 kPa for 1 hour. Next, the temperature was raised to 150 ° C., and EO was introduced into the 4538 g autoclave at a pressure of 343 kPa and reacted until the pressure decreased and became constant. Then, after cooling to 120 ° C. and extracting 2400 g of a part of the product for volume adjustment, 442 g of PO442 was 343
It was introduced into the autoclave at a pressure of kPa and reacted until the pressure dropped and became constant. Again raise the temperature to 150 ° C,
2283 g of EO was introduced into the autoclave and reacted until the pressure dropped and became constant. After completion of the reaction, the temperature was lowered and the synthesized sample was taken out to obtain about 7.5 kg of polyoxyalkylene alkyl ether as an intermediate. The molecular weight of the intermediate was 7,500.

500 g of this intermediate and 30.2 g of Lunac O-LL (oleic acid) manufactured by Kao Corporation as a fatty acid were placed in a 1 L flask. 1 g of diphtyl tin oxide as a catalyst, 0.4 g of butylhydroxytoluene as an antioxidant, and 0.07 g of defoaming silicone TSA730 manufactured by GE Toshiba Silicone Co., Ltd. as a defoaming agent,
The reaction was carried out at 220 ° C. for 8 hours in a nitrogen stream to obtain the endcap type nonionic surfactant of Example 1. The nonionic surfactant corresponded to the general formula (1) and had a molecular weight of 8000.

Production Example 2 500 g of the intermediate of Example 1 and 20 g of 5% Pd-C (pH 6.6) as a catalyst were charged in a 1 L flask equipped with a hydrogen gas introducing tube, a rotary stirring device and a dehydration / reflux device, and then charged. Under atmospheric pressure, 25 g of dodecyl aldehyde was added dropwise at a rate of 2 g / hr while continuously flowing hydrogen at a rate of 0.3 L / min, and a stirring reaction was performed at 150 ° C. for 14 hours. After completion of the reaction, the catalyst was removed by filtration, and excess dodecyl aldehyde was distilled off under reduced pressure to obtain an end-cap type nonionic surfactant of Example 2. The nonionic surfactant corresponded to the general formula (1) and had a molecular weight of 8000.

Production Example 3 500 g of Tetronic 908 Pastille (polyoxyalkylene-ethylenediamine complex) manufactured by BASF Corporation
As a fatty acid, 63.6 g of Emazol 874 (isostearic acid) manufactured by Cognis Japan Ltd. was charged into a 1 L flask. Diftyltin oxide 1 g as a catalyst, butyl hydroxytoluene 0.4 g as an antioxidant, 0.07 g of a defoaming silicone TSA730 manufactured by GE Toshiba Silicone Co., Ltd. as a defoaming agent were added, and the mixture was reacted at 220 ° C. for 8 hours in a nitrogen stream to carry out. An ester type nonionic surfactant corresponding to the general formula (2) of Example 3 was obtained.

Production Example 4 500 g of Tetronic 908 Pastille (polyoxyalkylene-ethylenediamine complex) manufactured by BASF Corporation
Was charged into a 1 L flask. Further, 6.3 g of 4,4′-diphenylmethane diisocyanate was added, and 170 ° C.
At room temperature for 5 hours to obtain a water-soluble solid urethane compound of Example 4.

Examples 1 to 4 and Comparative Examples 1 to 5 The nonionic surfactants of Examples 1 to 4 shown in Table 1 were obtained in Production Examples 1 to 4, respectively. Comparative Examples 1 and 2 are the nonionic surfactants shown in Table 1, and Comparative Examples 3 and 4 are
The three-block structure polymers of Examples 1 and 2 or Examples 3 and 4 (no end cap or urethanization), respectively.

[Evaluation of Slow Solubility and Shape Retention of Solid Detergent Base] The nonionic surfactants shown in Table 1 and the comparative nonionic surfactant were heated to 100 ° C. and dissolved. To confirm the solubility behavior, 0.5% by weight of Blue No. 1 was added thereto. These are stirred and mixed to form a uniform solution, which is then poured into a polypropylene cylindrical container having an inner diameter of 32 mm to be molded and solidified into a column having a height of 13.5 mm. The obtained tablet was placed in a beaker containing 500 g of water, the inner diameter and the thickness of the tablet after standing for 12 hours were measured, and the volume change rate was calculated. Based on this, sustained dissolution and shape retention were evaluated according to the following criteria.

(Sustainability) x: Remarkably larger volume than that before evaluation (15 by volume ratio)
Larger than 0%) Δ: Larger than the volume before evaluation (larger than 120% to 150% by volume ratio) ○: Almost equivalent to the volume before evaluation (3 by volume ratio)
0: Greater than 0% to 120%) △: Less than 30% compared to the volume before evaluation ×: Completely soluble (shape retention) ○: Original shape and similar shape △: Collapse of shape, Deformation x: Large deformation of shape, large deformation.

When the solid detergent base is applied to a solid detergent, it is generally molded and placed in a container for use. Therefore, at the stage where the molded solid detergent is dissolved, it is required for the product to maintain the original shape and gradually dissolve in a similar shape. Therefore, in the evaluation of sustained dissolution property, swelling significantly protrudes from the container (evaluation x), completely dissolves (evaluation x), or becomes larger than the volume before evaluation (evaluation △), or the degree of decrease is too large. Both (evaluation △) and those that dissolve in shape retention evaluation (evaluation ×, △) have insufficient sustained solubility (balance of solubility and sustainability) and cause swelling or deformation. Since the shape retention property is poor, it means that the performance required for the product is not satisfied.

