JP3581041B2 - Detergent meter - Google Patents

Description

【００２７】
以下に、表１中の各成分について詳述する。
・ＬＡＳ：直鎖アルキル（炭素数１２〜１３）ベンゼンスルホン酸ナトリウム
・α−ＳＦＥ：α−オレフィン（炭素数１６〜１８）スルホン酸ナトリウム
・ＡＥ：ポリオキシエチレンアルキル（炭素数１２〜１６）エーテル、エチレンオキサイド平均付加モル数７．０
・石鹸：牛脂脂肪酸ナトリウム
・ゼオライト：４Ａ型ゼオライト、平均粒子径３μｍ（東ソー製）
・吸油担体：Ａｌ_２Ｏ_３ ＝２９．６重量％、ＳｉＯ_２ ＝５２．４重量％、Ｎａ_２Ｏ＝１８．０重量％の非晶質アルミノ珪酸塩。Ｃａイオン捕捉能は１８５ＣａＣＯ_３ ｍｇ／ｇ、吸油能は２８５ｍｌ／１００ｇ。
・非晶質珪酸塩：１号ケイ酸ナトリウム（東ソー製）
・結晶性珪酸塩：粉末ＳＫＳ−６、平均粒径５０μｍ（ヘキストトクヤマ製）
・アクリル酸−マレイン酸共重合体：７０モル％中和のナトリウム塩、モノマー比はアクリル酸／マレイン酸＝７／３（モル比）、重量平均分子量７万
・蛍光染料：チノパールＣＢＳ−Ｘ（チバガイギー社製）とホワイテックスＳＡ（住友化学（株）製）の等量混合物
・酵素：セルラーゼ（特開昭６３−２６４６９９号公報記載）を０．７重量％、リポラーゼ１００Ｔ（ノボ社製）を０．１重量％用いた。
【００２８】
＜洗剤粒子の物性＞
（Ａ）嵩密度
ＪＩＳ：Ｋ．３３６２の方法に従って測定した。結果を表２に示す。
（Ｂ）粒度分布
目開きが２０００μｍ、１４１０μｍ、１０００μｍ、７１０μｍ、５００μｍ、３５５μｍ、２５０μｍ、１８０μｍ及び１２５μｍの９つの篩を、目開きの小さなものから順に受け皿に積み重ね、最上の篩の上に洗剤粒子を１００ｇを入れ、ロータップマシン（ＨＥＩＫＯ ＳＥＩＳＡＫＵＳＨＯ社製、タッピング：１５６回／分、ローリング：２９０回／分）で５分間振動後のそれぞれの篩及び受け皿に残った洗剤粒子を回収し、粒度分布とＣＶ値を求めた。結果を表２に示す。
【００２９】
【表２】

【００３０】
＜洗剤粒子の付着試験＞
表１、２の洗剤粒子１、２と、表３に示す材質からなる計量スプーンを用いて以下の洗剤粒子の付着試験を行った。なお、この計量スプーンは、上部が開口した逆四角錐台形の掬取部（容積４１ｃｍ^３ ）と該掬取部の矩形の開口端の一辺から延伸する把持部（長さ６ｃｍ）とを有する。
【００３１】
掬取部に洗剤が充填されるように計量スプーン全体を洗剤に埋没させた状態から取り出し、計量部から洗剤粒子を排出した後に、把持部に付着した洗剤粒子を払い落とす。このとき、計量スプーンは予め重量を測定しておき、試験前の重量と洗剤粒子を払い落とした後の重量との差を洗剤粒子付着量とした。表面固有抵抗値が１×１０^１４Ω以下の計量スプーンが優れた洗剤粒子付着防止効果を示すことがわかる（表３）。
【００３２】
【表３】

【００３３】
（注）
・紙１：板紙（坪量３５０ｇ／ｍ^２ ）
・紙２：ラミネート紙（紙／ポリエチエレン）
・帯電防止剤Ａ：ステアリン酸ジエタノールアミン／モノ牛脂脂肪酸グリセリルエステル＝６／４（重量比）
・帯電防止剤Ｂ：アルキル（炭素数１６〜１８）ジエタノールアミン
・帯電防止剤の添加量：樹脂１００重量部に対する重量部
・計量スプーンの表面固有抵抗値の測定方法
計量スプーン掬取部から１ｃｍ×１ｃｍの試験片を切り出し、Ｈｉｇｈ Ｒｅｓｉｓｔａｎｃｅ Ｍｅｔｅｒ（横河・ヒューレット・パッカード社製４３２９Ａ）に接続されているＲｅｓｉｓｔｉｖｉｔｙ Ｃｅｌｌ（ヒューレット・パッカード社製１６００８Ａ）に乗せる。試験電圧１００Ｖ、１０秒間印加後、Ｍｅａｓｕｒｅモードに切り替え、５０秒後に表面固有抵抗値を読みとる。
・計量スプーンの表面粗さの測定方法
計量スプーン把持部のほぼ中央付近の表面粗さを、表面粗さ測定器サーフコーダーＳＥ−３０Ｈ−Ｒ（株式会社小坂研究所製）を用いて測定した。測定条件は以下の通りであり、測定ポイントに対し、縦、横、斜めの３方向で測定し、その平均値を表面粗さＲａ（μｍ）とした。
スキャン距離（Ｌ）；２．５ｍｍ
フィルター；Ｎ ｐｈａｓｅ ｔｙｐｅ
カットオフ；λｃ０．８ｍｍ
触針先端径；２μｍ
移動速度；０．１ｍｍ／ｓ
【００３４】
【発明の効果】
本発明によれば、微粉が付着しない高密度粒状洗剤用の計量器が得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a meter for a high-density granular detergent composition.
[0002]
Problems to be solved by the prior art and the invention
The high bulk density detergent is often marketed as a product in which a powder detergent and a measuring instrument such as a measuring spoon are filled in a packaging container. Various studies have been made on powder detergents to be filled, and high bulk density detergents in which the particle size of detergent particles is increased for the purpose of improving the flowability, appearance, and dust prevention of the powder detergent are known. On the other hand, in order to improve the solubility, it is desirable that the particle size of the detergent particles is small.
[0003]
The present inventors have found that a high bulk density detergent having a specific particle size distribution has excellent solubility per detergent particle, but when such a high bulk density detergent is weighed using a conventional measuring spoon. In some cases, fine powder may adhere to the spoon depending on use conditions.
