CN1204361A - Improved compositions containing organic compounds - Google Patents

Abstract

Pine oil type concentrate compositions and cleaning compositions providing sanitizing effects comprise a germicidal active cationic surfactant, a co-solvent, a non-ionic surfactant system, and generally include a relatively high amount of fragrance and/or fragrance adjuvant compositions. The preferred embodiments of the pine oil type cleaning compositions provide the benefits of good cleaning, effective sanitizing action, good blooming upon addition to an excess of water and long lasting fragrance, and low irritancy levels notwithstanding the relatively high levels of organic solvents comprised in the compositions.

Description

Improved compositions containing organic compounds

The present invention relates to improved detergent compositions. More particularly, the present invention relates to improved pine oil-type cleaning compositions and concentrates thereof which are particularly useful for cleaning hard surfaces.

A specific class of detergent compositions are pine oil type detergent compositions, typically such substances include one or more resins or oils extracted from coniferous trees, and are usually diluted with water for use as a diluent for washing in a milky or turbid state. Such pine oil-based cleaning compositions are typically provided as concentrated compositions which are subsequently diluted with water by the end user/consumer to form a cleaning composition. Pine oil is however known to leave an undesirable surface residue, especially on hard surfaces, and is also known to be an irritant, especially to the eyes, skin and mucous membranes. Also, while pine oil is known for its detersive properties, it is not generally considered a useful broad-spectrum antimicrobial or disinfectant.

It is an object of the present invention to provide improved pine oil-type detergent compositions in "concentrated" form having one or more of the above identifiable characteristics, particularly when the amount of pine oil in the composition is reduced, with a significant effect Cream effect, effective cleansing action and long-lasting fragrance. In another aspect, the present invention provides "cleaning compositions" which are aqueous dilutions of these improved pine oil-type cleaning compositions which, when prepared, exhibit good blooming and good hard surface cleaning and/or disinfection effect.

These and other advantages of the invention will be apparent from the following detailed description of the invention.

The compositions of the present invention contain the following components:

A) a pine oil formulation comprising at least about 60% alpha-terpineol;

B) a cosolvent;

C) a nonionic surfactant system, desirably comprising two or more nonionic surfactants, at least one of which has a cloud point in water of 20°C or less;

D) at least one quaternary ammonium cationic surfactant with bactericidal activity;

E) Fragrance/flavor enhancers; and

F) water.

In addition to the aforementioned components, the compositions of the present invention may optionally include conventional amounts of additives known in the art.

The concentrate of the pine oil type cleaning composition is different from the cleaning composition in the prior art, and also includes a bactericidal effect, a good blooming effect and a high concentration of fragrance and/or fragrance solubilizer components, so the present invention The inventors have discovered that the concentrate compositions of the present invention can be produced using these components selected in a particular formulation. It is surprising that these compositions of the present invention, despite their inclusion of relatively high levels of perfume and/or perfume solubilizing components, still possess many of the characteristics desired in the above-mentioned pine oil-type cleaning compositions, especially "blooming". This is an important and surprising feature of the present invention, since such concentrates, due to the use of higher levels of perfume and/or perfume solubilizer components (known to be organic components), would have It is believed that the desired blooming effect will be significantly reduced or inactivated when further used for dilution. The observed "blooming" can be interpreted as a change in the appearance of the water, from essentially colorless and clear to milky white or creamy yellow to cloudy. This state of affairs achieved in compositions of the present invention containing relatively high levels of perfume and/or perfume solubilizer components is surprising to say the least. Component A) The composition of the present invention contains a pine oil component. Pine oil is an organic solvent, a complex mixture of oils, alcohols, acids, esters, aldehydes and other organic compounds. These include terpenes, which include a number of related alcohols or ketones. Some important components include terpineol, one of three isomers with _the molecular formula _C10H17OH . Useful pine oils include synthetic pine oils, also their vapors and pine sulfates, and generally contain relatively high levels of pinoresinol. Other important compounds include α- and β-pinene (pine resin), abietic acid (rosin) and other isoprene derivatives.

Particularly potent pine oils currently available include ^Glidco_Pine Oil ^™ 60 (contains approximately 60% terpene alcohols); ^Glidco_Pine Oil 80 (contains approximately 80% terpene alcohols); ^Glidco_Pine Oil 150 (contains approximately 85% % terpene alcohols); and ^{Glidco_Terpene} SW (containing about 75% terpene alcohols); and ^{Glidco_Terpineol} 350 (containing about 100% terpene alcohols). Each of the above is available from Glidco Organics Corp. Purchased from Jacksonville, FL (USA). Other products containing up to 100% pure alpha-terpineol may also be used in the present invention.

