JP2012024537A - Polymeric deodorant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the deodorizing capacity of a deodorant based on a conventional acrylic polymer aqueous solution to cope with every malodor.SOLUTION: The deodorant containing an acrylic polymer with a molecular weight of 500,000 or more, trehalose and a polyphenol compound as main components is an aqueous deodorant obtained by dissolving these components in water together with alcohol to obtain an aqueous solution, adding acid to adjust pH to 4-8 and further adding an antibacterial agent. This deodorant is applicable to a wide range of malodor objects and malodor generation sources by a method of spraying, sprinkling, dipping, absorbing (contact), etc.

Description

The present invention is an aqueous antibacterial deodorant composition comprising an acrylic polymer as a main component. In particular, by diluting with water, a kind of hydrated film (hydroplane) is formed to cover and hydrate malodorous substances. The present invention relates to a polymer antibacterial deodorant that can be converted into a deodorant.

As the deodorant, types that repel, decompose, neutralize, cover, adsorb, and absorb the target malodor component are scattered as publicly known ones.
In addition, acrylic acid esters, methacrylic acid amides and the like (for example, Japanese Patent Publication No. 6-57238), ultra-high polymers (those having a molecular weight exceeding 10 million) using alcohol (C ₂ ), glycerin and chelate salts are petroleum products. There is also a gel-type product that masks volatile solvent (VOC), but it does not have a definite purpose for deodorizing, but each has its merits and demerits. Nearly impossible, after all, there is no choice but to deal with a lineup of several products, especially non-aqueous (not compatible with water) malodorous ingredients are in reality.

Of course, some acrylamide and polyamines are mainly used for adsorbing dirt components, and deodorization has been put into practical use on a molecular basis, but it is only an individual response.

Problems to be solved by the present invention

The malodorous substance is required to respond appropriately to odorous components that cause a person's olfaction and feel uncomfortable, cause mental inconvenience, or cause harmful physical effects.

It is more appropriate to focus on analogy, that is, human sensory tests, rather than digitally. That's the law of that German psychologist Weber Fechner: "The human sense is proportional to the logarithm of the amount added (LOGARYTHM)." For example, when you add sugar to a cup of coffee, try to see if you feel sweeter than the original sweetness when you add 1 g of sugar or when you add 2 g of sugar. If you look at it, you get the answer. Depending on the amount of coffee and the initial sweetness, you should feel sweet at some point. As for the brightness, humans have a human talent that it feels bright when one more candle is lit, but it is hard to feel that it has become brighter even if one is lit. An analogy. Weber ratio is different depending on the type of sensation (visual, auditory, olfactory, gustatory, perceptual), indicating weight is 1/53, light is 1/62, sound is 1/11, salty is 1/5, etc. is doing.
The same is true for olfaction, and this fact requires physical, chemical, biological, and psychological methods. Because it is not possible to standardize uniformly so that each person has ten colors. In other words, analog psychology must be taken in.
Based on this reality, the present inventor decided to prove the effect by requiring monitoring. In fact, Weber Fechner's idea is also adopted in the revised Odor Control Act (1990).

As in the present invention, the acrylic polymer has a high molecular weight (over 100,000), such as JP-A-2-149310 and JP-A-62-106766, which use a substance having a large molecular weight of an acrylic acid polymer as a deodorizing source. The radicals are chemically absorbed by the odorous substances with molecular weights of several hundreds of nitrogen and sulfur and adsorbed physicochemically to eliminate old-fashioned deodorization such as masking, offset, neutralization and adsorption. It is the configuration of the present invention in view of the fact that the handicapped one grasps the limit of forming a cluster on a kind of acrylic molecule, and the effect cannot be demonstrated by the sensory test described above.

That is, in view of the limitation of -OH radicals possessed by acrylic polymers, we obtained the suggestion that a consistent system such as the second and third polyhydroxy substances can eliminate the deodorant limitation. .
In particular, an acrylic anion / nonionic polymer (water-soluble) may be added with adhesiveness to suppress the function of the product.
In other words, it is free from agglomeration in long-term aqueous stability.
Of course, a large amount (10% or more) of a solubilizing solvent such as ethanol or propanol can be added to this, but alcohol odors and alcohol problems (odor, aldehyde formation, irritation, decreased endurance, etc.) occur simultaneously. May end up.

