TWI608094B - Cleaning composition, preparation thereof and method of using the same - Google Patents

Description

Cleaning composition, method of making and using same

The present invention relates to cleaning compositions for removing stains and adhesives, methods of making and using same.

Undesirable substances on the substrate (such as acrylic plastics, industrial greases, adhesives, glues, rubber glues, aircraft adhesives, and stains) have long been removed with cleaning compositions and mixtures. However, conventional cleaning compositions and mixtures typically contain an industrial solvent such as toluene and other aromatic hydrocarbons which results in the conventional cleaning compositions and mixtures themselves being quite toxic.

The composition of a typical composition for removing stains and adhesive residues is mainly a combination of acetone, toluene, xylene, mineral solvent and 1,2,4-trimethylbenzene, all of which are highly skin irritating. Toxic to specific target organs and low ACGIH TLV-TWA/TLV-STEL low limit (the abbreviation "ACGIH" means "American Conference of Industrial Hygienists", abbreviation "TLV-TWA "Low limit - eight hours of daily average allowable concentration", the abbreviation "TLV-STEL" means "low limit - short time average allowable concentration"), so when the user inadvertently or deliberately inhales When ingested or absorbed through the skin, it is toxic to the human body.

U.S. Patent No. 7,977,294 discloses a method of removing adhesive residue on a rigid substrate, particularly for adhesive residues on vehicles such as automobiles, trucks, buses, air vehicles (including aircraft, etc.). The method utilizes an adhesive remover composition comprising one or more non-halogenated organic solvents, a non-stick thickener, a surfactant, and a vapor pressure modifier. The total Hansen solubility parameter (δ _t ) of each of the non-halogenated organic solvents at 25 ° C is about 14 MPa ^1/2 to about 24 MPa ^1/2 . This U.S. patent is primarily intended to remove aircraft components and large areas of pressure sensitive adhesives on aluminum surfaces. However, the composition comprising the non-halogenated organic solvent is not a safe and environmentally friendly adhesive remover, and the non-halogenated organic solvent causes the surface of the substrate to be cleaned to be staggered and adhered to the substrate. More unwanted stains and adhesives. Again, the composition must comprise a thickening agent such as vermiculite, cellulose, cellulose derivatives or combinations thereof.

U.S. Patent Publication No. 20090038650 discloses a composition comprising a fatty acid ester (e.g., mustard oil) and an essential oil (e.g., borneol), and an example of such a composition comprises mustard oil and lime oil as a constituent. This U.S. Patent Publication also provides a method of dissolving a primary organic material and a cleaning method comprising exposing a substrate to be treated (e.g., a paint apparatus) to a composition comprising a fatty acid ester and an essential oil.

China Mainland Patent Licensing Publication No. CN 101899365 B discloses a degumming agent and a preparation method thereof, the basic composition of the degumming agent is: 12-25% of a fatty alcohol polyoxyethylene ether sulfate and a fatty alcohol polyoxyethylene ether decane, 20-30% alkylphenol ethoxylate, 4-5% ethylene oxide/propane block copolymer, 5-7.9% sodium chloride, 10-12% triethyl phosphate and adipic acid Dimethyl ester, 5-10% tricarboxytriethylamine, triethylamine, diethanolamine, EDTA, urea, triethanolamine and hexamethylenetetramine, 2-10% ethylene glycol ether, ethylene glycol Dibutyl ether, propylene glycol methyl ether, ethanol, isopropanol, benzyl alcohol and methyl Isoamyl ketone, and 0.1-42% deionized water, the above percentages are by weight. The degumming agent of this Mainland China Patent Licensing Notice does not contain a hydrophobic alkyl hydrocarbon solvent.

There is still a need to find a cleaning composition for removing stains and adhesives having low skin irritation, low toxicity, high ACGIH TLV-TWA/TLV-STEL low limit and low cost.

One object of the present invention is to provide a cleaning composition for removing stains and/or adhesives consisting essentially of: about 40 to 99 wt% having a TWA value greater than or equal to 150 ppm and at least 5 or more alkyl hydrocarbons of up to 18 carbon atoms; about 0.01-10% by weight of a nonionic surfactant having an HLB value of less than or equal to 12; and about 1 to 30% by weight of an alcohol.