The pine oil component may be present in the concentrate composition in an amount of about 0.001-15% by weight, preferably about 4-12% by weight, most preferably 6-10% by weight of pine oil. Preferred among these are pine oil preparations containing at least 60% terpene alcohols, more preferably those containing at least 80% terpene alcohols. As with all of the above weight percentages of individual components, these weight percentages represent the weight percent of the active material in the ingredients comprising the formulation. Component B) Another component of the present invention is a co-solvent present in addition to pine oil, which itself is a known organic solvent, which helps to improve the diffusibility and/or the water-insoluble pine oil in water or miscibility. The co-solvent may also improve the miscibility of the other components of the invention, including any water-insoluble or poorly soluble components. A number of known co-solvents useful for dispersing pine oil in water can be used as component B, especially those based on organic solvents; indeed any co-solvent that is not expected to destroy the useful features of the invention, especially those that do not Any solvent that affects bloom can be used. A mixture of two or more cosolvents can be used as component B.

Typical co-solvents for use as component B include glycols and glycol ethers having the properties described above. Examples of such glycol ethers include those of the general formula _R9 - _OR10 -OH, wherein _R9 is an alkoxy group of 1-20 carbon atoms or an aryloxy group of at least 6 carbon atoms, and R10 is Ether condensation products of propylene glycol and/or ethylene glycol with 1-10 glycol monomer units. Examples of such useful glycol ethers include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol isobutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, Ethylene glycol phenyl ether, propylene glycol phenol ether, and mixtures thereof. Preferred are ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, and mixtures thereof. Such glycol ethers are currently commercially available from a number of sources, including DOWANOL ^™ glycol ethers from The Dow Chemical Company (Midland MI, USA).

Further typical cosolvents used as component B also include C ₁ -C ₈ alcohols, especially C ₁ -C ₃ alcohols, preference being given to isopropanol.

It will generally be found that the co-solvent used in the concentrated composition need only be added in the minimum effective amount to disperse or solubilize the pine oil and any other water-insoluble or sparingly soluble components. This is because the amount of such volatile organic components in the concentrate compositions of the present invention is desirably minimized from an environmental standpoint. The inventors have found that the addition of about 0.001% to about 15% by weight of a solubilizing agent according to component B is effective in solubilizing pine oil, as well as other less water soluble components present in the concentrate compositions of the present invention. Preferably the Component B solubilizer is present in an amount of about 4-12% by weight, most preferably 8-10% by weight. Component C) The concentrate compositions of the present invention comprise a nonionic surfactant system comprising a mixture of two or more nonionic surfactants, the first nonionic surfactant component being turbid in water. A nonionic surfactant with a temperature of 20°C or below 20°C or a mixture of several such nonionic surfactants, the second nonionic surfactant component is active in water to the first nonionic surfactant A nonionic surfactant or a mixture of several such surfactants that have a solubilizing effect on the agent component. The aforementioned first nonionic surfactant component is usually selected from one or more optional water-insoluble or slightly soluble nonionics, but preferably has a cloud point in water of 20°C or lower. The second nonionic is capable of solubilizing the first nonionic surfactant. This solubilizing effect contributes to the long-term storage stability of the prepared concentrate composition as well as to ensuring the optical clarity of the concentrate composition, especially the clarity of the concentrate composition prepared during storage.

In general, suitable nonionic surfactants for use in the Component C nonionic surfactant system include condensation products of one or more alkylene oxides with an organic hydrophobic compound, such as an aliphatic or alkyl aromatic Family compounds. Typical suitable nonionic surfactants include surfactant compositions based on polyethoxylated, polypropoxylated or polyglycerylated alcohols, alkylphenols or fatty acids.

A typical class of nonionic surfactants for use in component C of the present invention includes certain alkoxylated linear fatty alcohol surfactants, which are considered to be C ₈ -C ₁₀ hydrophilic moieties combined with polyoxyethylene / Polyoxypropylene moiety condensation product. Such alkoxylated linear alcohol surfactants are currently commercially available under the tradename Poly- ^Tergent® (Olin Chemical Co. Stamford CT), of which Poly-Tergent® SL-22, Poly- ^Tergent® SL-22, Poly-Tergent® ^_ SL-42, Poly- ^Tergent_ SL-62 and Poly- ^Tergent_ SL-29, of which Poly- ^Tergent_ SL-62 is particularly advantageous. Poly-Tergent ^_ SL-42 is described as a moderately foaming, biodegradable alkoxylated linear alcohol surfactant containing an average of 5 moles of oxyethylene groups per molecule. Poly- ^Tergent_SL -62 is described as a moderately foaming, biodegradable alkoxylated linear alcohol surfactant containing an average of 8 moles of oxyethylene groups per molecule. These alkoxylated linear alcohol surfactants provide good detergency, removal of many types of fats and greases, such as stains often found on hard surfaces, and also have a solubilizing effect.

Another class of useful typical nonionic surfactants are alkoxylated alcohols, especially alkoxylated fatty alcohols. These include ethoxylated and propoxylated fatty alcohols and ethoxylated and propoxylated alkylphenols, all having an alkyl chain length of about 7 to 16 carbon atoms, more preferably about 8 - Alkyl chain length of 13 carbon atoms. Typical alkoxylated alcohols include certain ethoxylated alcohol compositions, currently available from Shell Chemical Company (Houston, TX) under the generic trade name ^Neodol® , which are ethoxylates of linear alcohols. Usable among these are those having a cloud point of 20°C or lower. The specific composition includes: ^{Neodol_91-2.5} , which is an ethoxylated alcohol, the average molar ratio of ethoxy groups to alcohol groups in each molecule is 2.7:1, and the molecular weight is 281, The cloud point in water is 20°C and lower: ^Neodol_23-3 , an ethoxylated alcohol with a molar ratio of ethoxy groups to ethanol groups of 2.9:1.1 per molecule, molecular weight 322, in water The cloud point is 20°C and lower.

