JPS5946559B2 - additives for detergents - Google Patents

Description

【発明の詳細な説明】 本発明は粉状乃至粒状の洗剤（以下、これらを粒状洗剤
と総称する）に、特にアニオン活性剤を含有する粒状洗
剤に配合して使用される添加剤に関するものであつて、
さらに詳しくは粒状洗剤と併用して洗濯時に優れた柔軟
性と帯電防止性を、被洗布に付与し得る洗剤用添加剤に
係る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an additive used in powdered or granular detergents (hereinafter collectively referred to as granular detergents), particularly in granular detergents containing anionic activators. It's hot,
More specifically, the present invention relates to a detergent additive that can be used in combination with a granular detergent to impart excellent flexibility and antistatic properties to washed fabrics during washing.

一般家庭に於て、衣類を洗濯し、さらにその被洗布に対
して柔軟性を付与せんとする場合には、洗剤溶液で衣類
を洗浄してから多量の水で洗剤成分を濯ぎ落し、しかる
後水難溶性のジ長鎖アルキル型四級アンモニウム塩を生
成分とする柔軟仕上げ剤にて、被洗布を処理する手順が
普通採用されている。In ordinary households, when washing clothes and adding flexibility to the washed fabric, wash the clothes with a detergent solution, rinse off the detergent components with a large amount of water, and then wash the clothes with a detergent solution. A commonly used procedure is to treat the fabric to be washed with a fabric softener containing a di-long-chain alkyl quaternary ammonium salt that is poorly soluble in water.

これは四級アンモニウム塩を液中に於て洗剤と共存させ
ると、被洗布に柔軟性や帯電防止能を十分付与できない
からである。すなわち、上記のジ長鎖アルキル型四級ア
ンモニウム塩は、繊維に柔軟性と帯電防止性を付与する
性質を本来備えているが、これが液中で洗剤と共存した
場合には、洗剤中の活性成分（通常これはアニオン活性
剤及び／又はノニオン活性剤である）の攻撃を受けてイ
オン性を失つたり、あるいは分散安定化されたりするた
め、被洗布に吸着され難くなり、その結果として四級ア
ンモニウム塩が本来の機能を十分には発揮できなくなる
のである。This is because if the quaternary ammonium salt coexists with the detergent in the solution, sufficient flexibility and antistatic ability cannot be imparted to the cloth to be washed. In other words, the di-long-chain alkyl type quaternary ammonium salt described above inherently has the property of imparting flexibility and antistatic properties to fibers, but when it coexists with detergent in a liquid, it reduces the activity in the detergent. They lose their ionicity or become dispersion-stabilized under attack by the components (which are usually anionic and/or nonionic activators), making them less likely to be adsorbed onto the fabric being washed; The quaternary ammonium salt will no longer be able to fully demonstrate its original function.

それ故に、被洗布に柔軟性と帯電防止性を付与する場合
には、まず洗剤を用いて衣類を洗濯し、その後改めて柔
軟仕上げ剤にて被洗布を処理する手順が一般に採用され
ている。しかしながら、このように洗濯工程と柔軟仕上
げ工程を別々に行なうことは、余分な時間と手間を必要
とするため、洗濯と柔軟仕上げが一挙に行なえる洗剤が
消費者から期待されている。既述の如く四級アンモニウ
ム塩は洗剤中の活性成分によつて本来の機能が損われて
しまうが、この欠点を解決する手段として従来技術は、
四級アンモニウム塩を無機塩や有機分散抑制剤にて造粒
乃至はコーテイングして四級アンモニウム塩の膨潤分散
を遅延させることを提案している（例えば特公昭３６−
８９２７号公報、米国特許第４０７３７３５号明細書、
特開昭４９−９８４０３号公報及び同５３−４１３１２
号公報など参照）。Therefore, when imparting flexibility and antistatic properties to washed fabrics, the procedure generally adopted is to first wash the clothes using a detergent and then treat the washed fabrics again with a fabric softener. . However, performing the washing process and softening process separately in this way requires extra time and effort, so consumers are looking forward to detergents that can perform both washing and fabric softening at the same time. As mentioned above, the original function of quaternary ammonium salts is impaired by the active ingredients in detergents, but as a means to solve this drawback, conventional technology has
It has been proposed to retard the swelling and dispersion of quaternary ammonium salts by granulating or coating quaternary ammonium salts with inorganic salts or organic dispersion inhibitors (for example, Japanese Patent Publication No. 1989-1999)
No. 8927, US Pat. No. 4,073,735,
JP-A-49-98403 and JP-A No. 53-41312
(Refer to the publication number, etc.)