[0004]
[Means for Solving the Problems]
The present invention relates to a measuring instrument for a high-density granular detergent composition containing 10 to 60% by weight of a surfactant and having a particle size distribution satisfying the following condition (1) or (2), wherein the ASTM of the measuring instrument is: Provided is a detergent measuring instrument having a surface specific resistance value of 1 × 10 ¹⁴ Ω or less based on D257.
<Conditions for particle size distribution>
(1) 85% by weight or more of particles having a particle diameter of 180 μm or more and less than 500 μm.
(2) Particles having a particle size of 180 μm or more and less than 500 μm are 50% by weight or more and less than 85% by weight, and a weight ratio of particles having a particle size of less than 180 μm to particles having a particle size of 500 μm or more is 0.5 or more.
[0005]
Further, the present invention provides a container obtained by filling a packaging container with the above specific high-density granular detergent composition and a detergent measuring device having a surface resistivity of 1 × 10 ¹⁴ Ω or less based on ASTM: D257. Provide a detergent.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
〔Meter〕
The measuring device of the present invention is a measuring device for a high-density granular detergent composition having a specific particle size distribution, and has a surface specific resistance value of 1 × 10 ¹⁴ Ω or less based on ASTM: D257, preferably It is 1 × 10 ¹³ Ω or less, more preferably 1 × 10 ⁹ Ω or less. The shape and size may be determined in consideration of the size of the container, the dose of the detergent composition, and the like. However, a shape such as a known measuring spoon having a scooping portion and a grip portion is suitable. Examples of the material of the measuring instrument include various plastics such as high-density polyethylene (HDPE), polypropylene (PP), hard vinyl chloride, and neoprene rubber; metals such as aluminum and stainless steel (for example, SUS304); and papers. When a plastic is used, a material to which an antistatic agent is added can be used. When paper is used, a paper having a basis weight of 200 to 600 g / m ² , particularly 300 to 400 g / m ² , or a laminated paper or a polysand paper in which a plastic such as polyethylene, polypropylene, or polyethylene terephthalate is laminated on the surface is used. Can be. The surface of the measuring device is preferably smoother for the purpose of reducing the amount of physical detergent particles attached, and has a surface roughness Ra of 4 μm or less, preferably 2 μm or less, more preferably 0.5 μm or less, most preferably Preferably it is 0.1 μm or less. In the case of a measuring spoon, it is preferable that the surface of the grip portion has a surface roughness in this range.
