JP4393598B2 - Liquid bleach composition filled in a bag-like packaging container - Google Patents

Description

【００１６】
HLB が 4.5未満の非イオン界面活性剤を使用した場合、たとえば使用する柔軟性袋状包装容器がプラスチック製であると非イオン界面活性剤が染み込み、プラスチックを劣化させたり包装容器表面をべたつかせ商品価値を著しく損なう。またHLB が10を越える場合は洗浄性能が低下する。
【００１７】
非イオン界面活性剤は、包装容器に充填される漂白剤組成物中に 0.5〜50重量％、好ましくは１〜30重量％、より好ましくは１〜20重量％配合される。非イオン界面活性剤が 0.5％に満たない場合は洗浄性能が著しく低下し、一方50重量％を越えると粘度が著しく上昇し使いづらくなるという問題が生じる。
【００１８】
(b) 成分のうち、水溶液中で過酸化水素を発生させる化合物としては、過炭酸ナトリウム、トリポリリン酸ナトリウム・過酸化水素付加物、ピロリン酸ナトリウム・過酸化水素付加物、尿素・過酸化水素付加物、硫酸ナトリウム・過酸化水素付加物、過ホウ酸ナトリウム−水和物、過ホウ酸ナトリウム四水和物、過ケイ酸ナトリウム、過酸化ナトリウム、過酸化カルシウムなどが挙げられる。(b) 成分としては、過酸化水素、過炭酸ナトリウム、過ホウ酸ナトリウム−水和物、過ホウ酸ナトリウム四水和物が好ましい。
【００１９】
本発明ではキレート剤(c) としてカルシウムキレート定数（pK_Ca）が４以上のものを使用する。ここでpK_Caはカルシウムイオン電極を用い、キレート剤 0.1％溶液、pH10、25℃、0.1M-NH₄Cl-NH₄OH緩衝液を用いて測定したものである。容器の膨れや破損を引き起こす原因として微量のFe、Cu、Ni等の金属が混入している場合が多い。そのためこのような金属を封鎖するためにキレート剤を添加する必要があるが、カルシウムキレート定数が４より小さいものを用いると金属の封鎖が十分でないため、貯蔵中に容器の膨れや破裂が引き起こされる。また、上記キレート剤は袋状包装容器に充填される漂白剤組成物中に 0.2〜2.0 重量％、好ましくは 0.2〜1.0 重量％配合する必要がある。 0.2重量％に満たない場合、貯蔵安定性が低下する。一方、2.0 重量％を越える場合は、組成物の分離や白濁が起こり、商品としての価値を損なう。
【００２０】
キレート剤(c) の具体的例としては、エチレンジアミン４酢酸、ニトリロトリ酢酸、ヒドロキシエチルイミノジ酢酸等のアミノ酢酸系キレート剤、１−ヒドロキシ−1,1 −ジホスホン酸、エタンヒドロキシ−1,1,2 −トリホスホン酸、エタン−1,2 −ジカルボキシ−1,2 −ジホスホン酸、メタンヒドロキシホスホン酸等のホスホン酸系キレート剤、アクリル酸マレイン酸コポリマー等のカルボン酸系ポリマー、トリポリリン酸等のポリリン酸系キレート剤などを挙げることができる。これらの中でもホスホン酸系キレート剤及びカルボン酸系ポリマーが特に優れている。特に(c) はホスホン酸化合物がよい。
【００２１】
本発明では上記(a) 〜(c) 成分を含有する酸性液体漂白剤組成物は、最終組成物1,000 ｍｌを20℃でpH６にするために1/10Ｎ−NaOH水溶液が50ｍｌ以上、好ましくは80ｍｌ以上必要であるような酸性に調製されている。例えば必要に応じ、酸性物質(d) を、更に上記(a) 〜(c) 成分を含有する組成物に添加する。酸性物質としては下記のような具体的化合物を挙げることができる。
【００２２】
▲１▼ 酢酸、プロピオン酸、ブタン酸、ヘキサン酸、オクタン酸、デカン酸、ドデカン酸、テトラデカン酸、ヘキサデカン酸、オクタデカン酸、グリコール酸、乳酸、コハク酸、クエン酸、フマール酸、安息香酸、サリチル酸、フタール酸、テレフタール酸、トリメット酸等の有機カルボン酸類
▲２▼ ドデカンジ過酸、モノ過フタール酸等の過カルボン酸類
▲３▼ アクリル酸、メタクリル酸、マレイン酸等の不飽和カルボン酸から得られたホモポリマー又はコポリマー等のポリカルボン酸類