しかし、この手段は洗濯条件が、殊に用水の温度が特定
な範囲にあれば、ある程度有効であるものの、洗濯用水
の温度が変わると、柔軟仕上げ効果に優劣が生ずる憾み
がある。この点をさらに詳述すると、夏と冬とでは水温
が異なる例からも解る通り、洗濯用水の温度が常に一定
であることは殆どありえない。従つてある場合には四級
アンモニウム塩の膨潤分散が十分に遅延されず、またあ
る場合には過度に遅延されて四級アンモニウム塩粒子が
そのまま被洗布に付着するといつた事態が生じやすく、
これに起因して被洗布の柔軟仕上げ効果にバラツキが出
るのである。本発明者らは上記した従来技術の問題点を
鑑みて、アニオン活性剤及び／又はノニオン活性剤と液
中で共存する四級アンモニウム塩の被洗物に対する吸着
機構に関し鋭意研究を重ねた結果、被洗物に対する吸着
には、洗液中に於ける四級アンモニウム塩粒子の界面状
態と液晶構造が重要な影響を及ぼすこと、さらにこの界
面状態と液晶構造を改良するには、脂肪族多価カルボン
酸塩が有効であることを見い出した。However, although this method is effective to some extent under washing conditions, especially when the temperature of the washing water is within a specific range, there is a problem in that the softening effect may vary as the temperature of the washing water changes. To explain this point in more detail, as can be seen from the example where the water temperature is different in summer and winter, it is almost impossible for the temperature of washing water to always be constant. Therefore, in some cases, the swelling and dispersion of the quaternary ammonium salt is not delayed sufficiently, and in other cases, it is delayed too much, which tends to cause the quaternary ammonium salt particles to adhere to the cloth being washed.
This causes variations in the softening effect of the cloth to be washed. In view of the problems of the prior art described above, the present inventors have conducted extensive research into the adsorption mechanism of quaternary ammonium salts coexisting with an anionic activator and/or nonionic activator in a liquid to washed items. The interfacial state and liquid crystal structure of the quaternary ammonium salt particles in the washing liquid have important effects on adsorption to the object to be washed.Furthermore, to improve this interfacial state and liquid crystal structure, aliphatic It has been found that carboxylic acid salts are effective.

而して本発明に係る洗剤用添加剤は、下記の一般式で示
される四級アンモニウム塩を加熱溶融し、これに脂肪族
多価カルボン酸塩を、四級アンモニウム塩対カルボン酸
塩の重量比が１／４〜２０／１になるように添加し、均
一混合後冷却した溶融混合物から構成される。Therefore, the detergent additive according to the present invention is obtained by heating and melting a quaternary ammonium salt represented by the following general formula, and adding an aliphatic polycarboxylic acid salt to the quaternary ammonium salt in a proportion of the weight of the quaternary ammonium salt to the carboxylic acid salt. It is composed of a molten mixture that is added in a ratio of 1/4 to 20/1, mixed uniformly, and then cooled.

