JPH0437183B2

JPH0437183B2 -

Info

Publication number: JPH0437183B2
Application number: JP62212221A
Authority: JP
Inventors: Masaaki Yamamura; Junichi Inokoshi; Kazuo Shimizu; Kazumitsu Furuta
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 1987-08-26
Filing date: 1987-08-26
Publication date: 1992-06-18
Also published as: JPS6461571A

Description

[Detailed description of the invention]

〔産業上の利用分野〕本発明は柔軟仕上剤、更に詳細には、各種繊維
に対して優れた柔軟性と帯電防止性を付与するこ
とのできる経時的な増粘の少ない濃縮型の衣料用
柔軟仕上剤に関する。〔従来の技術及びその問題点〕衣料は、着用及び洗濯を繰り返し行う間に繊維
処理剤が洗い落とされたり、あるいは繊維自体の
劣化により硬くなつたりして好ましからざる風合
を生ずる。そのため、近年、多くの家庭におい
て、繊維に柔軟性、帯電防止性を付与することが
できる柔軟仕上剤が多用されている。現在、家庭用柔軟仕上剤として市販されている
ものは、その殆どが、一分子中に１〜２個の長鎖
アルキル基を有するカチオン性活性剤、なかんず
くジ（硬化牛脂アルキル）ジメチルアンモニウム
塩を主成分とするものである。これらの第４級アンモニウム塩を主成分とする
柔軟基剤は水に難溶であり、通常、３〜５重量％
の水分散液又は乳濁液の形で製造されている。柔
軟仕上剤を使用する対象衣料の増加に伴い、流通
コストや包装コストの減少、家庭や販売店等での
在庫スペースの縮小を目的に、高濃度の水分散液
である濃縮型の衣料用柔軟仕上剤が強く要望され
ている。しかしながら、濃度が５重量％以上になると、
上記の水分散液は著しく増粘し、ハンドリング
上、種々のトラブルを生ずる。従来から、このような高濃度の柔軟仕上剤を製
造するためには１水溶性のカチオン活性剤を添加する方法２高級アルコールやアルキルフエノールのエチ
レンオキシド付加物を添加する方法３尿素やエチレングリコールなどを添加する方
法４水溶性の塩を添加する方法などが知られている。しかしながら、１）〜３）の場合は濃縮の程度
が不十分であつたり、経時的増粘を生じ十分な効
果は得られない。４）の場合は初期の粘性の低下効果は認められ
るものの、経時的な増粘に対する抑制効果が少な
い。又、塩を多量に添加すると水分散液が分離し
易くなる傾向があり、満足できる濃縮型の衣料用
柔軟仕上剤は得られていない。〔問題点を解決するための手段〕かかる実情において、本発明者らは上記の問題
点を解決せんと鋭意研究を行つた結果、高濃度の
第４級アンモニウム塩を分散させる際、特定のカ
チオンポリマーを作用させると、初期物性を改善
し、かつ経時的な増粘を著しく抑制出来るという
知見を得、この知見に基づいて、濃縮型の衣料用
柔軟仕上剤に関する本発明を完成するに至つた。即ち本発明は (a) 第４級アンモニウム塩、 (b) 次の一般式（１）の構造を有するカチオン界
面活性剤モノマーを必須成分とする重合体（式中、R₁は水素又はメチル基を表し、R₂
は炭素数８〜24の直鎖又は分岐状のアルキル基
またはアルケニル基又は置換基を有する炭素数
８〜24の直鎖又は分岐状のアルキル基又はアル
ケニル基を表し、R₃，R₄は水素、炭素数１〜
３のアルキル基、炭素数２〜４のヒドロキシア
ルキル基又はポリオキシアルキレン基（平均付
加モル数＝１〜３）を表す。Ｙは酸素又は−
NH−基を表し、Z₁は炭素数２〜４のヒドロキ
シアルキレン基を表す。また、Ｘはハロゲンま
たは酸残基を表す。）を有効成分として含有することを特徴とする濃縮
型の衣料用柔軟仕上剤を提供するものである。本発明において、衣料用柔軟基材として用いら
れる(a)第４級アンモニウム塩としては、次のよう
なものを挙げることが出来、これらは二種以上混
合して用いてもよい。 R_1a：C₈〜C₂₂の飽和又は不飽和の直鎖又は分
岐アルキル基又はヒドロキシアルキル基 R_2a：C₈〜C₂₄の飽和又は不飽和の直鎖又は分
岐アルキル基又はヒドロキシアルキル基 R_3a，R_4a，R_6a：C₁〜C₃のアルキル基又はヒド
ロキシアルキル基又は
[Industrial Field of Application] The present invention relates to a fabric softener, and more particularly, to a concentrated type clothing fabric softener that can impart excellent flexibility and antistatic properties to various types of fibers and that does not thicken over time. Regarding fabric softeners. [Prior Art and its Problems] When clothing is repeatedly worn and washed, the fiber treatment agent may be washed off, or the fibers themselves may deteriorate and become stiff, resulting in an undesirable feel. Therefore, in recent years, fabric softeners that can impart flexibility and antistatic properties to fibers have been frequently used in many households. Currently, most of the commercially available household fabric softeners contain cationic surfactants with one to two long-chain alkyl groups in one molecule, especially di(hardened tallow alkyl) dimethylammonium salts. It is the main ingredient. These soft bases mainly composed of quaternary ammonium salts are poorly soluble in water, and are usually 3 to 5% by weight.