Another object of the present invention is to provide a method of making the above cleaning composition for removing stains and/or adhesives.

Another object of the present invention is to provide a method of removing stains and/or adhesives from the surface of a substrate.

The present invention utilizes a combination of a hydrophobic alkyl hydrocarbon, a hydrophilic solvent and a nonionic surfactant to swell the stain and/or the adhesive to be removed and form a ball with the composition, thereby achieving stain removal and/or The purpose of the adhesive.

Accordingly, one aspect of the invention is a cleaning composition for removing stains and/or adhesives consisting essentially of the following ingredients: about 40 to 99 wt% having a TWA value greater than or equal to 150 ppm and at least 5 and at least 18 carbon atoms of one or more alkyl hydrocarbons; about 0.01-10 wt% having a HLB value less than or equal to 12 a surfactant; and about 1-30% by weight of an alcohol. The compositions of the present invention have the advantages of low skin irritation, low toxicity, and high ACGIH TLV-TWA/TLV-STEL low limits.

The alkyl hydrocarbon used in the composition of the present invention is a class of aliphatic chain hydrocarbons containing only carbon atoms and hydrogen atoms, which may be saturated or unsaturated, linear or branched, and the alkyl hydrocarbons have greater than or equal to A TWA value of 150 ppm and having at least 5 and up to 18 carbon atoms. It is well known in the art to which the present invention pertains that the greater the TWA value of a substance, the lower the irritation of the substance to the skin. Those skilled in the art to which the present invention pertains can determine the TWA value of an alkyl hydrocarbon having 5 to 18 carbon atoms according to conventional detection methods and/or knowledge, and arbitrarily select a suitable TWA having a ratio of 150 ppm or more. The invention is practiced with one or more alkyl hydrocarbons. In the present invention, the alkyl hydrocarbon preferably has a TWA value of greater than or equal to 175 ppm, more preferably has a TWA value of greater than or equal to 200 ppm; and the alkyl hydrocarbon has at least 7 and up to 14 carbon atoms. More preferably, it has at least 7 and at most 10 carbon atoms. In a preferred aspect, the composition of the present invention comprises a plurality of alkyl hydrocarbons selected from the group consisting of n-heptane, isoheptane, octane, decane, decane, undecane and dodecane.

The alkyl hydrocarbon used in the composition of the present invention is preferably used in an amount of from about 50 to 99% by weight, more preferably from about 50 to 95% by weight, most preferably from 50 to 92% by weight.

The nonionic surfactant used in the composition of the present invention is any HLB value known to those of ordinary skill in the art to which the present invention pertains. A nonionic surfactant of less than or equal to 12. The present invention achieves the desired consistency of the composition by adjusting the HLB value without the need to add a thickener. The nonionic surfactant used in the composition of the present invention preferably has an HLB value of from 0 to 11, more preferably an HLB value of from 0 to 10. Examples of specific nonionic surfactants include, but are not limited to, ethoxylated alcohols, cetyl alcohol, stearyl alcohol, ethoxylated alkyl phenols, ethoxylated fatty alcohol amines, and ethoxylated groups. Lanolin derivative. Other suitable nonionic surfactants can be found in U.S. Patent Nos. 4,556,509, 5,990, 065, and 6, 069, the entire disclosures of According to a preferred embodiment of the present invention, wherein the nonionic surfactant is Ecosurf EH-3 (available from Dow Chemical Corp., which is 2-ethylhexanol, an EO/PO Nonionic surfactant, CAS 64366-70-7).

The amount of the nonionic surfactant used in the composition of the present invention is preferably from about 0.05 to 8 wt%, more preferably from about 0.1 to 6 wt%.

The alcohol used in the composition of the present invention is not particularly limited, and any alcohol known to those skilled in the art to which the present invention pertains can be used in the present invention. Examples of specific alcohols include, but are not limited to, ethanol, propanol, isopropanol (IPA), n-butanol, isobutanol, n-pentanol, isoamyl alcohol or a combination thereof, preferably isopropanol .

The amount of the alcohol used in the composition of the present invention is preferably from about 1 to 25 wt%, more preferably from about 2 to 20 wt%.