但し、Ｒ１、Ｒ２はＣｌ２〜Ｃ２６のアルキル基を示し
Ｒ３、Ｒ４はＣ１〜Ｃ４のアルキル基、ベンジル基、Ｃ
２〜Ｃ４ヒドロキシアルキル基又はポリオキシアルキレ
ン基を示し、Ｘはハロゲン、ＣＨ３ＳＯ４、Ｃ２Ｈ５Ｓ
Ｏ４又は本発明の洗剤用添加剤に使用される四級アンモ
ニウムは、その融点が３０〜１００℃、好ましくは４０
〜９０℃の範囲にあつて、高温で分解乃至変質する四級
アンモニウム塩は、本発明への使用に適さない。However, R1 and R2 represent a Cl2 to C26 alkyl group, and R3 and R4 represent a C1 to C4 alkyl group, a benzyl group, and a C1 to C4 alkyl group.
2-C4 hydroxyalkyl group or polyoxyalkylene group, X is halogen, CH3SO4, C2H5S
O4 or the quaternary ammonium used in the detergent additive of the present invention has a melting point of 30 to 100°C, preferably 40°C.
Quaternary ammonium salts that decompose or deteriorate at high temperatures in the range of ~90°C are not suitable for use in the present invention.

使用可能な四級アンモニウム塩の具体例にはジステアリ
ルジメチルアンモニウム塩、ジ水添牛脂アルキルジメチ
ルアンモニウム塩、ジ水添牛脂アルキルベンジルメチル
アンモニウム塩、ジステアリルメチルベンジルアンモニ
ウム塩、ジステアリルメチルヒドロキシエチルアンモニ
ウム塩、ジステアリルメチルヒドロキシプロピルアンモ
ニウム塩、ジステアリルジヒドロキシエチルアンモニウ
ム塩などが包含され、その対イオンとしては塩素イオン
、臭素イオンなどが挙げられる。尚、市販の四級アンモ
ニウム塩は通常エタノール、イソプロパノールなどの低
級アルコールを含有するが、これら低級アルコールは予
め除去しておくことが好ましい。これらの低級アルコー
ルは本発明の洗剤用添加剤を粒状品とした場合、その自
由流動性乃至は保存安定性に悪影響を及ぼすからである
。一方、本発明で使用される脂肪族多価カルボン酸塩は
常温で固体であつて、その具体例としてはシユウ酸、マ
ロン酸、コハク酸、グルタル酸、マレイン酸、シトラコ
ン酸、クエン酸、酒石酸、リンゴ酸のアルカリ金属塩な
どが例示できる。Specific examples of usable quaternary ammonium salts include distearyldimethylammonium salt, dihydrogenated tallow alkyldimethylammonium salt, dihydrogenated tallow alkylbenzylmethylammonium salt, distearylmethylbenzylammonium salt, and distearylmethylhydroxyethylammonium. Salts, distearylmethylhydroxypropylammonium salts, distearyldihydroxyethylammonium salts, etc. are included, and counter ions thereof include chloride ions, bromide ions, etc. Note that commercially available quaternary ammonium salts usually contain lower alcohols such as ethanol and isopropanol, but it is preferable to remove these lower alcohols in advance. This is because these lower alcohols have an adverse effect on the free-flowing properties and storage stability of the detergent additive of the present invention when it is made into granules. On the other hand, the aliphatic polycarboxylic acid salts used in the present invention are solid at room temperature, and specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, citraconic acid, citric acid, and tartaric acid. , alkali metal salts of malic acid, and the like.

そしてこのアルカリ金属塩は無水塩、含水塩の何れでも
差支えない。上記した四級アンモニウム塩と多価カルボ
ン酸塩との混合比は、本発明にとつて極めて重要であつ
て、前者対後者の重量は１／４〜２０／１の範囲になけ
ればならない。This alkali metal salt may be either an anhydrous salt or a hydrated salt. The mixing ratio of the above-mentioned quaternary ammonium salt and polycarboxylic acid salt is extremely important for the present invention, and the weight of the former to the latter must be in the range of 1/4 to 20/1.