▲４▼ アルキル硫酸エステル、アルキルエーテル硫酸エステル、α−スルホ脂肪酸、α−スルホ脂肪酸エステル、アルキルベンゼンスルホン酸、ｐ−トルエンスルホン酸、ｐ−ヒドロキシスルホン酸等の有機スルホン酸や有機硫酸エステル類
▲５▼ １−ヒドロキシ−1,1 −ジホスホン酸、エタンヒドロキシ−1,1,2 −トリホスホン酸、エタン−1,2 −ジカルボキシ−1,2 −ジホスホン酸、メタンヒドロキシホスホン酸等のホスホン酸類
▲６▼ 硫酸、リン酸、塩酸、ポリリン酸、硝酸、珪酸等の無機酸
これらの中でも特に▲１▼、▲３▼、▲５▼、▲６▼が好ましい。また、(d) 成分の酸性物質がキレート能を有し、且つpK_Caが４以上であれば、これを(c) 成分のキレート剤として用いてもよい。
【００２３】
本発明の袋入り液体漂白剤は、上記必須成分を含有する液体漂白剤組成物を、200 〜800nm の光透過率が30％以下であるプラスチック製、又は紙製等の柔軟性の袋状包装容器に充填してなるものである。
【００２４】
柔軟性の袋状包装容器はプラスチックフィルム又は紙がよい。包装容器は５〜1,000 μｍ、好ましくは５〜500 μｍ、より好ましくは50〜500 μｍの厚さを有するプラスチックフィルムよりなることが好ましい。
【００２５】
プラスチック材料として線状低密度ポリエチレン、低密度ポリエチレン、無延伸ポリプロピレン、延伸ナイロン、延伸ポリプロピレン及びポリエチレンテレフタレートから選ばれる少なくとも１種を使用することが好ましい。また本発明のプラスチック製包装容器は多層積層構造を有するプラスチックフィルムからなるものが好ましい。例えば、容器の内側には線状低密度ポリエチレンを使用することが好ましく、最外層には機械的強度のあるプラスチック、例えば延伸ナイロンや、延伸ポリプロピレン等を用いることが好ましい。これら各層の厚さは５〜300 μｍが好適である。さらにこれらのプラスチック容器にはバリアー層、耐ピンホール層、引き裂き誘導層等を設けることも可能である。
【００２６】
また、光透過率を30％以下にするためにプラスチック製容器を多層構造のフィルムから形成し、その層間にアルミ箔や着色層を挟み込む方法等が考えられる。着色層は例えばグレーグラビアインキや白グラビアインキ、ブラックインキ、シルバーインキ等を塗布することなどで作製することができる。
【００２７】
本発明の袋状包装容器に使用されるプラスチックフィルムは、公知の方法で容易に製造できる。特に積層フィルムが好ましく、その製造方法としては、ドライラミネート法、Ｔダイ法、共押し出しラミネート法、インフレーション法、タンデムラミネート法等を挙げることができる。包装容器の形態は限定されないが、たとえば所望の大きさのプラスチックフィルムの周囲をヒートシールして所望の容量の袋（小袋）状とした容器を用いるのが好適である。
【００２８】
本発明の製品は使用者が容易に手で扱い使用できるような大きさの袋に分包されている。
【００２９】
本発明の製品では、内容物が容器にしみこんだり、しみだすことを防ぎ、よって容器がべたついたり、変形することがない。さらには内容物が分解しガスが発生することをと防ぎ、容器が膨れるような変形を防ぐ。
【００３０】
本発明において、プラスチック製、又は紙製等の柔軟性包装容器に充填する液体漂白洗浄剤組成物には、上記成分(a) 〜(d) 以外に所望によりアニオン界面活性剤あるいはカチオン界面活性剤から選ばれる少なくとも１種を配合することもできる。
【００３１】
アニオン界面活性剤としては平均炭素数８〜22のアルキルベンゼンスルホン酸塩、アルキル又はアルケニルエーテル硫酸エステル塩、アルキル又はアルケニル硫酸エステル塩類、α−オレフィンスルホン酸塩、飽和又は不飽和脂肪酸塩、Ｎ−アシルアミノ酸型界面活性剤、アルキル又はアルケニルエーテルカルボン酸塩、アミノ酸型界面活性剤、アルキル又はアルケニルリン酸エステル塩等が例示される。これらの中でもアルキルベンゼンスルホン酸塩が特に好ましい。
カチオン界面活性剤としては一般式(3) で示される化合物が好ましい。
【００３２】
【化２】