The abbreviation "ACGIH" means "American Conference of Industrial Hygienists".

The abbreviation "TLV-TWA" means "low limit - eight hours of daily average volume "Concentration", which is the average exposure value based on a working cycle of 8 hours per day and 40 hours per week.

The abbreviation "TLV-STEL" means "low limit - short-term average allowable concentration", which is a point-like exposure measured within a 15-minute tolerance period but not more than 4 times per day.

The term "consisting essentially of" is a semi-open representation, meaning that the combination of the components does not exclude additional ingredients that are described in the description of the present invention and do not substantially affect the principal technical features of the present invention. If desired, the compositions of the present invention for removing stains and/or adhesive residues may further comprise one or more additives such as pigments, colors, flavors, propellants, pH adjusters, and metal complexing agents.

In the term "HLB value", H is "hydrophilic", L is "lipophilic", and B is "equilibrium", so the term "HLB value" means the equilibrium value of the hydrophilic group and the lipophilic group in the surfactant. The larger the HLB value, the stronger the hydrophilicity, and the smaller the HLB value, the stronger the lipophilicity. In general, the HLB value is between 1 and 40.

As used herein, the term "stain" means the soil commonly found on the surface of a substrate, such as soil, clay, oil, pigments, pigments, paints, and the like.

As used herein, the term "adhesive" means a viscous material commonly found on the surface of a substrate, such as pressure sensitive adhesives, silicones, superglue, etc., or when peeled off, for example, security labels, aluminum foil tape, sonic/vibration damping tape. A substance that remains on the surface of the substrate after the double-sided tape or the like.

According to another aspect, the present invention provides a method of making a cleaning composition for removing stains and/or adhesives comprising comprising a TWA value of substantially greater than or equal to 150 ppm from about 40 to 99 wt% And at least 5 And a nonionic surfactant having a HLB value of less than or equal to 12; and from about 1 to 30% by weight of an alcohol, and one or more alkyl hydrocarbons of up to 18 carbon atoms; The step of mixing the ingredients.

In general, the above-described method for producing a cleaning composition for removing stains and/or an adhesive of the present invention is carried out at a normal temperature.

The "mixing" step can be carried out using any means known to those of ordinary skill in the art, such as mechanical agitation (e.g., magnet stirring or stirring with a glass rod) or physical shock (e.g., ultrasonic vibration). The order of addition of the ingredients is not critical to the invention and does not affect the properties of the final composition.

According to still another aspect, the present invention provides a method of removing stains and/or an adhesive from a surface of a substrate, comprising: applying a composition of the present invention to the stain and/or adhesive on a surface of a substrate; The composition is contacted with the stain and/or adhesive for a time sufficient to form a conjugate; and the conjugate is removed from the substrate.

The substrate described herein is not particularly limited and may be, but not limited to, wood, stone, metal (such as stainless steel) and plastic materials (such as acrylic, polyvinyl chloride (PVC), polycarbonate (PC). , acrylonitrile-butadiene-styrene (ABS), ethylene terephthalate (PET) and polypropylene (PP), and the like.

The contact time of the stain and/or adhesive with the composition depends on the nature of the stain and/or the adhesive, the relative amount, and the characteristics of the components. The length of contact should be sufficient to allow the stain and/or adhesive to soften and swell, and Compound ball. The "sufficient time" includes, but is not limited to, 5 minutes, 10 minutes, 20 minutes, 30 minutes or longer, but should not exceed the time during which the solvent will substantially dry out of the composition.

Compared with the conventional adhesive remover composition, the cleaning composition for removing stains and/or adhesives of the present invention mainly has low skin irritation, low toxicity and high ACGIH TLV-TWA/TLV-STEL low limit value. The advantages. When the composition of the present invention is used to remove stains and/or adhesives on a substrate, the stain and/or the adhesive can be easily formed into balls for easy removal without sticking of the adhesive and without causing the substrate ( Especially plastic substrates) corrosion or atomization. The compositions of the present invention are relatively inexpensive compared to adhesive removers comprising natural solvents such as citric acid extracts.

The invention is further described in the following examples, which are not intended to limit the scope of the invention, and any modifications and variations which may be made without departing from the spirit of the invention are intended to be included in the invention. range.