混合に際しての重量比がこの範囲を逸脱した場合には、
被洗布に対する柔軟効果と帯電防止効果が劣化する。ま
た、四級アンモニウム塩と多価カルボン酸塩とは均一に
混合されなければならない。従つて本発明では洗剤用添
加剤の調製に際して、四級アンモニウム塩を加熱溶融し
、これに多価カルボン酸塩を添加する方式が採用される
。粉体混合方式では四級アンモニウム塩と多価カルボン
酸塩との混合状態が不均一になりやすいため、所期の効
果が得られない虞れがある。さらに混合に際して水分が
存在すると、四級アンモニウム塩と多価カルボン酸塩が
柔軟仕土げ効果にとつてマイナスな錯体を形成すること
があるので、水分は少ない方が好ましい。一般に、四級
アンモニウム塩と多価カルボン酸塩との溶融混合物は、
洗液中で（１）膨潤（軟化）液晶化、（２）被洗物への
吸着、（３）被洗物表面での拡散、（４）均質膜の形成
といつた一連の現象を伴いながら、被洗物に対して柔軟
性と帯電防止性を付与するものと考えられる。If the weight ratio during mixing deviates from this range,
The softening effect and antistatic effect on the cloth to be washed deteriorate. Further, the quaternary ammonium salt and the polycarboxylic acid salt must be uniformly mixed. Therefore, in the present invention, when preparing a detergent additive, a method is adopted in which a quaternary ammonium salt is heated and melted, and a polyvalent carboxylic acid salt is added thereto. In the powder mixing method, the mixing state of the quaternary ammonium salt and the polyvalent carboxylate tends to be non-uniform, so there is a risk that the desired effect may not be obtained. Furthermore, if moisture is present during mixing, the quaternary ammonium salt and the polycarboxylic acid salt may form a complex that is negative for the softening effect, so the lower the moisture content, the better. Generally, a molten mixture of a quaternary ammonium salt and a polycarboxylic acid salt is
In the washing liquid, a series of phenomena occur: (1) swelling (softening) and liquid crystallization, (2) adsorption to the object to be washed, (3) diffusion on the surface of the object to be washed, and (4) formation of a homogeneous film. However, it is thought that it imparts flexibility and antistatic properties to the items to be washed.

本発明の洗剤用添加剤では、四級アンモニウム塩に対し
て特定比率の多価カルボン酸塩が混合されているため、
特に上記（１）の膨潤液晶化の過程で特殊な液晶構造を
とり、その結果洗液中に共存するアニオン活性剤やノニ
オン活性剤の攻撃を受けにくくなるので、被洗物への吸
着が実質的に阻害されなくなつて、被洗物に対して優れ
た柔軟性と帯電防止性が付与されるものと推定される。
本発明の洗剤用添加剤は粒状洗剤に配合されて使用され
る。In the detergent additive of the present invention, a specific ratio of polycarboxylic acid salt is mixed with quaternary ammonium salt.
In particular, in the process of swelling liquid crystal formation in (1) above, a special liquid crystal structure is formed, and as a result, it becomes less susceptible to attack by anionic activators and nonionic activators coexisting in the washing liquid, so that adsorption to the items to be washed is substantially reduced. It is presumed that the washing material is no longer inhibited by the oxidation process, thereby imparting excellent flexibility and antistatic properties to the items to be washed.
The detergent additive of the present invention is used by being mixed into a granular detergent.

この場合、添加剤粒子の平均粒径は、叫Ｂ５Ｏ〜２５０
μの範囲にあることが好ましい。粒径が大きくなると被
洗物に満遍なく柔軟性を付与できないことがあるばかり
でなく、添加剤粒子がそのまま被洗物に付着する虞れが
あり、また粒径が小さ過ぎると洗液中で粒子が分散され
すぎて被洗物に吸着されにくくなるので好ましくない。
粒状洗剤に対する添加剤の配合量は、四級アンモニウム
塩基準で０．５〜５重量％の範囲を可とする。０．５％
未満では柔軟仕上げ効果が不充分となり、逆に５％を越
えると洗剤の洗浄力及び泡立ちを損うからである。In this case, the average particle size of the additive particles is B5O~250
It is preferably in the range of μ. If the particle size is too large, it may not be possible to evenly impart flexibility to the items to be washed, and there is a risk that the additive particles will adhere to the items to be washed, and if the particle size is too small, particles may not be imparted evenly to the items to be washed. is not preferable because it becomes too dispersed and becomes difficult to be adsorbed onto the items to be washed.
The amount of the additive added to the granular detergent may range from 0.5 to 5% by weight based on the quaternary ammonium salt. 0.5%
If it is less than 5%, the softening effect will be insufficient, and if it exceeds 5%, the cleaning power and foaming of the detergent will be impaired.