Typical alkoxylated alcohols further include those available from Union Carbide Co. (Danbury, CT) a composition commercially available under its generic tradename ^Tergitol® , which is described as an ethoxylate of a secondary alcohol. And usable are those having a cloud point of 20°C and lower. Specific compositions include: ^Tergitol_15 -S-3, which is described as an ethoxylated secondary alcohol having an average molar ratio of ethoxy groups to alcohol groups per molecule of 3.2:1, and in water The cloud point of ^Tergitol_15 -S-5, which is described as an ethoxylated secondary alcohol with an average molar ratio of ethoxyl groups/alcohol groups per molecule of 5:1, in water The cloud point is below 20°C.

Still other typical nonionic surfactants that may be used in Component C include certain alkanolamides, including monoethanolamides and diethanolamides, especially aliphatic monoalkanolamides and aliphatic bisalkanolamides. Commercially available monoethanolamides and diethanolamides include Rhone-Poulenc Co. (Cranbury, NJ) under the trade names Alakamide ^_ and Gyclmide ^_ . These surfactants include coconut diethanolamide; coconut monoethanolamide; 2:1 modified coconut monoethanolamide; fatty acid diethanolamide; lauric/linoleic diethanolamide; linoleic diethanolamide; lauric acid Monoethanolamide; Diethanolamide Laurate; Diethanolamide Laurate/Myristate; Diethanolamide Oleate; Diethanolamide Stearate; Diethanolamide Cocoate; Monoisopropanolamide Laurate; Stearic Acid Monoethanolamides; diethanolamides of unsaturated fatty acids; alkanolamides can be used alone or in combination. Particularly useful are those surfactants of linoleic acid diethanolamide and lauric diethanolamide.

Typical alkoxylated alkylphenols useful in composition C include those available from Rhone Poulenc. Co． (Cranbury, NJ) certain compositions are commercially available under the generic trade name of octyl and nonylphenols of ^Igepal® . Also, those having a cloud point of 20°C or less can be used. These include ^Igepal_CA -210, an ethoxylated octylphenol with an average of 1.5 ethoxy groups per molecule and a cloud point in water below 20°C, and ^Igepal_CA -420, a An ethoxylated octylphenol with an average of 3 ethoxy groups per molecule and a cloud point in water below 20°C.

The first nonionic surfactant component which is particularly preferred according to the invention as component C is Neodol ^- 91-2.5, the average molar ratio of ethyl groups to alcohol groups per molecule is 2.7 : 1 Ethoxylated alcohol; molecular weight 281, cloud point in water 20°C and lower.

Of course, mixtures of two or more nonionic surfactants having a cloud point of 20°C or less may also be incorporated into the compositions of the present invention. Other known nonionic surfactants not listed here may also be used.

The cloud point of the first nonionic surfactant of component C of the present invention can be determined according to known methods, such as "Standard Test Method for Cloud Point of Nonionic Surfactants" according to ASTM D2024 (reapproved in 1986). A simpler and more efficient method of determining which nonionic surfactant can be used as the first nonionic surfactant component in the compositions of the present invention is as follows: Add 99 wt. Parts of deionized water at 20°C±5°C and 1 part by weight (the weight of the active agent) of the surfactant composition to be tested. Stir the test sample and allow the temperature to drop to 20°C; if the sample becomes dark or cloudy in appearance when the test sample temperature reaches 20°C and below 20°C, it is considered to have a suitable cloud point of 20°C and lower , can be used in component B of the concentrate composition of the present invention.

Component C may be present in any effective amount, but desirably ranges from about 0.001% to 25%, preferably from 0.1% to 20%, most preferably from 8% to 15% by weight of the concentrate composition. Desirably, when Component C comprises an alkanolamide, dialkanolamide, or trialkanolamide in the composition, Component C is present in the concentrate composition in a weight percent that is substantially equal to or greater than that of Component B. quantity. Component D)

The concentrate compositions of the present invention comprise as an essential ingredient at least one cationic quaternary ammonium surfactant which has been found to have broad antimicrobial or disinfectant properties, such materials are well known in the art.