[0007]
(High-density granular detergent composition)
In the high-density granular detergent composition of the present invention, the particle size distribution measured from the weight fraction satisfies the following condition (1) or (2).
<Conditions for particle size distribution>
(1) 85% by weight or more of particles having a particle diameter of 180 μm or more and less than 500 μm.
(2) Particles having a particle size of 180 μm or more and less than 500 μm are 50% by weight or more and less than 85% by weight, and a weight ratio of particles having a particle size of less than 180 μm to particles having a particle size of 500 μm or more is 0.5 or more, preferably 1.0 Above, more preferably 1.5 or more.
[0008]
Further, the high-density granular detergent composition of the present invention, the standard deviation of the particle size distribution when sieved with a sieve of 2000 μm, 1410 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm and 125 μm, The CV value obtained by dividing by the average value of the distribution is preferably 0.5 or less, more preferably 0.45 or less, and particularly preferably 0.4 or less. The CV value is determined by, for example, placing the nine-stage sieve on a tray in ascending order of opening, placing a predetermined amount of detergent on the uppermost sieve, and vibrating each sieve. Calculate the particle size distribution measured from the weight fraction of the residual particles on each sieve, calculate the standard deviation and average value of the particle size distribution from the logarithmic average and frequency (%) of the residual particles between each sieve, and average the standard deviation It is determined by dividing by a value. With this method, the particle size distribution of the above (1) or (2) can also be measured.
[0009]
The amount of the surfactant in the composition of the present invention is preferably 15 to 60% by weight, more preferably 20 to 50% by weight, and particularly preferably 27 to 45% by weight in terms of detergency. Examples of the surfactant include at least one selected from a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.
[0010]
The nonionic surfactant preferably has a melting point of 40 ° C. or less, more preferably 30 ° C. or less, and particularly preferably 25 ° C. or less, from the viewpoint of sebum stain detergency. Examples of the nonionic surfactant include polyoxyalkylene alkyl (phenyl) ether, alkylene polyglycoside, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, and polyoxyalkylene alkyl. Roll (fatty acid) amide and the like. Particularly, a polyoxyalkylene alkyl ether is preferable. The content of the nonionic surfactant is preferably at least 8% by weight, more preferably from 10 to 25% by weight, particularly preferably from 10 to 18% by weight, from the viewpoint of detergency and scattering of fine powder.
[0011]
Examples of the anionic surfactant include linear alkyl benzene sulfonate, α-sulfo fatty acid salt or its ester salt, α-olefin sulfonate, alkyl or alkenyl sulfate, and polyoxyethylene alkyl ether sulfate. is there. As these counter ions, alkali metal ions are preferable in terms of detergency. From the viewpoint of improving the dissolution rate, potassium ions are preferred, and the proportion of potassium ions in all counterions is preferably 5% by weight or more, more preferably 20% by weight or more, and particularly preferably 40% by weight or more. The compounding amount of the anionic surfactant is preferably 50% by weight or less, more preferably 1 to 30% by weight, particularly preferably 3 to 20% by weight in terms of detergency.
[0012]
Examples of the cationic surfactant include quaternary ammonium salts such as an alkyltrimethylammonium salt, and examples of the amphoteric surfactant include amphoteric surfactants such as a carbobetaine type and a sulfobetaine type. .