【００３３】
式中；R³、R⁴、R⁵、R⁶はこれらの内少なくとも１つは炭素数６〜20のアルキル基又はアルケニル基であり、残りが炭素数１〜３のアルキル基もしくはヒドロキシアルキレン基を示す。また、Y は有機又は無機の陰イオンである。
より具体的には以下の化合物が挙げられる。
【００３４】
【化３】

【００３５】
本発明では、所望により一般式(2) で示される漂白活性化剤を配合することができる。その好ましい含有量は0.1 〜10重量％である。
【００３６】
【化４】

【００３７】
〔式中、R²は炭素数５〜19のアルキル基あるいはアルケニル基を示し、Z は-SO₃M 又は-COOM を示す。M は有機又は無機の陽イオンである。〕
これらの具体例としては以下の化合物が挙げられる。
【００３８】
【化５】

【００３９】
【実施例】
以下実施例にて本発明を説明するが、本発明はこれらの実施例に限定されるものではない。
【００４０】
〔プラスチック製小袋の調製〕
・小袋Ａ：厚さ20μｍの延伸ナイロン、厚さ 100μｍの線状低密度ポリエチレン、厚さ50μｍのアルミ箔及び厚さ15μｍの延伸ナイロンをこの順に重ね合わせて長方形の形状としたものを二組用意し、それぞれの厚さ15μｍの延伸ナイロンが内側になるように重ね合わせ、その三辺をヒートシールして容積1000mlの小袋を作成した。この小袋の 200〜800nm の光透過率を測定したところ５％以下であった。なお、液体漂白剤組成物は、厚さ15μｍの延伸ナイロンの間に充填し、袋の残りの一辺をヒートシールして小袋入りの液体漂白剤組成物を得た。
【００４１】
・小袋Ｂ：厚さ20μｍの延伸ナイロン及び厚さ 100μｍの線状低密度ポリエチレンを重ね合わせたプラスチックシートにグレーグラビアインキ３μｍ、白グラビアインキ３μｍを順次塗布し、さらにその上に厚さ50μｍの延伸ナイロンを重ね合わせて長方形の形状としたものを二組用意し、厚さ50μｍの延伸ナイロンが内側になるように重ね合わせ、小袋Ａと同様の方法で小袋を作成した。この小袋の光透過率は25％であった。なお、液体漂白剤組成物は、厚さ50μｍの延伸ナイロンの間に充填し、袋の残りの一辺をヒートシールして小袋入りの液体漂白剤組成物を得た。
【００４２】
・小袋Ｃ：厚さ20μｍの延伸ナイロン、厚さ 100μｍの線状低密度ポリエチレン、厚さ15μｍ延伸ナイロンをこの順に重ね合わせて長方形の形状としたものを二組用意し、それぞれの厚さ15μｍの延伸ナイロンが内側になるように重ね合わせ、小袋Ａと同様の方法で小袋を作成した。この小袋の 200〜800nm の光透過率を測定したところ75％であった。なお、液体漂白剤組成物は、厚さ15μｍの延伸ナイロンの間に充填し、袋の残りの一辺をヒートシールして小袋入りの液体漂白剤組成物を得た。
【００４３】
・小袋Ｄ：厚さ20μｍの延伸ナイロン及び厚さ 100μｍの線状低密度ポリエチレンを重ね合わせたプラスチックシートにグレーグラビアインキ１μｍ、白グラビアインキ１μｍを順次塗布し、さらにその上に厚さ50μｍの延伸ナイロンを重ね合わせて長方形の形状としたものを二組用意し、厚さ50μｍの延伸ナイロンが内側になるように重ね合わせ、小袋Ａと同様の方法で小袋を作成した。この小袋の光透過率は35％であった。なお、液体漂白剤組成物は、厚さ50μｍの延伸ナイロンの間に充填し、袋の残りの一辺をヒートシールして小袋入りの液体漂白剤組成物を得た。
【００４４】
〔袋入り漂白剤の調製及び評価〕
下記の成分を使用して表２〜５に示す液体漂白剤組成物を調製し、上記で示した小袋に入れ太陽光がよく当たる６Ｆ建てビルの屋上に３ヶ月間放置した。その後、下記の基準で容器の外観を目視にて評価した。その結果を表２〜５に示す。また、小袋に充填する液体漂白剤組成物1000mlををpH６（20℃）にするために必要なN/10-NaOH の量も併せて表２〜５に示す。
【００４５】
(a) 成分：
ａ−１ C₁₂H₂₅(OC₂H₄)₄-OH （HLB ＝4.50）
ａ−２ C₁₀H₂₁(OC₂H₄)₆-OCH₃ （HLB ＝5.70）
ａ−３ C₁₂H₂₅(OC₂H₄)₂₀-OH （HLB ＝9.80）
ａ−４ C₁₂H₂₅(OC₂H₄)₈-OH （HLB ＝5.84）
ａ’−１ C₁₈H₃₇(OC₂H₄)₃₅-OH （HLB ＝11.90 ）
ａ’−２ C₁₀H₂₁(OC₂H₄)₃-OCH₃ （HLB ＝4.07）
(b) 成分：H₂O₂（過酸化水素）
(c) 成分：
ｃ−１ ニトリロトリ酢酸 (pK_Ca＝6.6)
ｃ−２ アクリル酸／マレイン酸コポリマー (分子量70000 、モノマー比＝７／３、pK_Ca＝5.0)
ｃ’−１ ポリアクリル酸ソーダ (分子量8000、pK_Ca＝3.2)
ｃ’−２ クエン酸ソーダ (pK_Ca＝3.2)
(d) 成分：
ｄ−１ 硫酸
ｄ−２ リン酸
ｄ−３ ディクエスト2010cs（日本モンサント社製）
(e) 成分：
【００４６】
【化６】