其中R₁、R₂、R₃和R₄至少是疏水的、含6-26个碳原子的脂肪族、芳基脂肪族或脂肪基芳香基团，并且分子中的全部阳离子部分的分子量至少为165，该疏水基团可以是长链烷基、长链烷氧基芳基、长链烷基芳基、卤代的长链烷基芳基、长链烷基苯氧基烷基、芳基烷基等。除疏水基外N原子上连接的剩余基团是总数不超过12个碳原子的烃结构的取代基。基团R₁、R₂、R₃和R₄可是直链的或为支链的，但优选直链的，并可包含一个或多个醚键或酰胺键。基团X可以是任何成盐阴离子基团。Typical useful and preferred compounds are quaternary ammonium compounds and their salts, characterized in that their general structure is

wherein R ₁ , R ₂ , R ₃ and R ₄ are at least hydrophobic, aliphatic, arylaliphatic or aliphatic aromatic groups containing 6-26 carbon atoms, and all cationic moieties in the molecule have a molecular weight of at least 165, the hydrophobic group can be long-chain alkyl, long-chain alkoxyaryl, long-chain alkylaryl, halogenated long-chain alkylaryl, long-chain alkylphenoxyalkyl, aryl Alkyl etc. Except for the hydrophobic group, the remaining groups connected to the N atom are substituents of hydrocarbon structures with a total of not more than 12 carbon atoms. The groups R ₁ , R ₂ , R ₃ and R ₄ may be linear or branched, but are preferably linear and may contain one or more ether linkages or amide linkages. The group X can be any salt-forming anionic group.

Typical quaternary ammonium salts within the above range include alkylammonium halides such as cetyltrimethylammonium bromide, alkylarylammonium halides such as octadecyldimethylbenzylammonium bromide, N-alkonium Cetylpyridinium halides such as N-cetylpyridinium bromide, and the like. Other suitable types of quaternary ammonium salts include those with amide or ether linkages in the molecule, such as octylphenoxyethoxyethyldimethylbenzyl ammonium chloride, N-(laurylcoconutcarbamoylmethyl )-pyridinium chloride, and the like. Other particularly effective quaternary ammonium compounds useful as fungicides include those having a hydrophobic base characterized by a substituted aromatic ring such as lauryloxyphenyltrimethylammonium chloride, cetylaminophenyltrimethylammonium chloride, Methyl ammonium methosulfate, dodecylphenyltrimethylammonium methylsulfate, dodecylbenzyltrimethylammonium chloride, dodecylbenzyltrimethylammonium chloride, and Similar substances.

其中R₂和R₃可为相同或不同的C₈-C₁₂烷基，或者R₂是C₁₂-C₁₆烷基，C₈-C₁₈烷基乙氧基，C₈-C₁₈烷基苯酚乙氧基，并且R₃是苯甲基，X是卤素，例如氯、溴或碘或者甲硫酸基。R₂和R₃所用的烷基可以是直链的或支键的，但实际上优选线性的。Particularly preferred quaternary ammonium compounds useful as fungicides and found useful in the practice of the present invention include those of the formula:

Wherein R ₂ and R ₃ can be the same or different C ₈ -C ₁₂ alkyl, or R ₂ is C ₁₂ -C ₁₆ alkyl, C ₈ -C ₁₈ alkylethoxy, C ₈ -C ₁₈ alkyl Phenolethoxy, and _R3 is benzyl, X is a halogen such as chlorine, bromine or iodine or methosulfate. The alkyl groups used for _R2 and _R3 may be linear or branched, but linear is preferred in practice.

Such quaternary ammonium fungicides are commercially available as either a single quaternary ammonium compound or as a mixture of two or more different quaternary ammoniums. Suitable substances include those bactericidal quaternary ammonium compounds available under the trade names BARDAC, BARQUAT and HYAMINE (Lonza Inc., Fail-lawn NJ (USA)), and those known as "BTC" (Stepan Co. Northfield IL (USA)).

The quaternary ammonium compound of component C) is ideally used in the minimum amount that provides the desired bactericidal and sanitizing effect, because when large amounts of water are added, the concentrated composition is hindered by the incorporation of excess amounts of this quaternary ammonium compound The blooming effect of the object. Typically, component C will be present in the concentrate compositions of the present invention in an amount up to 5% by weight or less, preferably 0.5-2% by weight, most preferably 0.8-12% by weight. The inventors have found that this preferred amount is motivated in part by toxicological considerations, since excess cationic ingredients can increase the risk of irritation to the eyes, skin and mucous membranes of the consumer.

Component E) Another component of the concentrate compositions of the present invention is a perfume and/or fragrance enhancer which provides the characteristic pine oil scent and scent persistence, especially when the concentrate composition is diluted to form a cleaning composition. As described in the specification below the claims, the term "perfume" is used to refer to and include any water-insoluble perfume substance or mixture of such substances, including those obtained naturally (i.e., from flowers, grasses, flower clusters, or plant those derived or prepared artificially (ie natural oils and/or mixtures of oil components), and those produced synthetically (musky substances). Usually fragrances are complex mixtures or mixtures of various organic compounds including (but not limited to) certain alcohols, aldehydes, ethers, aromatic compounds and various amounts of essential oils such as about 0-85% by weight, usually At about 10-70% by weight, the essential oils themselves are volatile compounds with a natural musky odor and serve to help dissolve the other components of the fragrance. In the present invention, the precise composition of the perfume is not particularly critical to detergency performance so long as it is effectively included as an ingredient. However, one or more fragrances characteristic of pine oil-type compositions are commonly used, such as natural or synthetic fragrance compositions, especially those which attempt to imitate the fragrance of one or more resins or oils obtained from coniferous trees , which is a detergent concentrate with pine oil-type fragrance characteristics. Laundry concentrates with a non-standard pine oil type scent may also be used. Perfume adjuvants for enhancing the odor effect of the perfume and/or for improving the miscibility of such perfume compositions include known perfume adjuvants such as fenzyl alcohol.