[0013]
The high-density granular detergent composition of the present invention includes an alkali metal salt such as a carbonate group, a hydrogen carbonate group, a sulfate group, a sulfite group, a hydrogen sulfate group, a hydrochloric acid group, or a phosphate group, and an aqueous solution such as an ammonium salt or an amine salt. Inorganic salts can be blended. Here, carbonate is preferable as an alkaline agent showing a suitable pH buffer region in the washing liquid. In addition, salts having a high degree of dissociation, such as sulfate groups and sulfite groups, increase the ionic strength of the washing liquid and are suitable for sebum stain cleaning properties and the like. Further, the sulfite group has an effect of preventing oxidative deterioration due to hypochlorite ions such as enzymes and fragrances. In addition, the total sum of carbonate groups and sulfate groups is preferably 30% by weight (in terms of anhydride) or less, more preferably 25% by weight or less, because the detergent composition particles have excellent non-aggregation properties and enhance solubility. It is preferably at most 20% by weight.
[0014]
In the composition of the present invention, a crystalline silicate can be blended in terms of alkali buffering ability and sequestering ability. From the viewpoint of sequestering ability and hygroscopicity, the molar ratio of SiO ₂ / M ₂ O (where M represents an alkali metal atom) is preferably 0.5 to 2.6. The ion exchange capacity of the crystalline silicate is preferably 100 mg CaCO ₃ / g or more, more preferably 200 to 600 mg CaCO ₃ / g. Further, the compounding amount of the crystalline silicate is preferably 0.5 to 40% by weight, more preferably 1 to 25% by weight, in view of the powder physical properties after storage and excellent detergency.
[0015]
As the sequestering agent other than the crystalline silicate, a carboxylic acid polymer and an aluminosilicate such as zeolite are preferable.
[0016]
As the carboxylic acid-based polymer, an acrylic acid-based polymer such as a salt of an acrylic acid-maleic acid copolymer or a polyacrylate is superior in terms of sequestering ability and dispersing ability of solid particle stains. The compounding amount of the carboxylic acid-based polymer is preferably 0.5 to 12% by weight, more preferably 1 to 7% by weight, and particularly preferably 2 to 5% by weight in the composition from the viewpoint of detergency.
[0017]
The aluminosilicate preferably has an ion exchange capacity of 200 mgCaCO ₃ / g or more. There are a crystalline type and an amorphous type, but synthetic zeolites having an average primary particle diameter of 0.1 to 10 μm such as A-type, X-type and P-type zeolites are preferred.
[0018]
Furthermore, re-staining agents, alkali agents, extenders, dispersants, color transfer inhibitors, bleaches, bleach activators, enzymes, enzyme stabilizers, fluorescent brighteners, defoamers, antioxidants, bluish Additives, fragrances and the like can be blended.
[0019]
Next, physical properties of the high-density granular detergent composition of the present invention will be described.
The bulk density based on JIS K3362 of the high-density granular detergent composition of the present invention is such that the dispersibility is not reduced by ensuring the simplicity of use and the space between particles, and suppressing the increase in the number of contact points between particles. In view of the above, it is preferably 600 to 1200 g / liter, more preferably 650 to 1000 g / liter.
[0020]
The average particle size is 400 μm or less, preferably 200 to 350 μm, more preferably 250 to 320 μm. The average particle diameter is measured from the weight fraction based on the size of the sieve after vibrating for 5 minutes using a standard sieve of JIS Z8801.
[0021]
The flow time required for 100 ml of the powder to flow out of the hopper for bulk density measurement defined in JIS K 3362 is preferably 10 seconds or less, more preferably 8 seconds or less, and particularly preferably 6.5 seconds. It is as follows.
[0022]
The method for producing the high-density granular detergent composition of the present invention includes, for example, a stirring tumbling granulation method using a vertical mixer or a horizontal mixer, a method of crushing a composition compressed by an extruder with a crusher, and the above-described operation. A method of classifying the manufactured crushed particles with a wind force or a sieve, or the like, may be used.
[0023]
(Packaging container)
The container in which the high-density granular detergent composition and the measuring instrument of the present invention are filled is preferably made of paper laminated with one or more resins selected from the group consisting of, for example, nylon, polypropylene and polyethylene. The container is chemically resistant to non-ionic surfactants. In addition, since the resin is laminated on paper, a small amount of the resin can be used as compared with a case where the resin is used alone, and a resin having high strength can be manufactured. The amount of the resin in the laminate is preferably 5 to 50 μm, more preferably 10 to 50 μm, as the thickness (as a single layer) of the resin to be coated on the paper. Within this range, resources can be reduced while maintaining container strength.