The deodorization due to the adsorption effect of the acrylic acid polymer is also related to the ionicity of the polymer, and plays a significant role with -OH ions and -COOH ions. In the present invention, it was proved that anions and nonions were practical, and it was confirmed that a polyol (polyhydric hydroxy compound) having an —OH bond was advantageous, and the present invention was achieved.

Means for solving the problem

That is, as a base of the present invention, using an aqueous acrylic polymer (anionic type, nonionic type) having a molecular weight of 1 million or more (first component), in examining the deodorant component having —OH as in the first component. The second component was trehalose. Trehalose is a starch-based polysaccharide that has been commonly used as an ancient Egyptian medicinal herb. Since it appeared in history as an old Jew who ate natural products to prevent hunger when moving largely under the leadership of Moses, it was made into a purer and more versatile ingredient with the power of biotechnology . As a deodorant component, it is well known as a deodorant for aging odor components such as Nonenal, and is useful as a deodorant for Nonenal.
It should be noted that —OH ions are bound uniformly (symmetry).
This proves that it is easy to adsorb on acrylic polymers and is an important partner for acrylic polymers. It goes without saying that ethanol and glycol are particularly excellent in this intervention. All result in a binding effect of -OH radicals.

当該成分は最終濃度として０．５〜１００ｐｐｍ、特に１〜５０ｐｐｍでベストバランスの濃度域を形成する。特にＰＧ，１．３ＢＧ，ＰＥＧ−４００，ＨＧ，ＤＰＧなどの多価アルコールを併用すると分散が良く、−ＯＨが互いに混合しあって一体となる。
これらは１〜２種以上を併用しても差し支えなく、それによって更にシナジー作用を予想できる。
第２成分のポリフェノールはタンニン系のものが好ましく、茶，グレープ，柿，トマト，南瓜，ケールなどの植物エキス内に存在する成分であり、基本的に複数の−ＯＨ基を保有することが特徴である。

当該物は固形分として０．０５〜１０ｗ％、とりわけ０．１〜５ｗ％がバランス組成として相応しい。
当該物も多価アルコール（ＰＧ，１．３ＢＧなど）との相性がコンビネーションを形成して使用されるのが好ましい。The present invention is an anionic or nonionic (can be used in combination) water-soluble acrylic polymer having a molecular weight of 1 million or more as the first component, and an average molecular weight of 500 to 30 million is particularly preferable.

The component forms a concentration range of best balance at a final concentration of 0.5 to 100 ppm, particularly 1 to 50 ppm. In particular, when a polyhydric alcohol such as PG, 1.3BG, PEG-400, HG, or DPG is used in combination, the dispersion is good, and -OH is mixed together and integrated.
One or more of these may be used in combination, and thereby further synergistic action can be expected.
The second component polyphenol is preferably a tannin-based one, and is a component present in plant extracts such as tea, grape, grape, tomato, nanban, kale, etc., and basically has a plurality of —OH groups. It is.

The product has a solid composition of 0.05 to 10 w%, particularly 0.1 to 5 w%, which is suitable as a balance composition.
The product is preferably used in combination with a polyhydric alcohol (PG, 1.3BG, etc.) to form a combination.

当該物は−ＯＨを６個以上有する水性の多糖類を構成している。炭水化物の主食料のでんぷんから分離・晶出・精製して合成される粉状物で、０．２〜１０ｗ％、好ましくは０．５〜７ｗ％がベストレシオとして使用される。
また本品も多価アルコールに助剤として利用することが好ましい。勿論１価アルコール（Ｃ_２〜４）の併有も妨げない。粘性を低下させることを考え、１価アルコールを配合した方が分散力が優れている。A representative starch-based polysaccharide as the third component is trehalose.