【００４７】
(f) 成分：
ｆ−１ C₁₂ アルキルベンゼンスルホン酸
ｆ−２ N −テトラデシル−N,N −ジメチル−N −エチルアンモニウムエチルサルフェート
＜小袋外観変化＞
全く変化がない … ５
やや膨れている … ４
膨れている … ３
著しく膨れている … ２
容器が破裂した … １
【００４８】
【表２】

【００４９】
【表３】

【００５０】
【表４】

【００５１】
【表５】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid bleach composition filled in a flexible bag-like packaging container, and more specifically, a liquid filled in a flexible bag-like packaging container that does not cause swelling or breakage of the container during storage. The present invention relates to a bleaching composition.
[0002]
[Prior art and problems to be solved by the invention]
Bleaching can be divided into chlorine bleach and oxygen bleach, but chlorine bleach is limited in the fibers that can be used, cannot be used for colors and patterns, and has a unique odor, Oxygen-based bleaches that do not have these drawbacks have recently become very popular. Among these oxygen bleaches, sodium percarbonate and sodium perborate are used as powder bleaches, and hydrogen peroxide is used as a liquid oxygen bleach, especially in terms of ease of use. Things are preferred.
[0003]
This liquid bleaching agent composition has poor stability of hydrogen peroxide used as a bleaching active species, and generates oxygen gas during storage. For this reason, as the container for the liquid bleach composition, a container having a strong structure as disclosed in JP-A-4-220499 is used. However, in recent years, liquid bleach for refilling in small plastic film sachets has been desired due to problems such as resource saving and plastic waste.
[0004]
Examples of the plastic bag-like packaging container used for such refilling bleaching agents include those disclosed in JP-T-3-505322 and JP-A-3-123847. When such a container is used, there has been a problem that the container is significantly swollen or ruptured during storage. This is because hydrogen peroxide is unstable with respect to light. In order to avoid this, it is conceivable that the plastic bag-like packaging container is provided with a light-shielding property. Examples thereof include a method of forming a metal layer such as an aluminum layer on the inner surface of a plastic container having a multilayer structure, a method of forming a gray ink layer, and the like. However, even when these plastic packaging containers are used, the storage stability is insufficient. Also, liquid bleach usually contains a nonionic surfactant as a cleaning component, but the nonionic surfactant penetrates into the resin layer of plastic packaging containers, causing problems such as deterioration of the packaging container and stickiness of the surface. There is.
[0005]
Accordingly, an object of the present invention is to provide a liquid bleaching composition filled in a flexible bag-like packaging container in which these drawbacks are improved.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have filled a specific liquid bleach composition into a flexible bag-shaped packaging container made of light-shielding plastic or paper. The inventors have found that the above object can be achieved, and have completed the present invention.
[0007]
That is, the present invention provides (a) 0.5 to 50% by weight of a nonionic surfactant represented by the general formula (1) having an HLB of 4.5 to 10 determined by the method of Davis,
R ¹ -X- (AO) _m -Y (1)
[Where,
R ¹ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms or an aryl group which may be substituted with a linear or branched alkyl group having 1 to 18 carbon atoms in total;
X is a -O- group,
A is a linear or branched alkylene group having 2 to 3 carbon atoms,
Y is H or an alkyl group having 1 to 3 carbon atoms,
m is a number having an average value of 3 to 50. ]
(b) Acid liquid bleach containing 0.1 to 30% by weight of hydrogen peroxide or a compound that generates hydrogen peroxide in an aqueous solution and (c) 0.2 to 2.0% by weight of a chelating agent having a calcium chelate constant (pK _Ca ) of 4 or more The final composition is prepared so that 50 ml of 1/10 N-NaOH aqueous solution, preferably 80 ml or more, is required to bring 1,000 ml of the composition to pH 6 at 20 ° C., and 200 to 800 nm. It is a liquid bleach composition filled in a flexible bag-shaped packaging container having a light transmittance of 30% or less, preferably 25% or less.
[0008]
Preferably, the final composition is 1000 ml of the final composition with at least one acidic substance (d) selected from carboxylic acids, percarboxylic acids, polycarboxylic acids, phosphoric acid, polyphosphoric acid, sulfuric acid, phosphonic acids and sulfonic acids. It is prepared so that 50 ml or more of 1/10 N-NaOH aqueous solution is required to adjust pH to 6 at 20 ° C.
[0009]
The present invention also provides the above-described composition and the liquid bleach composition product filled in the flexible bag-shaped packaging container containing the composition.
[0010]
Accordingly, the present invention can provide a liquid bleach composition filled in a flexible bag-like packaging container that does not cause swelling or breakage of the container during storage.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
As the nonionic surfactant (a) of the present invention, a nonionic surfactant represented by the general formula (1) having an HLB of 4.5 to 10 determined by the method of Davis is used.
[0012]
R ¹ -X- (AO) _m -Y (1)
[Where,
R ¹ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms or an aryl group which may be substituted with a linear or branched alkyl group having 1 to 18 carbon atoms in total;
X is a -O- group,
A is a linear or branched alkylene group having 2 to 3 carbon atoms,
Y is H or an alkyl group having 1 to 3 carbon atoms,
m is a number having an average value of 3 to 50. ]
In the general formula (1), the A group is a linear or branched alkylene group having 2 to 3 carbon atoms, for example, an ethylene group or a propylene group (preferably a branched propylene group). The polymer may be polymerized in a random type.
[0013]
In the composition, preferably, in formula (1), R ¹ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, X is an —O— group, and A is an ethylene group. Y is H or methyl, and m is a number having an average value of 3-50. In formula (1), R ¹ is preferably a linear alkyl group having 10 to 18 carbon atoms.
[0014]
Here, HLB by Davis' method is “surfactant properties, application, chemical ecology” 7th edition, 24 pages, Fumio Kitahara, Yasukatsu Tamai, Shigeo Hayano, Ichiro Hara, Kodansha Scientific, published (1990) In the present invention, it is preferable to use a nonionic surfactant having HLB = 4.5 to 10, preferably 4.5 to 8, more preferably 4.5 to 7. A more specific example is shown in Table 1.
[0015]
[Table 1]