[Evaluation of Dissolution Time of Solid Detergent] The nonionic surfactants shown in Table 1 and the comparative nonionic surfactant were heated to 80 ° C. and dissolved. 7.5 wt% of Blue No. 1 and 7.5 wt% of citrus fragrance were added thereto.
After stirring and mixing these to make a uniform solution, the inner diameter is 42 mm
Pour into aluminum cylindrical container of 8mm, height 8mm
It is molded and solidified into a disk shape. 28 on the obtained tablets
Time until the solid detergent dissolves and disappears by continuously supplying water at a flow rate of 1 L / min at ℃ (dissolution time) (minutes)
Was measured. Dissolution time by this test is 200-300
Minutes are practical and suitable.

[0052]

[Table 1]

As shown in Table 1, all the products of the present invention of Examples 1 to 4 had a slow solubility and had a good shape-retaining property. In Comparative Examples 1 and 2, the solubility is low and the swelling is remarkable. In Comparative Examples 3 and 4, the solubility was too high and completely dissolved, and the slow solubility was also poor.

[0054]

The solid detergent produced by using the solid detergent base of the present invention has a low swelling property, a good shape retention property and a good sustainability. Therefore, it becomes possible to use a container having a simplified structure and to contain a larger amount of fragrance and other components than the conventional one, which contributes to higher performance of the product.

Claims (9)

[Claims] 1. A solid detergent base containing a nonionic surfactant represented by the general formula (1). _{Y 1 O- (A 1 O)} n -XO- (A 2 O) n '-Y 2 (1) ( wherein, Y ₁ represents an alkyl group or an alkenyl group having 2 to 24 carbon atoms, or carbon atoms 7 18 is an alkylphenyl group, Y ₂ is a hydrogen atom, or an acyl group or an alkyl group having 1 to 24 carbon atoms, A ₁ O and A ₂ O are each independently an alkylene having 2 to 4 carbon atoms. The content of the alkylene oxide having 3 and 4 carbon atoms is 5% by weight or less in each of (A ₁ O) _{n and} (A ₂ O) _{n ′} , and n and n ′ are respectively Independently, it is a number of 20 to 350. X is a polymer chain containing a hydrophobic monomer unit and having a molecular weight of 300 or more.) 2. The solid detergent base according to claim 1, wherein X in the general formula (1) is a polymer chain of an alkylene oxide containing 50% by weight or more of an alkylene oxide unit having 3 or more carbon atoms. 3. The X in the general formula (1) is a polymer chain of an alkylene oxide having 3 and / or 4 carbon atoms.
Alternatively, the solid detergent base according to item 2. 4. The solid detergent according to claim 1, wherein the nonionic surfactant represented by the general formula (1) has a melting point of 25 ° C. or higher and a number average molecular weight of 2000 or higher. Base. 5. A solid detergent base containing a nonionic surfactant represented by the general formula (2). _{[Y 3 -O- (A 1 O} ) n - (B 1 O) m] l -Z - [(B 2 O) m '- (A 2 O) n' -Y 4] l '(2) ( In the formula, Y ₃ and Y ₄ are each independently a hydrogen atom or an acyl group having 1 to 24 carbon atoms, and l Y ₃ and l ′ are
The Y _4's may be the same or different, but Y ₃ and Y ₄
Not all of which become hydrogen atoms at the same time. A ₁ O and A ₂ O are each independently an alkylene oxide having 2 to 4 carbon atoms, and the content of the alkylene oxide having 3 or 4 carbon atoms is (A ₁ O) _n or (A ₂ O). It is 5% by weight or less in each of _{n '} . Also, n and n ′ are
Each is independently a number from 20 to 350. B ₁ O and B ₂ O are each independently an alkylene oxide having 2 or more carbon atoms, and contain 50% by weight or more of an alkylene oxide having 3 or more carbon atoms. m and m'are
Each is independently a number from 2 to 300. Z is a group derived from a compound having three or more active hydrogen groups. l and l ′ are each independently a number of 1 or more, and l + l ′ is equal to the total number of active hydrogen groups of the compound from which Z is derived. ) 6. The solid detergent base according to claim 7, wherein Z in the general formula (2) is a group derived from glycerin, trimethylolpropane, pentaerythritol, sorbitol or ethylenediamine. 7. A solid detergent base containing a water-soluble solid urethane compound obtained by reacting a compound represented by the following general formula (3) with an organic isocyanate compound. _{[Y 5 -O- (A 1 O} ) n - (B 1 O) m] l -Z - [(B 2 O) m '- (A 2 O) n' -Y 6] l '(3) ( In the formula, Y ₅ and Y ₆ are each independently a hydrogen atom or an acyl group having 2 to 24 carbon atoms, and 1 Y ₅ and 1 ′
The Y _6's may be the same or different, but all Y _5's
And at least one of Y ₆ is a hydrogen atom. A ₁ O and A ₂ O are each independently an alkylene oxide having 2 to 4 carbon atoms, and the content of the alkylene oxide having 3 or 4 carbon atoms is (A ₁ O) _n or (A ₂ O). It is 5% by weight or less in each of _{n '} . Also, n and n '
Are each independently a number from 20 to 350. B ₁
O and B ₂ O are each independently an alkylene oxide having 2 or more carbon atoms and contain 50% by weight or more of an alkylene oxide having 3 or more carbon atoms. m and m '
Are each independently a number from 2 to 300. Z is 3
A group derived from a compound having one or more active hydrogen groups. l and l ′ are each independently a number of 1 or more, and l + l ′ is equal to the total number of active hydrogen groups of the compound from which Z is derived. ) 8. The solid detergent base according to claim 3, wherein Z in the general formula (3) is a group derived from ethylenediamine. 9. A solid fragrance detergent containing the solid detergent base according to claim 1.