Example 1

The composition of the present invention is selected from the group consisting of alkyl hydrocarbons 1: commercially available from China Petroleum Chemical Corporation, "industrial grade heptane", which contains about 35% heptane (CAS 142-82-5), about 64% of other C6, C7 and C8 alkyl hydrocarbons and petroleum ethers, and trace amounts (about 1%) of methylcyclohexane.

Alkyl Hydrocarbon 2: Commercially available from China Petroleum Chemical Corporation, "DC-1 Alcohol Free Cleaning Solvent", which contains about 13% octane, about 27% decane, and about 60% other C6. , C7 and C8 alkyl hydrocarbons (CAS 64742- 49-0).

Alcohol: Isopropyl alcohol (IPA) available from LCY Chemical Corp.

Conventional adhesive removers typically comprise toluene, xylene and hexane as constituents.

The properties of the ingredients selected in the above compositions of the present invention and the conventional adhesive removers generally include the following:

Example 2-6 raw material

3M ^TM Adhesive Transfer Tape: Model 300LSE, where the adhesive is a high strength acrylic adhesive.

Alkyl hydrocarbon 1: commercially available from China Petrochemical Corporation, "industrial grade heptane", containing about 35% heptane (CAS 142-82-5), about 64% of other C6, C7 and C8 Alkyl hydrocarbons and petroleum ethers, and trace amounts (about 1%) of methylcyclohexane.

Nonionic surfactant: Ecosurf EH-3 from Dow Chemical Corp., hereinafter referred to as "EH-3"

Alcohol: Isopropyl alcohol (IPA) available from LCY Chemical Corp.

Flavor: Bamboo salt and Happy Lemon Flavor from Firmenich.

Sample preparation

A. Depending on the composition, the adhesive remover solution of each example is prepared in any of the following ways:

1. Add the nonionic surfactant to the alcohol (or water) and mix for 5 minutes.

2. A mixture of a nonionic surfactant and an alcohol (or water) is added to the alkyl hydrocarbon 1 and mixed for 5 minutes.

3. Add perfume to the above mixture as needed until homogeneous.

testing method 1. Swelling test method

This test describes the effect of testing the adhesive remover solution to swell the adhesive. Cut the 300 kel tape that is 1.5 cm wide and 6 cm long. After removing the release paper from the tape, pour the adhesive into pellets and measure and record the net weight of the adhesive pellet.

Adhesive pellets were placed in a 15 ml glass vial with 3 grams of a commercially available detergent containing D-Lemon Lyme or the above example adhesive remover solution, and the adhesive pellet was immersed for 10 minutes, then The adhesive remover solution was removed and the expanded weight of the adhesive pellet after expansion was measured. The swelling is calculated by subtracting the weight of the original adhesive pellet from the expansion weight of the adhesive pellet after 10 minutes of expansion.

2. Wipe test

Cut the 300 kel tape that is 1.5 cm wide and 3 cm long and attach it to the stainless steel flat plate. After removing the release paper from the tape, leave only the adhesive on the stainless steel flat plate. A commercially available detergent containing D-Lemon Lyme or an adhesive remover solution of each of the above examples is dropped or sprayed on top of the adhesive. First, spray Sprinkle the solution and let the adhesive swell for 1 minute. Use a cloth rag to wipe the adhesive for the first time. After the second and third wipes, do not wait for the expansion time and wipe the adhesive directly.

The first time you wipe, you can feel and adjust the "expansion and penetration" effect of the adhesive remover solution on the adhesive in each case, which is classified into good, good and bad grades. For the second and third wiping, you can adjust the "balling (not trailing)" nature and classify them into good, good and bad grades.

result:

From the above results, it was found that the cleaning compositions of the present invention (Examples 4, 5 and 6) can make the adhesive more comparable to the commercially available detergents containing D-Lemon Lyme and the adhesive remover solutions of Examples 2 and 3. It is easy to form a ball and does not cause sticking of the adhesive.

Example 7-9 raw material

3M ^TM Adhesive Transfer Tape: Model 300LSE, where the adhesive is a high strength acrylic adhesive.