[0016]
If a nonionic surfactant with an HLB of less than 4.5 is used, for example, if the flexible bag-like packaging container used is made of plastic, the nonionic surfactant will permeate and the plastic will deteriorate or the packaging container surface will become sticky. Significantly detracts from value. If the HLB exceeds 10, the cleaning performance will be degraded.
[0017]
The nonionic surfactant is added in an amount of 0.5 to 50% by weight, preferably 1 to 30% by weight, more preferably 1 to 20% by weight, in the bleaching composition filled in the packaging container. When the nonionic surfactant is less than 0.5%, the cleaning performance is remarkably deteriorated. On the other hand, when it exceeds 50% by weight, the viscosity is remarkably increased and it becomes difficult to use.
[0018]
(b) Among the components, compounds that generate hydrogen peroxide in aqueous solution include sodium percarbonate, sodium tripolyphosphate / hydrogen peroxide adduct, sodium pyrophosphate / hydrogen peroxide adduct, urea / hydrogen peroxide addition Sodium sulfate / hydrogen peroxide adduct, sodium perborate-hydrate, sodium perborate tetrahydrate, sodium persilicate, sodium peroxide, calcium peroxide and the like. As the component (b), hydrogen peroxide, sodium percarbonate, sodium perborate-hydrate, and sodium perborate tetrahydrate are preferable.
[0019]
In the present invention, a chelating agent (c) having a calcium chelate constant (pK _Ca ) of 4 or more is used. Here, pK _Ca was measured using a calcium ion electrode and using a 0.1% chelating agent solution, pH 10, 25 ° C., and 0.1 M NH ₄ Cl—NH ₄ OH buffer. In many cases, trace amounts of metals such as Fe, Cu, and Ni are mixed as a cause of causing swelling and damage of the container. Therefore, it is necessary to add a chelating agent to sequester such a metal, but if a calcium chelate constant smaller than 4 is used, the metal is not sequestered sufficiently, which causes the container to swell or burst during storage. . The chelating agent should be blended in the bleach composition filled in the bag-like packaging container in an amount of 0.2 to 2.0% by weight, preferably 0.2 to 1.0% by weight. When it is less than 0.2% by weight, the storage stability is lowered. On the other hand, when the content exceeds 2.0% by weight, the composition is separated and clouded, which impairs the value as a product.
[0020]
Specific examples of the chelating agent (c) include aminoacetic acid-based chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid and hydroxyethyliminodiacetic acid, 1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1, 2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, phosphonic acid-based chelating agents such as methanehydroxyphosphonic acid, carboxylic acid-based polymers such as acrylic acid maleic acid copolymer, and polyphosphoric acid such as tripolyphosphoric acid Examples include acid-based chelating agents. Among these, phosphonic acid chelating agents and carboxylic acid polymers are particularly excellent. In particular, (c) is preferably a phosphonic acid compound.
[0021]
In the present invention, the acidic liquid bleach composition containing the components (a) to (c) described above has a 1/10 N NaOH aqueous solution of 50 ml or more, preferably 80 ml in order to make 1,000 ml of the final composition pH 6 at 20 ° C. It is prepared to be acidic as necessary. For example, if necessary, the acidic substance (d) is further added to the composition containing the components (a) to (c). Examples of the acidic substance include the following specific compounds.
[0022]