This product constitutes an aqueous polysaccharide having 6 or more —OH. It is a powdery substance synthesized by separating, crystallizing and refining from starch of carbohydrate main food, and 0.2 to 10 w%, preferably 0.5 to 7 w% is used as the best ratio.
This product is also preferably used as an auxiliary agent for polyhydric alcohols. Of course, coexistence of monohydric alcohol ( _C2-4 ) is not prevented. In consideration of lowering the viscosity, the dispersion power is superior when blended with a monohydric alcohol.

ーダ，トリクロロサリチルアニリド，ヘキサクロロフェン，トリブロムサラン，臭化アルキルイソキノリウム，ハロカルバン，レゾルシン，塩酸クロルヘキシジン，感光素２０１号などが挙げられる。これらは２種以上を併用しても良い。ＭＩＣとの関係で使用濃度はそれぞれ決定されるが、一般的には１００〜２００００ｐｐｍ位のレンジが選ばれるであろう。The above 1st-3rd component makes a -OH radical a common term, and makes a water medium, and comprises a composition. This cooperating substance of water molecules captures the malodorous component and the covalently bonded to hydrogen bonded chain results in the deodorizing effect.
In addition to these three components, it is necessary to add an antibacterial agent of water or an alcohol solvent. It is an indispensable substance to assist and support that the three components are defenseless against bacteria and reduce the deodorizing function. For example, triclosan, trichlorocarbanilide, PCMX, salicylic acid, α-bromocyanamide, gluconic acid, chlorhexidine, paraben, phenoxyethanol, benzalkonium chloride, aminoglycine amphoteric activity

, Trichlorosalicylanilide, hexachlorophene, tribromosaran, alkylisoquinolium bromide, halocarban, resorcin, chlorhexidine hydrochloride, photosensitizer 201 and the like. Two or more of these may be used in combination. The concentration used is determined in relation to the MIC, but generally a range of about 100 to 20000 ppm will be selected.

As a matter of course, the composition of the present invention is solidified by aerosol (LPG, DME), gelation (xanthan gum, metrose, locust bean gum, vinylpyrrolidone, CMC, carrageenan, cyclodextrin, PVM / MA, gelatin, casein, etc. ), Ethanol, propanol, PG, 1.3BG, HG, glycol ether, diacetone alcohol, alkane (heptane, hexane, undecane, dodecane, etc.), sorbitol, maltose, octanol, decanol, terpene series (limonene, pinene, myrcene, etc.) ) Solvent (for thinner) can be sprayed or made mousse. Of these, foaming surfactants such as higher alcohol alkyl fatty acid amide esters, alkyl glucosides, amine oxides, alkyl imidazolinium betaines, and sorbitan fatty acid esters are used as water-soluble surfactants for coating, impregnation and mousse processing. You can also deodorize.

The present invention is provided in the form of an aqueous solution (aqueous body).
That is, among the three main components, the first acrylic polymer is an ultra-polymer, so that a base agent is prepared before mixing with other components directly, and this is mixed with other components through water as appropriate. Is.
First, the acrylic polymer is completely dissolved in water together with polyhydric alcohol and ethanol, and adjusted to an aqueous solution of about 0.1 to 0.8%. In itself, as an antibacterial agent and best pH balancer (buffer agent), phosphate, citrate, sulfate, EDTA salt, gluconate, silicate, lactate, acetate, etc. are added as appropriate. Adjust the pH to 6-9. This base liquid of the first component is used as the first component in combination and mixed with the following components.

As the second component polyphenol compound, an aqueous solution (solid content: 10 to 15%) of a tannin-based one is blended in an amount of about 5 to 30 w%. The component is pretreated with ethanol, butanol, PG, DPG, methylmethoxybutanol or the like in advance, and blended in a form so as to fall within the range of at least 500 to 50,000 ppm as polyphenol.

The third component, trehalose, may be pre-dissolved in water or / and ethanol to make a 5-20% solution and added to the formulation 10-50%.
In order to improve these compatibility, hydrotropes such as sodium cumene sulfonate, sodium xylene sulfonate, urea, and sodium toluene sulfonate can be added.
This center is water, and an aqueous solution of the first to third components becomes the standard of the present invention.