In any type of composition, the pine oil smell is the characteristic fragrance released by pine oil, and it is considered that the persistence of such a pine oil fragrance is closely related to the content of the concentrated composition or cleaning composition described in this specification. Therefore, it is generally desirable to increase the amount of pine oil in order to increase the characteristic pine oil flavor and flavor persistence, but increasing the amount of pine oil incorporated is not always desirable in other respects for the reasons noted above in this invention. . In order to provide the desired characteristic pine oil fragrance and pine oil fragrance persistence without increasing the amount of pine oil, the inventors have found that the amount of pine oil can be reduced and the unique pine oil can be maintained by selecting spices and/or flavoring agents. Oil fragrance and fragrance persistence. This purpose is achieved without affecting the blooming behavior of the aforementioned pine oil cleaning composition. Also, avoiding another undesired characteristic is the increase of organic solvents such as perfume/perfume solubilizers which are known to contain volatile components, which may cause increased irritation, especially to the eyes, skin and mucous membrane tissues. Component F) Water is added in order to obtain 100% by weight of the concentrated composition. The water may be tap water, but distilled and/or deionized water is preferred. The amount of water added should be sufficient to form a concentrated composition in an amount sufficient to ensure that the prepared concentrate retains essential cleaning properties, but at the same time ensures that when the concentrated composition is added to another quantity of water or added to the concentrate It can have good blooming phenomenon when adding additional amount of water. Usually the water in the concentrate composition is more than 80% by weight, preferably more than 75% by weight, but the most preferred amount is between 60-75%, all of which are the total of components A-F of the concentrate composition described herein. Quantity based. Optional components:

A further optional but beneficial component is one or more colorants which can be used to modify the appearance of the concentrate composition, in particular it can impart a characteristic appearance to a pine oil type concentrate composition characteristic. However, other colorants than standard pine oil-based detergents can also be used. Light stabilizers known to maintain the appearance of the concentrated composition permanence may also be used. Non-limiting examples of other optional components that may be used include pH adjusters, pH buffers, sudsing agents, surfactants (including anionic, cationic, nonionic, amphoteric, and zwitterionic, particularly to provide deep cleaning effect), and water softeners. These optional, i.e., non-essential, ingredients are chosen to have little or no detrimental effect on the desired properties of the present invention, namely blooming performance, detergency, disinfectant activity and low Toxicity, and in most cases, avoid anionic surfactants that can inactivate quaternary ammonium cationic surfactants. Typically, these conventional additives may be added in an additional amount of up to 10% by weight of the concentrate composition formulation.

The term "concentrate" as used in this specification is the cleaning composition before it is diluted by the consumer, usually in the form in which the product is made for sale to the consumer or end user. The term "cleaning composition" is a water-diluted composition in which a precise amount of a "concentrate" is mixed with water by the consumer or other end user to form a suitable diluted cleaning composition suitable for cleaning purposes, especially hard surfaces . Such preparations are readily prepared by the consumer or other end user by diluting a measured amount of the concentrate composition in water at a weight ratio of concentrate to water, and optionally agitating to ensure distribution of the concentrate in the water uniform. It should be noted that the concentrate can also be used undiluted, ie the ratio of concentrate to water is 1:0, to an extreme dilution such as 1:10,000. The ideal dilution range of the concentrate is 1:0.1-1:1000, preferably 1:1-1:500, most preferably 1:10-1:100. However, it is to be understood that the "concentrated composition" is the composition without any dilution, and may be used as such.

Unless otherwise stated, it is understood that the percentages of components herein generally refer to percentages by weight or ratios of parts by weight based on 100% by weight.

Preparation of Example Formulation Example Formulation:

The example formulations of the present invention listed in Table 1 below were prepared according to the following general procedure.