[0024]
【Example】
<Preparation of detergent particles>
(1) Production Example 1
Among the components shown in Table 1, an aqueous slurry having a water content of 50% by weight is prepared by using components other than the enzyme, flavor, and crystalline silicate for 5% by weight of zeolite and spray-drying. Next, granulated particles are obtained by a screw extrusion granulator. The granulated particles were placed in a rotary kiln, and 5% by weight of zeolite, an enzyme and a crystalline silicate were blended, and simultaneously sprayed with a fragrance to obtain detergent particles 1 in Table 1.
[0025]
(2) Production example 2
Among the components shown in Table 1, a slurry having a water content of 50% by weight was prepared using components other than AE, an oil-absorbing carrier, an enzyme, a flavor, and a crystalline silicate, and spray-dried. The obtained spray-dried particles, 5% by weight of the oil-absorbing carrier and the crystalline silicate were stirred in a Loedige mixer (stirring-rolling granulator, manufactured by Matsusaka Giken). AE was spray-added thereto and granulated. Next, 3.5% by weight of the oil-absorbing carrier was charged to perform surface modification. The obtained granulated particles were put into a rotary kiln, and the remaining oil-absorbing carrier and the enzyme were blended, and at the same time, a fragrance was sprayed to obtain detergent particles 2 in Table 1.
[0026]
[Table 1]

[0027]
Hereinafter, each component in Table 1 will be described in detail.
LAS: straight chain alkyl (C12-13) sodium benzenesulfonate α-SFE: α-olefin (C16-18) sodium sulfonate AE: polyoxyethylene alkyl (C12-16) ether , Average ethylene oxide mole number 7.0
・ Soap: Sodium tallow fatty acid ・ Zeolite: 4A zeolite, average particle size 3 μm (Tosoh)
Oil-absorbing carrier: amorphous aluminosilicate having Al ₂ O ₃ = 29.6% by weight, SiO ₂ = 52.4% by weight, and Na ₂ O = 18.0% by weight. The ability to capture Ca ions was 185 CaCO ₃ mg / g, and the ability to absorb oil was 285 ml / 100 g.
・ Amorphous silicate: No. 1 sodium silicate (Tosoh)
Crystalline silicate: powder SKS-6, average particle size 50 μm (made by Hoechst Tokuyama)
Acrylic acid-maleic acid copolymer: 70 mol% neutralized sodium salt, monomer ratio: acrylic acid / maleic acid = 7/3 (molar ratio), weight average molecular weight 70,000 Fluorescent dye: Tinopearl CBS-X ( Equivalent mixture of Ciba-Geigy) and Whitex SA (Sumitomo Chemical Co., Ltd.). Enzyme: Cellulase (described in JP-A-63-264699), 0.7% by weight, and Lipolase 100T (Novo) were used. 0.1% by weight was used.
[0028]
<Physical properties of detergent particles>
(A) Bulk density JIS: K. It was measured according to the method of 3362. Table 2 shows the results.
(B) Particle size distribution Nine sieves having openings of 2000 μm, 1410 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm and 125 μm are stacked on a tray in order from the one with the smallest opening, and detergent particles are placed on the uppermost sieve. 100 g, and the detergent particles remaining on each sieve and tray after vibration for 5 minutes with a low tap machine (manufactured by HEIKO SEISAKUSHO, tapping: 156 times / minute, rolling: 290 times / minute) are collected, and the particle size distribution is obtained. And the CV value were determined. Table 2 shows the results.
[0029]
[Table 2]

[0030]
<Detergent particle adhesion test>
Using the detergent particles 1 and 2 shown in Tables 1 and 2 and a measuring spoon made of the material shown in Table 3, the following detergent particle adhesion test was performed. The measuring spoon has a trapezoidal truncated square pyramid-shaped scooping unit (capacity 41 cm ³ ) with an open top and a gripping unit (length 6 cm) extending from one side of the rectangular opening end of the scooping unit.