Specifically, 2000 ppm of sodium acrylate polymer is mixed with purified water (deionized water) in an amount of 1 to 5% in advance, then 0.5 to 5 w% (solid content) as a polyphenol compound as the second component, and the third component. Trehalose is contained in an amount of 0.5 to 7 w% (solid content) to form a complete aqueous solution, and a buffer agent such as potassium lactate and lactic acid, sodium citrate and citric acid, sodium bicarbonate and soda ash, acidic sodium phosphate And potassium pyrophosphate and the like as an antibacterial agent, for example, an ethanol solution (10w%) of PCMX in an amount of 5 to 15w% and a paraben 0.05 to 1.2w% in an i-propanol solution of 10 to 10% The balance which produces a solution body to the last, such as 20w%, is required.

In particular, the present invention forms a kind of enclosing network by adding an ionic compound capable of dealing with malodorous substances as follows together with an antibacterial agent in order to promote the conjugation action of -OH radicals and malodorous substances of the polymer compound. .
Among them, various organic materials and salts thereof are preferable. Gluconic acid, glycolic acid, itaconic acid, maleic acid, succinic acid, malic acid, succinic acid, sebacic acid, tartaric acid, adipic acid, glutaric acid, lactic acid, citric acid, pyruvin Alkali salts (K, Na, NH ₄ , alkanolamine, Mg, Al, etc.) such as acid, salicylic acid, benzoic acid, metaphosphoric acid, pyrophosphoric acid and boric acid are preferably blended in an amount of 10 to 15000 ppm. On the other hand, for acidic deodorization, salts such as acetic acid, propionic acid, sulfamic acid, alkylsulfonic acid, ascorbic acid, sulfuric acid (K, Na, NH ₄ , alkanolamine, Mg, Al, etc.) are used as appropriate pH controllers. Containing 5 to 10000 ppm does not prevent it.
In addition, it has been proved that the combination of these acids and salts may serve as a controller for the viscosity and dispersibility of the acrylic polymer, and also exhibits better deodorizing action by sharing -OH radicals.

Effects of the present invention

The deodorant application obtained from the present invention is a method of spray (trigger), aerosol, spraying, watering, spraying, dipping, absorption (contact), etc. All liquid crystal forms can be applied.
For general household use, bath, toilet, kitchen, living room, bedroom, entrance, drainage, trash, garbage, clothes (after washing, after undressing), fresh food equipment (refrigerator, refrigerator), socks, shoes, hat , Sports goods, car care, tobacco odor, food odor, solvent odor, rot odor, acid odor, carpets and mats, filter surfaces of air conditioners and air purifiers, fresh flowers, etc.
For industrial use, industrial waste, solvent (thinner, ketone, organic halogen, kerosene, gasoline, etc.), paint, varnish, garbage dump, rubber, tire, tobacco odor, fresh food processing plant, factory (pulp, food processing, plastic Lockers, trains, airplanes, buses, trains, warehouses, poultry farms, pig farms, livestock and their processing plants (butter, cheese, margarine, etc.), printing factories, display processing plants, etc. , Recycling, coal mining, kitchen, bento processing plant, post-fire odor, hospitals, nursing homes, nurseries, and other odors and (sudden) unpleasant odors.

Moreover, all are connected to —OH radicals, and have good compatibility with people and the environment (nature), and as a product with harmony, its uses and values are wide-ranging. In addition, the total cost can be reduced by 1/2 to 1/10 or more of the products of other companies and conventional products, and economic efficiency can be expected.
Furthermore, if necessary, pigments, aromas, fragrances, medicinal ingredients, cleaning ingredients, etc. can be added to make it easy and quick to convert to new uses, and processability and handling are simple and secure, anytime, anywhere.・ It can be an intimate product that anyone can use immediately.

Next, specific effects of the present invention will be described with reference to examples.