(1) Acetic acid, propionic acid, butanoic acid, hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, glycolic acid, lactic acid, succinic acid, citric acid, fumaric acid, benzoic acid, salicylic acid , Organic carboxylic acids such as phthalic acid, terephthalic acid, trimetic acid, etc. (2) percarboxylic acids such as dodecanediperic acid and monoperphthalic acid (3) obtained from unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, etc. Polycarboxylic acids such as homopolymers or copolymers (4) alkyl sulfates, alkyl ether sulfates, α-sulfo fatty acids, α-sulfo fatty acid esters, alkylbenzene sulfonic acids, p-toluenesulfonic acids, p-hydroxysulfonic acids, etc. Organic sulfonic acids and organic sulfates (5) 1 Phosphonic acids such as hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, etc. (6) sulfuric acid, Among these inorganic acids such as phosphoric acid, hydrochloric acid, polyphosphoric acid, nitric acid and silicic acid, (1), (3), (5) and (6) are particularly preferable. If the acidic substance of component (d) has chelating ability and pK _Ca is 4 or more, it may be used as the chelating agent of component (c).
[0023]
A liquid bleaching agent in a bag according to the present invention is a flexible bag-like packaging made of a plastic or paper or the like having a light transmittance of 200 to 800 nm of 30% or less. The container is filled.
[0024]
The flexible bag-like packaging container is preferably a plastic film or paper. The packaging container is preferably made of a plastic film having a thickness of 5 to 1,000 μm, preferably 5 to 500 μm, more preferably 50 to 500 μm.
[0025]
It is preferable to use at least one selected from linear low density polyethylene, low density polyethylene, unstretched polypropylene, stretched nylon, stretched polypropylene and polyethylene terephthalate as the plastic material. The plastic packaging container of the present invention is preferably made of a plastic film having a multilayer laminated structure. For example, it is preferable to use linear low density polyethylene for the inside of the container, and it is preferable to use plastic with mechanical strength, such as stretched nylon or stretched polypropylene, for the outermost layer. The thickness of each of these layers is preferably 5 to 300 μm. Further, these plastic containers can be provided with a barrier layer, a pinhole-resistant layer, a tear induction layer, and the like.
[0026]
Further, in order to reduce the light transmittance to 30% or less, a method of forming a plastic container from a multilayer film and sandwiching an aluminum foil or a colored layer between the layers can be considered. The colored layer can be produced, for example, by applying gray gravure ink, white gravure ink, black ink, silver ink or the like.
[0027]
The plastic film used for the bag-shaped packaging container of the present invention can be easily produced by a known method. A laminated film is particularly preferred, and examples of the production method include a dry lamination method, a T-die method, a coextrusion lamination method, an inflation method, and a tandem lamination method. Although the form of the packaging container is not limited, for example, it is preferable to use a container that is heat-sealed around a plastic film having a desired size to form a bag (small bag) having a desired capacity.
[0028]
The product of the present invention is packaged in a bag of a size that can be easily handled and used by the user.
[0029]
In the product of the present invention, the contents are prevented from soaking into the container, and the container is not sticky or deformed. Furthermore, the contents are prevented from being decomposed and generating gas, and the container is prevented from being swelled.
[0030]
In the present invention, the liquid bleaching detergent composition filled in a flexible packaging container made of plastic or paper is preferably an anionic surfactant or a cationic surfactant in addition to the components (a) to (d). It is also possible to blend at least one selected from
[0031]
Examples of the anionic surfactant include alkylbenzene sulfonates having an average carbon number of 8 to 22, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, saturated or unsaturated fatty acid salt, and N-acyl. Examples include amino acid type surfactants, alkyl or alkenyl ether carboxylates, amino acid type surfactants, alkyl or alkenyl phosphate esters, and the like. Among these, alkylbenzene sulfonate is particularly preferable.
As the cationic surfactant, a compound represented by the general formula (3) is preferable.
[0032]
[Chemical formula 2]