進んで実施例を示し本発明をさらに具体的に説明する。The present invention will now be described in more detail by way of examples.

実施例 １ 表１に示す四級アンモニウム塩と多価カルボン酸塩を使
用し、加熱溶融した四級アンモニウム塩に平均粒径１５
０〜２００μの多価カルボン酸塩を添加して均一に混合
後、冷却固化させ、しかる後これを粉砕して平均粒度６
０〜１００メツシユの添加剤組成物を得た。Example 1 Using the quaternary ammonium salt and polyvalent carboxylate shown in Table 1, the quaternary ammonium salt heated and melted had an average particle size of 15
After adding 0 to 200μ of polyhydric carboxylic acid salt and mixing uniformly, it is cooled and solidified, and then crushed to obtain an average particle size of 6.
Additive compositions of 0 to 100 meshes were obtained.

但し、．４６．１７〜２６は対照例である。次に上記の
各添加剤組成物を下記の組成の粒状洗剤に配合して洗濯
を行ない、各添加剤組成物の被洗物に対する柔軟性付与
効果、帯電防止性付与効果、付着粒子の多寡並びに洗浄
力に対する影響を検定した。however,. 46.17-26 are control examples. Next, each of the above additive compositions is blended into a granular detergent having the composition shown below, and washing is carried out. The effect on cleaning power was examined.

粒状洗剤の組成 からなる試験布を前記の粒状洗剤と６０℃の水道水を用
いて１５分間洗浄した後、６０℃の水道水を用いて３分
間ずつ３回濯いで試験布を前処理する。A test fabric consisting of a granular detergent composition is washed for 15 minutes using the above granular detergent and tap water at 60°C, and then rinsed three times for 3 minutes each using tap water at 60°C to pre-treat the test fabric.

次いでこの試験布を噴流式家庭用電気洗濯機に収め、前
記の粒状洗剤と各添加剤組成物と２５℃の水道水を用い
て、洗剤濃度０．１３％、浴比３０倍の条件下に１０分
間洗浄し１分間脱水した後、２５℃の水道水で３分間濯
いでから１分間脱水する操作を２回繰り返した。Next, this test cloth was placed in a jet-type domestic electric washing machine, and was washed with the above-mentioned granular detergent, each additive composition, and tap water at 25°C at a detergent concentration of 0.13% and a bath ratio of 30 times. After washing for 10 minutes, dehydrating for 1 minute, rinsing with tap water at 25° C. for 3 minutes, and dehydrating for 1 minute, the procedure was repeated twice.

しかる後、試験布を２４時間風乾し、次に２５℃、６５
％ＲＨの条件下に風乾試験布をコンデイシヨニングした
。こうして得られた試験布のなかからナイロントリコツ
ト布を取り出し、その感触を５人の判定者に判定させ、
判定者５人の平均から添加剤組成物の柔軟性付与効果を
評価した。After that, the test cloth was air-dried for 24 hours, and then heated at 25℃ and 65℃.
The air-dried test fabrics were conditioned under conditions of %RH. A nylon tricot cloth was taken out of the test cloths obtained in this way, and five judges judged its feel.
The flexibility imparting effect of the additive composition was evaluated based on the average of five judges.