In a suitable sized container add the following ingredients in the following order: pine oil, co-solvent, nonionic surfactant system, perfume/fragrance, cationic surfactant, water and lastly optional ingredients. The order of mixing is not critical to obtain the desired concentrated composition. All components are provided in weight percent at room temperature, and magnetic stirring is used to obtain a mixture of these components. The mixing process is generally continued for 1-15 minutes, and is maintained until uniform color and uniform clarity of the specific example formulation are obtained. Each formulation had the following physical characteristics: clear appearance, light orange to medium orange-brown color, and a distinct pine oil odor. This typical formulation pours easily and has good mixing characteristics (ie, a stable mixture) for several weeks when left standing at room temperature (approximately 68°F). The stability of this concentrated formulation was assessed by heating it to 120°F to determine if clouding or phase separation occurred; none were observed. Table 1: Formulations components E1 E2 E3 E4 E5 E6 E7 E8 Pine Oil 1 8 -- -- -- -- 8 8 8 Pine Oil 2 -- 8 5 5 6 -- -- -- Isopropanol 9.25 9 5 5 4 9.25 9.25 9.25 Diethylene glycol n-butyl ether -- -- 6 6 5 -- -- -- Poly- ^Tergent_SL -62 8 8 8 8 8.75 8 8 8 ^{Neodol_91-2.5} 5 5 4 4 1.75 5 5 5 Alkyldiethanolamide 1.4 1.2 1 -- 1 1.18 1.5 1.8 BTC-8358 0.9 0.9 1 1 1 0.9 0.9 0.9 BTC-818 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Spice 1 1.2 -- -- -- -- -- 1.2 1.2 Spice 11 -- 0.1 0.1 0.1 0.1 -- -- -- Spice 111 -- -- -- -- -- 0.6 -- -- Fenchol 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Colorant 0.001 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 0.0008 Deionized water 65.65 67.2 69.29 70.29 71.8 66.47 65.55 65.25 Pine Oil 1 is a pine oil preparation containing at least 60% terpene alcohols. Pine Oil 2 is a pine oil preparation containing at least 80% terpene alcohol Poly- ^Tergent_ SL-62 is a nonionic alkoxylated linear alcohol surfactant ^Neodol_ 91-25 is a linear alcohol ethoxylate Based, its characteristic cloud point is less than 20 ℃. BTC-8358 is an alkylbenzyldimethylammonium chloride (80% active), available from Stepan Chemical Co. BTC-818 is commercially available as dialkyldimethylammonium chloride (50% active) from Stepan Chemical Co. purchased.

The determination of the amount of solubilizing agent (here isopropanol) required in the formulations of Table 1 to clarify provides a useful indication of the amount of co-solvent required in a typical concentrate composition. The weight percent of isopropanol (100%) added to each formulation is shown in Table 1. It should be noted that the values indicated in Table 1 are based on 100% of the total weight of the components actually added. To prepare the washing composition:

Washing tests were performed using one or more of the typical compositions within the scope of the present invention shown in Table 1, and a washing composition prepared from a commercially available washing product was designated as a comparative example.

Comparative example "C1"

A washing combination is prepared by mixing an aqueous dilution of 1 part by weight of ^Lysol_Pine -Action Cleaner (commercially available detergent concentrate) with 61 parts by weight of water at approximately 20°C, followed by manual agitation to form a homogeneous mixture things.

Comparative example "C2"

A detergent composition was prepared by mixing one part by weight of Spic and ^Span_Ultra Pine Deodorizing Cleaner (commercially available detergent concentrate) with 128 parts by weight of water at room temperature (about 20° C.) and stirring manually to form a homogeneous mixture.

Comparative example "C3"

Mix one part of a commercially available detergent preparation, Pine Sol ^_ Cleaner, a pine oil-type detergent concentrate, with 64 parts of water at room temperature (about 20°C), and manually stir it to form a detergent composition, and evaluate the detergent performance;

Detergency performance was determined using a test protocol developed in accordance with ASTM D4488 Test Method A2, which evaluates the efficacy of the detergent composition on samples of insulating fiber siding coated with wall coatings, the stain sample being a greasy stain , including vegetable oils, food residues and animal oils. The sponge (water soaked) of the Gardner Abrasian Tester was sprayed with 15 g of the sample of the cleaning composition to be tested and the tester was cycled 10 times. When one side of each test sample was treated with the composition of the present invention and the other side was treated with the composition of the control example, so the evaluation results were "paired", and a "head-to-head" comparison could be made. Each of these tests was repeated on 20 panels and the results of the statistical analysis and the average results are shown in Table 2 below. The detergency of the compositions tested was evaluated using a Minolta Chroma Meter CF-100 with a data processor D ^- 100, which measures the spectrophotoelectric interaction characteristic of the samples. The results are shown in Table 2 below. Table 2 Composition丨Comparative composition E1丨C1 E1丨C2 E1丨C3 E2丨C3 Reflection Readings: Composition丨Compare Combination Numbers 69.04丨67.19 63.68丨62.22 70.93丨69.82 65.63丨65.14

In the results of Table 2, the value "100" refers to a white (unstained) background and the value "0" refers to a black background. A heavily soiled (unwashed) surface typically gets a value of 20-30.

As can be seen from the results in Table 2, the compositions of the present invention provide satisfactory results compared to known art cleaning products. 1. Determination of light transmission (blooming) of preparations

Each of the formulations listed in Table 1 was assayed for the degree of light transmission, a measure of the opacity of the concentrated formulations. Also tested were comparative formulations designated "C1" and "C2" as above.