It is produced in the form of an aqueous dispersion or emulsion. With the increase in the number of garments that use fabric softeners, concentrated fabric softeners, which are highly concentrated aqueous dispersions, have been developed to reduce distribution costs, packaging costs, and inventory space at homes and retail stores. Finishing agents are in high demand. However, when the concentration exceeds 5% by weight,
The above aqueous dispersion greatly thickens, causing various troubles in handling. Conventionally, in order to produce such high-concentration fabric softeners, 1. A method of adding a water-soluble cationic activator. 2. A method of adding ethylene oxide adducts of higher alcohols and alkylphenols. 3. A method of adding urea, ethylene glycol, etc. Addition method 4 A method of adding a water-soluble salt is known. However, in cases 1) to 3), the degree of concentration is insufficient or the viscosity increases over time, making it impossible to obtain sufficient effects. In the case of 4), although the initial viscosity reduction effect is observed, the effect of suppressing the increase in viscosity over time is small. Furthermore, when a large amount of salt is added, the aqueous dispersion tends to separate easily, and a satisfactory concentrated clothing fabric softener has not been obtained. [Means for Solving the Problems] Under these circumstances, the present inventors conducted intensive research to solve the above problems, and found that when dispersing a high concentration of quaternary ammonium salt, a specific cation We have found that when a polymer is applied, initial physical properties can be improved and thickening over time can be significantly suppressed. Based on this knowledge, we have completed the present invention regarding a concentrated clothing fabric softener. . That is, the present invention provides a polymer comprising (a) a quaternary ammonium salt, and (b) a cationic surfactant monomer having the structure of the following general formula (1) as an essential component. (In the formula, R ₁ represents hydrogen or a methyl group, and R ₂
represents a straight chain or branched alkyl group or alkenyl group having 8 to 24 carbon atoms or a straight chain or branched alkyl group or alkenyl group having 8 to 24 carbon atoms having a substituent, and R ₃ and R ₄ are hydrogen , carbon number 1~
represents an alkyl group of 3, a hydroxyalkyl group having 2 to 4 carbon atoms, or a polyoxyalkylene group (average number of added moles = 1 to 3). Y is oxygen or -
It represents an NH- group, and Z ₁ represents a hydroxyalkylene group having 2 to 4 carbon atoms. Moreover, X represents a halogen or an acid residue. ) as an active ingredient. In the present invention, (a) quaternary ammonium salts used as the flexible base material for clothing include the following, and two or more of these may be used as a mixture. R _1a : C ₈ to C ₂₂ saturated or unsaturated linear or branched alkyl group or hydroxyalkyl group R _2a : C ₈ to C ₂₄ saturated or unsaturated linear or branched alkyl group or hydroxyalkyl group R _3a , R _4a , R _6a : C ₁ to C ₃ alkyl group or hydroxyalkyl group or