[0033]
Wherein at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is an alkyl group or alkenyl group having 6 to 20 carbon atoms, and the remainder is an alkyl group or hydroxyalkylene group having 1 to 3 carbon atoms. Indicates. Y is an organic or inorganic anion.
More specifically, the following compounds may be mentioned.
[0034]
[Chemical 3]

[0035]
In the present invention, a bleaching activator represented by the general formula (2) can be blended if desired. Its preferred content is 0.1 to 10% by weight.
[0036]
[Formula 4]

[0037]
[Wherein R ² represents an alkyl group or alkenyl group having 5 to 19 carbon atoms, and Z represents —SO ₃ M or —COOM. M is an organic or inorganic cation. ]
Specific examples thereof include the following compounds.
[0038]
[Chemical formula 5]

[0039]
【Example】
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
[0040]
[Preparation of plastic sachet]
・ Sachet A: Two sets of rectangular shape with 20μm thick stretched nylon, 100μm thick linear low density polyethylene, 50μm thick aluminum foil and 15μm thick stretched nylon in this order Then, each stretched nylon having a thickness of 15 μm was superposed so as to be on the inner side, and the three sides were heat-sealed to prepare a 1000 ml capacity pouch. When the light transmittance of 200 to 800 nm of this sachet was measured, it was 5% or less. The liquid bleach composition was filled between stretched nylons having a thickness of 15 μm, and the remaining side of the bag was heat sealed to obtain a liquid bleach composition in a small bag.
[0041]
・ Sachet B: Apply gray gravure ink 3μm and white gravure ink 3μm sequentially on a plastic sheet with 20μm thick stretched nylon and 100μm thick linear low density polyethylene, and then stretch 50μm thick Two pairs of nylons with a rectangular shape were prepared and overlapped so that the stretched nylon with a thickness of 50 μm was inside, and sachets were created in the same manner as sachet A. The light transmittance of this sachet was 25%. The liquid bleach composition was filled in stretched nylon having a thickness of 50 μm, and the remaining side of the bag was heat sealed to obtain a liquid bleach composition in a small bag.
[0042]
・ Sachet C: Prepare two sets of rectangular shape by overlapping stretched nylon with thickness of 20μm, linear low density polyethylene with thickness of 100μm, stretched nylon with thickness of 15μm in this order, each with thickness of 15μm The stretched nylon was superposed so that it was on the inside, and a pouch was prepared in the same manner as pouch A. The light transmittance of 200 to 800 nm of this sachet was measured and found to be 75%. The liquid bleach composition was filled between stretched nylons having a thickness of 15 μm, and the remaining side of the bag was heat sealed to obtain a liquid bleach composition in a small bag.
[0043]
・ Sachet D: Gray gravure ink 1μm and white gravure ink 1μm are sequentially applied to a plastic sheet on which stretched nylon with a thickness of 20μm and linear low density polyethylene with a thickness of 100μm is layered, and further stretched with a thickness of 50μm Two pairs of nylons with a rectangular shape were prepared and overlapped so that the stretched nylon with a thickness of 50 μm was inside, and sachets were created in the same manner as sachet A. The light transmittance of this sachet was 35%. The liquid bleach composition was filled in stretched nylon having a thickness of 50 μm, and the remaining side of the bag was heat sealed to obtain a liquid bleach composition in a small bag.
[0044]
[Preparation and Evaluation of Bag Bleach]
Liquid bleaching compositions shown in Tables 2 to 5 were prepared using the following ingredients, placed in the sachets shown above, and left for 3 months on the roof of a 6F building where the sunlight hits well. Thereafter, the appearance of the container was visually evaluated according to the following criteria. The results are shown in Tables 2-5. Further, Tables 2 to 5 also show the amount of N / 10-NaOH necessary for adjusting 1000 ml of the liquid bleach composition to be filled in the sachet to pH 6 (20 ° C.).
[0045]
(a) Ingredients:
a-1 C ₁₂ H ₂₅ (OC ₂ H ₄ ) ₄ -OH (HLB = 4.50)
a-2 C ₁₀ H ₂₁ (OC ₂ H ₄ ) ₆ -OCH ₃ (HLB = 5.70)
a-3 C ₁₂ H ₂₅ (OC ₂ H ₄ ) ₂₀ -OH (HLB = 9.80)
a-4 C ₁₂ H ₂₅ (OC ₂ H ₄ ) ₈ -OH (HLB = 5.84)
a'-1 C ₁₈ H ₃₇ (OC ₂ H ₄ ) ₃₅ -OH (HLB = 11.90)
a'-2 C ₁₀ H ₂₁ (OC ₂ H ₄ ) ₃ -OCH ₃ (HLB = 4.07)
(b) Component: H ₂ O ₂ (hydrogen peroxide)
(c) Ingredients:
c-1 Nitrilotriacetic acid (pK _Ca = 6.6)
c-2 Acrylic acid / maleic acid copolymer (molecular weight 70000, monomer ratio = 7/3, pK _Ca = 5.0)
c′-1 Sodium polyacrylate (molecular weight 8000, pK _Ca = 3.2)
c'-2 Sodium citrate (pK _Ca = 3.2)
(d) Ingredients:
d-1 Sulfuric acid d-2 Phosphoric acid d-3 Dequest 2010cs (manufactured by Monsanto Japan)
(e) Ingredients:
[0046]
[Chemical 6]