［検討−２］
トリガー（０．２３ｍｌ／回），アトマイザー（０．０７ｍｌ／回）により吐出。
一般人１５人を含む２５人のモニターに対し、現在使用している代表的市販品（ＦＢ，ＡＳ）と比べて、それぞれの用途における消臭効果をアンケート式で調査した。その結果は以下の通りである。
評価法は単純に３点式とし、本発明品（表１の１）を用いた。
評価は下記として、その点数の合計が大きな程、商品としての効果があることを確認した。
評価：優れている…＋３
どちらとも言えない…０
劣っている…−３
評価対象
Ａ：トイレの使用後
Ｂ：排水溝のにおい
Ｃ：生ゴミ（三角コーナー）のにおい
Ｄ：タバコ臭
Ｅ：ソルベント（シンナー，石油，ガソリン，油性ペイントのにおい）
Ｆ：靴下や靴のにおい
Ｇ：キッチンの食品臭（特に魚や焼肉などのタンパク質系食品焼き付け時の煙臭）
Ｈ：車内のにおい
Ｉ：調理後のまな板のにおい

以上の結果、本発明品が市販品の物を大きく凌駕していることと、他社品は香料やアルコールのマスキングがかえって負の効果を招いている事が判った。
［検討−３］
検知管とガスクロマトグラフィーによって、本発明品と比較品の使用前後の消臭率（＝（最初の量−使用後の量）／最初の量×１００［％］），ｎ＝３の平均）を示す。
各悪臭物質の量は悪臭防止法を参考にしたもの

コメント：以上、検討の結果、本発明は市販品及び従来の技術より、いずれの悪臭物質にも圧倒的な効果を如実に証明している。[Examination-1]
The state of each composition is filled in a glass bottle at -15 to 40 ° C. for 30 days, and the change is observed (item: appearance and liquid)
Evaluation: ◎ ... almost unchanged
○… Slightly haze or thickening (reverts to some form)
△… Slightly lump, thickened, or more cloudy than the original
X: Agglomeration or sediment generation

[Examination-2]
Discharge by trigger (0.23 ml / time) and atomizer (0.07 ml / time).
The deodorizing effect in each application was investigated with a questionnaire system for 25 monitors, including 15 general people, compared to typical commercial products (FB, AS) currently used. The results are as follows.
The evaluation method was simply a three-point method, and the product of the present invention (1 in Table 1) was used.
The evaluation was as follows, and it was confirmed that the larger the total score, the more effective the product.
Evaluation: Excellent ... + 3
I can't say either ... 0
Inferior ...- 3
Evaluation target A: After use of toilet B: Smell of drainage c: Smell of garbage (triangular corner) D: Tobacco odor E: Solvent (thinner, petroleum, gasoline, scent of oil paint)
F: Smell of socks and shoes G: Food odor in the kitchen (especially smoke odor when baking protein foods such as fish and yakiniku)
H: Smell in car I: Smell of cutting board after cooking

As a result of the above, it was found that the product of the present invention greatly surpassed that of the commercial product, and that the products of other companies had a negative effect by changing the masking of fragrance and alcohol.
[Examination-3]
Deodorization rate before and after use of the product of the present invention and the comparative product (= (initial amount−amount after use) / initial amount × 100 [%]), average of n = 3) by detector tube and gas chromatography Indicates.
The amount of each malodorous substance is based on the Malodor Control Law

Comment: As described above, as a result of the examination, the present invention clearly proves an overwhelming effect on any offensive odor substances from commercial products and conventional techniques.

［官能テスト］
各試料をトリガースプレー（０．１２ｍｌ／回）に充填して、５人のモニターに５回スプレーした。そして１分後，１０分後のそれぞれの臭気を判定させた。
［悪臭物質の調整］
７０ｍｍφ，１２ｍｍ厚の円筒形シャーレに市販脱脂綿を３ｍｍ厚で敷布して、所定濃度（ｐｐｍ）の悪臭物質（１０種）を付有させて次の６ステージでの採点法により判定した。ｎ＝３として５人のモニターに実施した。数値が大きいほど効果があることを示す。結果は下表（表５）の通り。
ステージ：＋５…殆ど臭わない（８０〜９０％以上）
＋４…多少臭気が残る（６０〜７０％程度）
＋３…かなり臭気が取れている（５０％程度）
＋２…臭気が明らかに残っており不快（３０〜４０％程度）
＋１…わずかに臭気が取れている（１０〜２０％程度）
０…効果無し（０〜１０％程度）
判定：満点は５点×３回×５人＝７５点であり、ほぼ効果有り〜効果不十分のボーダーラ インは５５点である