【式】但しｎ＝１〜 10，Y_a＝水素又はCH₃ R_5a：C₂₄〜C₃₆の飽和又は不飽和の分岐アルキ
ル基又はヒドロキシアルキル基 R_7a，R_8a：C₇〜C₂₁の飽和又は不飽和の直鎖又
は分岐アルキル基又はヒドロキシアルキル
基Ａ，Ｂ：C₁〜C₃のアルキレン基 X_a：CH₃SO₄，C₂H₅SO₄，C_oH_2o+1COOでｎ＝
０〜17，C_oH_2o+1OPO₃でｎ＝８〜18，
HOCH₂COO、[Formula] However, n = 1 to 10, Y _a = hydrogen or CH ₃ R _5a : C ₂₄ to C ₃₆ saturated or unsaturated branched alkyl group or hydroxyalkyl group R _7a , R _8a : C ₇ to C ₂₁ Saturated or unsaturated linear or branched alkyl group or hydroxyalkyl group A, B: C ₁ to C ₃ alkylene group X _a : CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , C _o H _2o+1 COO n=
0~17, n=8~18 for C _o H _2o+1 OPO ₃ ,
HOCH ₂ COO,

〔Effect of the invention〕

(a)成分と(b)成分を必須として含む本発明の濃縮
型の衣料用柔軟仕上剤は通常濃度の柔軟仕上剤に
比べて有効成分にほぼ反比例した使用量で効果を
発揮する。このため輸送、包装、在庫の各段階で
大幅な省エネ、省資源に結びつく優れたものであ
る。〔実施例〕以下に実施例により、本発明を具体的に説明す
るが、本発明はこれらに限定されるものではな
い。 (b)成分の製造例イソプロパノール（100部）を加熱還流させ、
２−ヒドロキシ−３−メタクリロイルオキシプロ
ピルジメチルステアリルアンモニウムクロライド
（5.4部）、〔（１）式のR₁＝メチル、R₂＝ステアリ
ル、R₃，R₄＝メチル、Ｙ＝酸素、Ｚ＝２−ヒド
ロキシプロピレン、Ｘはハロゲン〕、 β−メタクリロイルオキシエチルジメチルエチ
ルアンモニウムエトサルフエート（37部）、スチ
レン（12.5部）、アクリルアミド（10.3部）及び
２，2′−アゾビスイソブチルニトリル（1.0部）
を含むイソプロパノール溶液150部を２時間かけ
て滴下した。滴下後３時間反応液を加熱還流させ
た後水200mlを加えて希釈し、イソプロパノール
を留去し、濃度調製して固形分20.0％の水溶液を
得た。実施例１〜25、比較例１〜８第１表に示す(a)成分、第２表に示す(b)成分を含
む第３表に示す柔軟仕上剤を用い、以下の評価を
行つた。１物性値及び安定性濃縮型の衣料用柔軟仕上剤を−10℃、室温、50
℃にて20日間保存し、外観及び流動性を測定し
た。結果を表３に示した。本発明の濃縮型の衣料
用柔軟仕上剤は、いずれも経時的な変化も殆ど無
く良好であつた。２柔軟性能市販の木綿タオル及びメリヤス肌着、アクリル
繊維、ポリエステル繊維、及び混紡繊維を市販洗
剤ザブ（花王株式会社製、登録商標）にて五回繰
り返し洗濯をし、布についている洗剤を除去した
後、本発明の濃縮型の衣料用柔軟仕上剤の0.1重
量％水溶液（有効分換算、3.5゜DH硬水）にて25
℃、浴比1/30で１分間撹拌下で処理した後、室内
で風乾後、25℃、65％RHの恒温恒湿室にて24時
間放置した。同様に通常濃度の柔軟仕上剤で処理
した衣料と柔軟性能を比較したところ、いずれも
十分な柔軟性能を有するものであつた。 The concentrated clothing fabric softener of the present invention, which essentially contains components (a) and (b), exhibits its effectiveness when used in an amount that is approximately inversely proportional to the active ingredient, compared to a fabric softener with a normal concentration. Therefore, it is an excellent product that leads to significant energy and resource savings at each stage of transportation, packaging, and inventory. [Example] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. Example of producing component (b) Heating isopropanol (100 parts) to reflux,
2-Hydroxy-3-methacryloyloxypropyldimethylstearylammonium chloride (5.4 parts) [in formula (1), R ₁ = methyl, R ₂ = stearyl, R ₃ , R ₄ = methyl, Y = oxygen, Z = 2- hydroxypropylene,
150 parts of an isopropanol solution containing the above was added dropwise over 2 hours. After the dropwise addition, the reaction solution was heated under reflux for 3 hours, diluted with 200 ml of water, and the isopropanol was distilled off to adjust the concentration to obtain an aqueous solution with a solid content of 20.0%. Examples 1 to 25, Comparative Examples 1 to 8 Using the softening agents shown in Table 3 containing the component (a) shown in Table 1 and the component (b) shown in Table 2, the following evaluations were performed. 1 Physical properties and stability Concentrated clothing fabric softener at -10°C, room temperature, 50°C
It was stored at ℃ for 20 days and its appearance and fluidity were measured. The results are shown in Table 3. All of the concentrated clothing fabric softeners of the present invention were good with almost no change over time. 2 Softness Ability After washing commercially available cotton towels, knitted underwear, acrylic fibers, polyester fibers, and blended fibers five times with commercially available detergent Zabu (manufactured by Kao Corporation, registered trademark) to remove detergent from the fabric. , a 0.1% by weight aqueous solution (effective content equivalent, 3.5゜DH hard water) of the concentrated clothing fabric softener of the present invention.
After stirring for 1 minute at a bath ratio of 1/30 at 1/30 °C, the mixture was air-dried indoors and then left in a constant temperature and humidity room at 25 °C and 65% RH for 24 hours. When the flexibility of the garments was similarly compared with that of clothing treated with a normal concentration of fabric softener, it was found that both had sufficient flexibility.

【表】【table】

【table】

Claims

[Claims] 1. A polymer containing as an essential component (a) a quaternary ammonium salt, (b) a cationic surfactant monomer having the structure of the following general formula (1) (In the formula, R ₁ represents hydrogen or a methyl group, and R ₂ represents a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms or a carbon number of 8 to 24 carbon atoms having a substituent.
represents a linear or branched alkyl group or alkenyl group, and R ₃ and R ₄ are hydrogen, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, or a polyoxyalkylene group (average addition molar Number = 1
~3). Y represents oxygen or -NH- group,
Z ₁ represents a hydroxyalkylene group having 2 to 4 carbon atoms. Moreover, X represents a halogen or an acid residue. ) as an active ingredient. 2. The concentrated clothing fabric softener according to claim 1, which contains component (a) in an amount of 7 to 30% by weight and component (b) in an amount of 0.2 to 10% by weight. 3. A patent claim in which the polymer of component (b) is a binary or ternary or more copolymer of a cationic surfactant monomer and another vinyl monomer, and the cationic surfactant monomer is 3 to 50% by weight. A concentrated clothing fabric softener according to item 1.