[0031]
The entire measuring spoon is removed from the state where the detergent is buried in the detergent so that the scooping portion is filled with the detergent, and after the detergent particles are discharged from the measuring portion, the detergent particles attached to the grip portion are removed. At this time, the weight of the measuring spoon was measured in advance, and the difference between the weight before the test and the weight after the detergent particles were removed was defined as the detergent particle adhesion amount. It can be seen that a measuring spoon having a surface resistivity of 1 × 10 ¹⁴ Ω or less exhibits an excellent detergent particle adhesion preventing effect (Table 3).
[0032]
[Table 3]

[0033]
(note)
・ Paper 1: paperboard (basis weight 350 g / m ² )
・ Paper 2: Laminated paper (paper / polyethylene)
Antistatic agent A: diethanolamine stearate / glyceryl mono-tallow fatty acid ester = 6/4 (weight ratio)
-Antistatic agent B: alkyl (C18-C18) diethanolamine-Addition amount of antistatic agent: parts by weight based on 100 parts by weight of resin-Measurement method of surface specific resistance value of measuring spoon 1cm x 1cm from measuring spoon scooping section Is cut out and placed on a Resistivity Cell (16008A manufactured by Hewlett-Packard Company) connected to a High Resistance Meter (4329A manufactured by Yokogawa-Hewlett-Packard Company). After applying a test voltage of 100 V for 10 seconds, the mode is switched to the Measurement mode, and the surface specific resistance value is read after 50 seconds.
Method of measuring surface roughness of measuring spoon The surface roughness near the center of the measuring spoon gripping part was measured using a surface roughness measuring device Surfcoder SE-30H-R (manufactured by Kosaka Laboratory Co., Ltd.). The measurement conditions were as follows, and the measurement was performed in three directions of vertical, horizontal, and oblique to the measurement point, and the average value was defined as the surface roughness Ra (μm).
Scan distance (L); 2.5 mm
Filter; N phase type
Cut off; λc 0.8mm
Stylus tip diameter: 2 μm
Moving speed; 0.1 mm / s
[0034]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the measuring instrument for high-density granular detergents to which fine powder does not adhere is obtained.

Claims (4)

A measuring spoon for a high-density granular detergent composition containing 10 to 60% by weight of a surfactant and having a particle size distribution satisfying the following condition (2), which has a scooping portion and a gripping portion. A measuring spoon for detergents having a surface roughness Ra of 2 μm or less and a surface resistivity of 1 × 10 ¹³ Ω or less based on ASTM: D257 of the measuring spoon.
<Conditions for particle size distribution>
(2) Particles having a particle size of 180 μm or more and less than 500 μm are 50% by weight or more and less than 85% by weight, and the weight ratio of particles having a particle size of less than 180 μm to particles having a particle size of 500 μm or more is 0.5 or more. The standard deviation of the particle size distribution when the high-density granular detergent composition is sieved with a sieve having openings of 2000 μm, 1410 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm and 125 μm is divided by the average value of the particle size distribution. The measuring spoon for detergents according to claim 1, wherein the CV value obtained by the above is 0.5 or less. A high-density granular detergent composition containing 10 to 60% by weight of a surfactant and having a particle size distribution satisfying the following condition (2), and a detergent having a surface specific resistance value of 1 × 10 ¹³ Ω or less based on ASTM: D257. A container-containing detergent obtained by filling a measuring spoon into a packaging container , wherein the measuring spoon has a scooping portion and a grip portion, and the surface roughness Ra of the grip portion is 2 μm or less. .
<Conditions for particle size distribution>
(2) Particles having a particle size of 180 μm or more and less than 500 μm are 50% by weight or more and less than 85% by weight, and the weight ratio of particles having a particle size of less than 180 μm to particles having a particle size of 500 μm or more is 0.5 or more. The standard deviation of the particle size distribution when the high-density granular detergent composition is sieved with a sieve having openings of 2000 μm, 1410 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm and 125 μm is divided by the average value of the particle size distribution. The detergent in a container according to claim 3 , wherein the CV value obtained by the above is 0.5 or less.