Water dilutions were prepared to determine the transmittance, opacity, and bloom of each water dilution. The antimicrobial efficacy of some of these aqueous dilutions was also determined. The result of light transmittance measurement is the percentage of light transmitted through a specific water dilution, where the transmittance of a water sample is defined as 100%. A 1:61 dilution of Example formulation: water was formed by mixing a 3 g aliquot of a particular example formulation with 192 g of tap water (approximately 100 ppm hardness), and the sample was then mixed for 60 seconds and colorimetrically measured by immersion, Model Brinkman PC801 Transmittance readings were obtained using the reagent, with a wavelength of 620nm set to determine the transmittance of each sample. Samples of each formulation were measured at 20°C and 40°C, also with water (pure tap water) to calibrate the colorimeter to 100%. The results obtained are shown in Table 3 below, which provides the experimental value "%T" of percent transmittance expressed as the degree of transparency of the diluted example formulations, where 0% is not transparent at all and 100% is the transparency of the above water samples.

Thus, the smaller the %T for a particular aqueous dilution, the better the bloom characteristics of that aqueous dilution. Table 3 Percent Transmittance (%T) Translucency E1 E3 E4 E5 E7 E8 C2 C3 %T 20°C 30-40 30-40 >80 >80 20-30 10-20 >80 >80 %T 40°C 10-20 30-40 - - 10-20 <10 >80 >80

It can be seen from Table 3 that the present invention is superior to the comparative examples in most cases compared with the preparations represented by the prior art comparative examples C1 and C2. 2. Determination of light transmission ("bloom") of formulations

Additional formulations of the invention as well as additional comparative formulations were prepared; their components are shown in Table 4 below. The ingredients used in Table 1 were the same, but different colorants (1% by weight active) and different fragrances were used. Table 4 C4 C5 E9 E10 components Pine oil 80 8.00 8.00 8.00 8.00 Isopropanol 9.25 9.25 9.25 9.25 ^{Polytergent_SL} -62 8.00 8.00 8.00 8.00 ^Neodo_91-2.5 5.00 5.00 5.00 5.00 Alkyldiethanolamide 0.00 0.50 1.50 2.00 Fenchol 0.10 0.10 0.10 0.10 spices 1.20 1.20 1.20 1.20 BTC-8358 0.90 0.90 0.90 0.90 BTC-818 0.50 0.50 0.50 0.50 Colorant 0.11 0.11 0.11 0.11 Deionized water 66.94 66.44 65.44 64.94

In a manner similar to that described above, the blooming characteristics of other compositions of the invention (designated "E9" and "E10") and other comparative examples ("C4" and "C5") were determined by measuring in water respectively A 1:64 dilution of the Example or Comparative formulations was made, the samples were then mixed for 60 seconds, and the light transmission readings were obtained for each sample by determining the light transmission using a Brinkman model PC801 immersion colorimeter set at 620 nm. Each formulation sample was tested at 20°C and 40°C, respectively, and the percent transmittance is shown in Table 5. Table 5 - Percent Transmittance (%T) C4 C5 E9 E10 Bloom at 20°C 97 97 28 13 Bloom at 40°C 86 92 11 2

As can be seen in Table 5, formulations C4 and C5 containing low diethanolamide levels and high levels of perfume (1.2% by weight) had high percent light transmission and exhibited very low blooming characteristics. E9 and E10 formulations have the same amount of perfume, but include at least a considerable amount (by weight percentage) of diethanolamide as perfume, and the surprising basic characteristics appear, and its blooming property is significantly improved, which can be obtained from high light Evidenced by percentage reduction. Determination of fragrance persistence:

Perfume persistence was determined from the comparative formulation "C1" and the example formulation "E1" in Table 1 above.

Individual cleaning compositions were prepared based on each of the formulations by mixing 4 g of the formulation with 256 g of water respectively to form a 1:64 dilution, which is a typical dilution of a household pine oil type product. Next pour each detergent composition on the floor of a different room, mop it with a sponge mop to cover a floor area of 40 square feet, turn on the circulation fan for five minutes and turn it off, wipe clean within 30 minutes, 40 tests The experts were divided into two groups and entered a room for 45 seconds. Then exit the room. Each expert was then asked to assess the scent emanating from the floor, and then they were left outside the room, with the aim of clearing their nasal passages and acclimatizing to their surroundings, and then the members of the group entered two more rooms, and stayed again. Wait for 45 seconds before exiting the room and assess the scent released from the floor of the room you just entered.

After 7 hours after mopping and then 24 hours after mopping, each expert repeated the above steps, evaluating the fragrance of the two treated floor surfaces at this time, in this way after a longer period of time after application, that is, 7 hours and 24 hours. A meaningful assessment of the scent of pine oil compared to commercially available pine oil-based detergent compositions is available after hours. Table 6 - Fragrance Persistence Washing composition 1 part formulation: 64 parts water Pine oil fragrance intensity after 0.5 hours of application Intensity of pine oil scent 7 hours after application Intensity of pine oil scent 24 hours after application C1 44% 16% 33% E1 56% 84% 67%

From the numbers in Table 6 and the illustration in Figure 1 it can be seen that the overall percentage of fragrance for one formulation is preferred over the other formulation. It can be seen that although the results are similar in the first 0.5 hours after application, the intensity of the pine oil fragrance left by the formulation E1 of the present invention is significantly higher than that of the prior art formulation C1, and has a longer persistence. Evaluation of eye irritation:

The eye irritation properties of the formulations of the present invention were evaluated using the known Draize eye test method. The evaluation was carried out on the composition shown in Example E7 in Table 1 of the present invention, ie without any dilution. As is well known, the Draize eye test measures the severity of irritant damage to the eye, obtaining values for damage to the cornea, iris and conjunctiva, respectively. For the cornea, after using the composition, A is the opacity of the cornea, divided into 1-4 grades; B is the area of the cornea involved, divided into 1-4 grades (assessment value=A×B×5, the maximum possible up to 80). For the evaluation of the iris after exposure to the composition, A is that the iris involved is classified into 1-2 grades (evaluation value=A×5, the maximum can be 10). For the evaluation of the conjunctiva, A is the degree of hyperemia, which is divided into grades 1-3; B is the degree of conjunctival edema, which is divided into grades 1-4; and C is discharge, and the measured value is divided into grades 1-3 [measured value = (A +B+C)×2, up to 20], the total maximum value is the sum of all the values obtained for the cornea, iris and conjunctiva (the maximum is 110).

The value of Draize on the first day of the test was 19.33, and it was further observed that on the seventh day of the test, all six subjects’ symptoms of opacity disappeared, but only one of the six subjects’ conjunctival irritation Observed for seven days. On the seventh day, the Draize value was 0.33. On day fourteen, any irritation, opacity, or conjunctival irritation was observed to disappear. The Draize test results indicate that EPA Tox Category "0" is suitable. It is particularly surprising that these results were achieved in a product having significant levels of each component and each being an irritant.

Claims (10)

1. a blooming type, pine tar type washing concentrating composition comprise following ingredients:

A. a pine tar preparation contains 60% Terpineol 350 at least;

B. solubility promoter;

C. nonionic surfactant system, it comprises two or more nonionogenic tensides, wherein at least a cloud point in water be 20 ℃ or/lower;

D. cationic quaternary ammonium tensio-active agent with fungicidal activity.

E. spices/sweetener; And

F. water.

2. pine tar type washing concentrating thing according to claim 1, wherein B is selected from C ₁-C ₈Alcohol, glycol ether and glycol.

3. pine tar type washing concentrating thing according to claim 1, wherein C comprises a kind of alkoxylate linear alcohol tensio-active agent.

4. pine tar type washing concentrating thing according to claim 1, wherein C comprises a kind of monoalkylol amide, di alkanolamide or three alkylolamide surfactant compositions.

5. pine tar type washing concentrating thing according to claim 1, wherein D is the quaternary ammonium compound that following array structure has fungicidal activity, Wherein:

R ₁, R ₂, R ₃And R ₄In have at least one to be selected from hydrophobic aliphatics, aromatic yl aliphat or the fatty group aromatic group that contains 6-26 carbon atom, and remaining R ₁, R ₂, R ₃And R ₄Any group be the alkyl that contains 1-12 carbon atom, wherein R ₁, R ₂, R ₃And R ₄All can be linear or side chain and can comprise one or more ethers or amido linkage; And X is salifiable anionic group.

6. pine tar type washing concentrating thing comprises following basal component:

A) a kind of pine tar preparation that contains 60% alpha-terpineol at least of 0.001-15% weight;

B) solubility promoter of 0.001-15% weight is selected from C ₁-C ₈Alcohol, glycol ether and glycol;

C) a kind of nonionic surfactant system of 0.001-15% weight comprises two or more nonionogenic tensides, and wherein at least a described nonionogenic tenside shows 20 ℃ or lower cloud point in water;

D) cationic quaternary ammonium compound of 0.5-5% weight, structure is:

Wherein:

R ₁, R ₂, R ₃And R ₄In at least one is selected from hydrophobic aliphatics, aromatic yl aliphat or the fatty group aromatic group that contains 6-26 carbon atom, remaining R ₁, R ₂, R ₃And R ₄Any group be the hydrocarbon that 1-12 carbon atom arranged, wherein R ₁, R ₂, R ₃And R ₄All can be linear or branched and can comprise one or more ethers or amido linkage; And X is halogenide or methyl-sulfuric acid group;

E.0.000001-1.5% spices/the sweetener of weight; And

F. make the water that reaches 100% weight.

7. according to claim 1 or 6 described a kind of blooming types, pine tar type cleaning composition, further comprise one or more inessential components that account for this cleaning composition gross weight 10% at the most, be selected from: tinting material, photostabilizer, pH regulator agent, pH buffer reagent, pore forming material, other composition comprise negatively charged ion, positively charged ion, nonionic, amphoteric and zwitterionic tensio-active agent and water-softening agent.

8. according to a kind of blooming type pine tar cleaning composition of claim 1 or 6, wherein in described composition, the weight percentage of component C approximately is equal to or greater than the amount of component E.

9. aqueous cleaning composition, it comprises claim 1 or 6 described pine tar type washing concentrating compositions with concentrate composition: water is 1: 0.1-1: 1000 weight ratio is dispersed in the water.

10. one kind is used for the method that crust need wash and disinfect, and this method may further comprise the steps:

Use the described composition of claim 1 with the amount that can provide effective cleaning and/or disinfect.

Images