コメント：以上のように本発明は３つの成分の相乗力により、明白な効果を上げている事が判明した。
［安定度テスト］
（１）試料に波長３９０ｎｍの紫外線を照射して、６０分後の外観及び臭気の変化を観察した
（２）長時間耐性テストとして４０℃の恒温室で４５日後の変化を観察した
容器はいずれもペットボトルを使用、結果は下表（表６）の通り。
所見：◎…変化無し
○…若干の色変有り
△…臭気（ＶＯＣ）有り、少し濁り有り
×…色変・臭気（ＶＯＣ）有り

コメント：本発明品は外観や臭気（物性変化）に対しても、極めて安定であることの確認を得た。The presence or absence of each component and the deodorizing effect of the product of the present invention were inspected to confirm the fact.

[Sensory test]
Each sample was filled in a trigger spray (0.12 ml / dose) and sprayed 5 times on 5 monitors. Then, after 1 minute and 10 minutes, the respective odors were judged.
[Adjustment of malodorous substances]
A commercially available absorbent cotton was spread with a thickness of 3 mm on a cylindrical petri dish of 70 mmφ and 12 mm thickness, and a malodorous substance (10 types) with a predetermined concentration (ppm) was attached, and the determination was made by the scoring method in the following 6 stages. n = 3 was carried out on 5 monitors. The larger the value, the more effective. The results are as shown in the following table (Table 5).
Stage: +5 ... hardly smell (80-90% or more)
+4 ... Some odor remains (about 60-70%)
+3 ... Smell odor (about 50%)
+2 ... Odor is clearly left and uncomfortable (about 30-40%)
+1 ... Slight odor is removed (about 10-20%)
0 ... No effect (0-10%)
Judgment: The perfect score is 5 points x 3 times x 5 people = 75 points, and the borderline that is almost effective-insufficient effect is 55 points

Comment: As described above, it has been found that the present invention has an obvious effect due to the synergistic force of the three components.
[Stability test]
(1) The sample was irradiated with ultraviolet rays having a wavelength of 390 nm, and changes in appearance and odor after 60 minutes were observed. (2) As a long-term durability test, any container that observed changes in a constant temperature room at 40 ° C. after 45 days PET bottles were used, and the results are shown in the table below (Table 6).
Findings: ◎ ... No change
○… Some color changes
Δ: Odor (VOC) present, slightly turbid
×… There is color change and odor (VOC)

Comment: It was confirmed that the product of the present invention is extremely stable with respect to appearance and odor (change in physical properties).

Claims (2)

As a deodorant component,
(1) Ultrahigh molecular acrylic polymer (molecular weight of 500,000 or more) 0.5-100 ppm
(1) Anionic

(2) or / and nonionic

(3) or / and cationic system

▲ 4 ▼ Trehalose

(5) Polyphenol compound

(2) Acids and their salts (carbonates, phosphates, silicates, hydroxycarboxylates) consisting of at least these three compounds as main components
(3) Alcohol compounds (1 to polyhydric alcohols: ethanol, IPA, PG, 1.3BG, HG, sorbitol, glycerin, DPG)
(4) Antibacterial agent A deodorant composition comprising these four components and having a pH set to 4-8. (1) As a deodorant main component,
(1) 1-50 ppm of ultra-high molecular acrylic (anion, nonionic) polymer with an average molecular weight of 500,000 or more
(2) Trehalose is 0.5-10w%
(3) 0.05-20 w% polyphenol compound
(2) 0.05-2 w% of acid and its salt
(3) 0.5-20 w% of alcohol compound (1-polyhydric alcohol)
Example) Monovalent: ethanol, propanol, butanol, hexanol, heptanol, etc. Divalent: EG, PEG, PG, 1.3BG, HG, DPG, etc. Trivalent or more: Glycerin, sorbitol, pentaerythritol, phenoxyethanol, maltitol, etc. (4) A deodorant composition in which water or an alcohol-soluble antibacterial agent is made into an aqueous body of 0.01 to 2 w% and the pH is adjusted to 4 to 8.