尚、この感触判定は添加剤組成物を使用しなかつた以外
は上記と全く同一の手順で得られたナイロントリコツト
布の感触をゼロとし、これとの比較から下記の基準で行
なつた。結果を表２に示す。また、触感判定に使用した
ものと同種のナイロントリコツト布を３．５儂平方に裁
断してオネストメータ一（菊水電気製）の回転板に取り
付け、一定速度で回転させながら高さ２？の電極から電
圧１万ボルトを印加して布の帯電圧の振幅を調製した後
、印加電圧を切り、布の帯電圧が半減するまでの時間「
半減期」を２５℃、６５％ＲＨの条件下に測定した。こ
の操作を同一試料について３回繰返し、その平均値にて
添加剤組成物の帯電防止付与効果を評価した。結果を表
２に示す。（４）付着粒子の多寡検定法 からなる洗濯物を噴流式家庭用電気洗濯機に収め、前記
の粒状洗剤と添加剤組成物と５℃の水道水を用いて洗剤
濃度０．２６％、浴比３０倍の条件下に５分間洗浄した
後、５℃の水道水にて３分間ずつ２回濯いで脱水し、被
洗物に付着した粒子の多寡を下記の基準で目視判定した
。The feel was evaluated based on the following criteria in comparison with the feel of a nylon tricot cloth obtained by the same procedure as above except that no additive composition was used. The results are shown in Table 2. In addition, a nylon tricot cloth of the same type as that used for the tactile evaluation was cut into 3.5 square pieces and attached to the rotary plate of an Honest meter (manufactured by Kikusui Denki), and while rotating at a constant speed, a height of 2 mm was cut. After adjusting the amplitude of the charged voltage on the cloth by applying a voltage of 10,000 volts from the electrode, the applied voltage is turned off and the time required for the charged voltage on the cloth to be halved is ``
The half-life was measured under conditions of 25° C. and 65% RH. This operation was repeated three times for the same sample, and the antistatic effect of the additive composition was evaluated based on the average value. The results are shown in Table 2. (4) Method for assaying the amount of adhered particles The laundry was placed in a jet-type household electric washing machine, and the detergent concentration was 0.26% using the above granular detergent, additive composition, and tap water at 5°C. After washing for 5 minutes under conditions of 30 times the ratio, the items were rinsed twice with tap water at 5° C. for 3 minutes each and dehydrated, and the amount of particles adhering to the items to be washed was visually determined based on the following criteria.

結果を表２に示す。１０洗浄力検定法 試験布（綿プロード）をワイシヤツの衿に取り付けて２
〜７日間着用後、試験布を取り外して左右対称に切断し
たものを２０枚ずつ用意する。The results are shown in Table 2. 10 Detergent power test method Attach the test cloth (cotton proud) to the collar of the dress shirt.2
After being worn for ~7 days, the test fabric was removed and cut symmetrically on both sides to prepare 20 pieces each.

同様にして２〜３日間着用した肌シャツ（綿メリヤス）
を左右対称に分割する。次に噴流式家庭用電気洗濯機を
使用し、２等分にした試験布及び肌シャツの一方（Ａ群
）を添加剤組成物と粒状洗剤の混合物で、他方（Ｂ群）
を粒状洗剤のみで洗濯した。洗濯には両群とも２５℃の
水道水を使用すると共に、洗剤濃度０．１３％、浴比３
０倍の条件を採用した。１０分間洗浄後、３分間ずつ２
回濯いで被洗物を脱水乾燥した。A skin shirt (cotton knitted) worn in the same way for 2 to 3 days
Divide symmetrically. Next, using a jet-type household electric washing machine, one of the test cloths and skin shirts (Group A), which was divided into two halves, was treated with a mixture of the additive composition and granular detergent, and the other (Group B)
was washed using only granular detergent. Both groups used tap water at 25°C for washing, detergent concentration 0.13%, and bath ratio 3.
The condition of 0 times was adopted. After washing for 10 minutes, wash 2 times for 3 minutes each.
The items to be washed were dehydrated and dried by repeated rinsing.