[0047]
(f) Component:
f-1 C ₁₂ alkylbenzene sulfonic acid f-2 N -tetradecyl-N, N-dimethyl-N-ethylammonium ethyl sulfate <Sachet appearance change>
No change at all ... 5
Slightly swollen… 4
Swelling ... 3
Swells significantly ... 2
Container ruptured ... 1
[0048]
[Table 2]

[0049]
[Table 3]

[0050]
[Table 4]

[0051]
[Table 5]

Claims (8)

(a) The HLB obtained by the method of Mr. Davis is 4.5 to 10, and the nonionic surfactant represented by the formula (1) is 0.5 to 50% by weight,
R ¹ -X- (AO) _m -Y (1)
[Where,
R ¹ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms or an aryl group which may be substituted with a linear or branched alkyl group having 1 to 18 carbon atoms in total;
X is a -O- group,
A is a linear or branched alkylene group having 2 to 3 carbon atoms,
Y is H or an alkyl group having 1 to 3 carbon atoms,
m is a number having an average value of 3 to 50. ]
(b) 0.1 to 30% by weight of hydrogen peroxide or a compound that generates hydrogen peroxide in an aqueous solution and
(c) An acidic liquid bleach composition containing 0.2 to 2.0% by weight of an aminoacetic acid chelating agent, phosphonic acid chelating agent, carboxylic acid polymer or polyphosphoric acid chelating agent having a calcium chelate constant (pK _Ca ) of 4 or more Because
The final composition is prepared so that more than 50 ml of 1/10 N-NaOH aqueous solution is necessary to bring 1,000 ml of the solution to pH 6 at 20 ° C.
Liquid bleaching agent obtained by filling the final composition into a plastic flexible bag-shaped packaging container having a light transmittance of 200 to 800 nm and having a light transmittance of 30% or less, comprising a plastic film having a thickness of 50 to 500 μm. Composition product. Final composition carboxylic acids, percarboxylic acids, polycarboxylic acids, phosphoric acid, polyphosphoric acid, by at least one acidic substance selected from sulfuric San及 beauty sulfonic acids (d), the final composition 1,000 ml 20 ° C. The liquid bleach composition product according to claim 1, which is prepared so that at least 50 ml of 1/10 N-NaOH aqueous solution is required to adjust the pH to 6.   The liquid bleach composition product according to claim 1 or 2, further comprising an anionic surfactant or a cationic surfactant. The liquid bleach composition product according to any one of claims 1 to 3, further comprising 0.1 to 10% by weight of a bleach activator represented by the formula (2).

[Wherein R ² is an alkyl group or alkenyl group having 5 to 19 carbon atoms, Z is —SO ₃ M or —COOM, and M is an organic or inorganic cation. ]   The liquid bleach composition product according to any one of claims 1 to 4, wherein the plastic is at least one selected from linear low density polyethylene, low density polyethylene, unstretched polypropylene, stretched nylon, stretched polypropylene and polyethylene terephthalate. . In the formula (1), R ¹ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, X is an —O— group, A is an ethylene group, and Y is H or methyl. M is a number having an average value of 3 to 50. The liquid bleach composition product according to any one of claims 1 to 5.   The liquid bleach composition product according to any one of claims 1 to 6, wherein (c) is a phosphonic acid compound. The liquid bleach composition product according to any one of claims 1 to 7, wherein in the formula (1), R ¹ is a linear alkyl group having 10 to 18 carbon atoms.