しかる後、Ａ．Ｂ両群の各被洗布を肉眼観察して、完全
に汚れが落ちているものを５点、殆ど落ちていないもの
を１点とする５段階評価で、各被洗布に評点を与え、Ａ
群の評点合計をＢ群の評点合計で割つて１００倍した値
から、次の基準で洗浄力を評価した。結果を表２に示す
。実施例 ２ ジステアリルジメチルアンモニウムクロライドとクエン
酸ソーダ（無水塩）とを１：１の重量比で使用し、両者
の混合法及び混合物の粒状化法を変えて各種の添加剤組
成物を調製し、各添加剤組成物について実施例１と同様
な実験を行なつた。After that, A. Each cloth to be washed in both groups B was observed with the naked eye, and each cloth to be washed was given a score on a five-point scale, with 5 points for completely clean stains and 1 point for hardly any stains. A
The detergency was evaluated using the following criteria based on the value obtained by dividing the total score of the group by the total score of Group B and multiplying the result by 100. The results are shown in Table 2. Example 2 Various additive compositions were prepared using distearyldimethylammonium chloride and sodium citrate (anhydrous salt) at a weight ratio of 1:1, and by changing the method of mixing the two and the method of granulating the mixture. The same experiment as in Example 1 was conducted for each additive composition.

但し、粒状洗剤に配合した添加剤組成物の平均粒度は、
いずれも６０〜１００メツシユとし、配合量は四級アン
モニウム塩基準で粒状洗剤に対し１ｗｔ％とした。実験
結果を表３に示す。However, the average particle size of the additive composition blended into the granular detergent is
In each case, the mesh size was 60 to 100, and the blending amount was 1 wt% based on the granular detergent based on the quaternary ammonium salt. The experimental results are shown in Table 3.

但し、Ａ６．５〜８は対照例である。実施例 ４ 表４に示す組成の粒状洗剤と添加剤組成物を使用して、
実施例１と同様な実験を行ない、次表に示す如き結果を
得た。However, A6.5 to A6.8 are control examples. Example 4 Using the granular detergent and additive composition shown in Table 4,
An experiment similar to that in Example 1 was conducted, and the results shown in the following table were obtained.

表４は本発明に係る洗剤用添加剤Ｃを使用すれば、粒状
洗剤の洗浄力に悪影響を及ぼすことなく、被洗物に充分
な柔軟性と帯電防止性を付与できることを示し、また被
洗物への付着粒子も少ないことを示している（慮４、８
、１２、１６参照）。Table 4 shows that by using additive C for detergents according to the present invention, it is possible to impart sufficient flexibility and antistatic properties to the items to be washed without adversely affecting the detergency of the granular detergent. This indicates that there are fewer particles adhering to objects (Considerations 4 and 8).
, 12, 16).

Claims (1)

【特許請求の範囲】 １ 下記の一般式で示される四級アンモニウム塩を加熱
溶融し、これに脂肪族多価カルボン酸塩を、四級アンモ
ニウム塩対カルボン酸塩の重量比が１／４〜２０／１に
なるように添加し、均一混合後冷却固化させて得られる
洗剤用添加剤▲数式、化学式、表等があります▼ 但し、Ｒ＿１、Ｒ＿２はＣ＿１＿２〜Ｃ＿２＿６のアル
キル基を示し、Ｒ＿３、Ｒ＿４はＣ＿１〜Ｃ＿４のアル
キル基、ベンジル基、Ｃ＿２〜Ｃ＿４のヒドロキシアル
キル基又はポリオキシアルキレン基を示し、Ｘはハロゲ
ン、ＣＨ＿３ＳＯ＿４、Ｃ＿２Ｈ＿５ＳＯ＿４又は▲数
式、化学式、表等があります▼を示す。[Claims] 1. A quaternary ammonium salt represented by the following general formula is heated and melted, and an aliphatic polycarboxylic acid salt is added to the quaternary ammonium salt at a weight ratio of 1/4 to the carboxylic acid salt. Additives for detergents obtained by adding at a ratio of 20/1 and cooling and solidifying after uniform mixing ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R_1 and R_2 represent alkyl groups of C_1_2 to C_2_6, R_3, R_4 represents an alkyl group of C_1 to C_4, a benzyl group, a hydroxyalkyl group of C_2 to C_4, or a polyoxyalkylene group, and X represents a halogen, CH_3SO_4, C_2H_5SO_4, or ▲a mathematical formula, chemical formula, table, etc.