Alkyl hydrocarbon 1: commercially available from China Petrochemical Corporation, "industrial grade heptane", containing about 35% heptane (CAS 142-82-5), about 64% of other C6, C7 and C8 Alkyl hydrocarbons and petroleum ethers, and trace amounts (about 1%) of methylcyclohexane.

Alkyl Hydrocarbon 2: Commercially available product "DC-1 Alcohol Free Cleaning Solvent" from China Petrochemical Co., Ltd., containing about 13% octane, about 27% decane, and about 60% other C6. C7 and C8 alkyl hydrocarbons (CAS 64742-49-0).

Nonionic surfactant: Ecosurf EH-3 from Dow Chemical Corp., hereinafter referred to as "EH-3"

Alcohol: Isopropyl alcohol (IPA) available from LCY Chemical Corp.

Fragrance: Bamboo salt and Happy Lemon Flavor from Firmenieh.

Sample preparation

A. Depending on the composition, the adhesive remover solution of each example is prepared in any of the following ways:

1. Add the nonionic surfactant to the alcohol (or water) and mix for 5 minutes.

2. A mixture of a nonionic surfactant and an alcohol (or water) is added to the alkyl hydrocarbon 1 or alkyl hydrocarbon 2 and mixed for 5 minutes.

3. Add perfume to the above mixture as needed until homogeneous.

testing method 1. Swelling test method

This test describes the effect of testing the adhesive remover solution to swell the adhesive. Cut the 300 kel tape that is 1.5 cm wide and 6 cm long. After removing the release paper from the tape, pour the adhesive into pellets and measure and record the net weight of the adhesive pellet.

Adhesive pellets were placed in a 15 ml glass vial with 3 g of each of the above example adhesive remover solutions, the adhesive pellets were immersed for 10 minutes, then removed from the adhesive remover solution, and the adhesion was measured. The expanded weight of the pellet after expansion. The swelling is calculated by subtracting the weight of the original adhesive pellet from the expansion weight of the adhesive pellet after 10 minutes of expansion.

2. Wipe test

Cut the 300 kel tape of 1.5 cm width and 3 cm length, attach it to the stainless steel flat plate, and then remove the release paper on the tape, then drop or spray the adhesive remover solution of each of the above examples. Above the adhesive. First, spray the solution and swell the adhesive for 1 minute. The first wipe of the adhesive is performed with a cloth rag. After the second and third wipes, the adhesive is directly wiped without waiting for the expansion time.

The first time you wipe, you can feel and adjust the "expansion and penetration" effect of the adhesive remover solution on the adhesive in each case, which is classified into good, good and bad grades. For the second and third wiping, you can adjust the "balling (not trailing)" nature and classify them into good, good and bad grades.

3. Evaporation rate (60 ° C ^* 10 minutes, unit: gram / 10 minutes)

Take 3 g of the above-mentioned various examples of the adhesive remover solution and place 15 ml. In the glass bottle, measure the total weight of the solution and the glass bottle. After the sample vial was placed in an oven at 60 ° C for 10 minutes, it was removed from the oven and cooled to room temperature, and the evaporation rate was calculated by subtracting the original total weight from the total weight after 10 minutes.

result:

The cleaning compositions of the present invention (Examples 7, 8, and 9) allow the adhesive to more easily form a ball without the sticking of the adhesive.

Claims (14)

A cleaning composition consisting essentially of: about 50 to 95 wt% having a TWA value of greater than or equal to 150 ppm and at least 5 and up to 18 carbon atoms of one or more alkyl hydrocarbons; about 0.01- 10% by weight of a nonionic surfactant having an HLB value of less than or equal to 12; and from about 1 to 30% by weight of an alcohol. The cleaning composition of claim 1 wherein the one or more alkyl hydrocarbons have a TWA value greater than or equal to 175 ppm. The cleaning composition of claim 2, wherein the one or more alkyl hydrocarbons have a TWA value greater than or equal to 200 ppm. The cleaning composition of claim 1 wherein the one or more alkyl hydrocarbons have at least 7 and up to 14 carbon atoms. The cleaning composition of claim 4, wherein the one or more alkyl hydrocarbons have at least 7 and up to 10 carbon atoms. A cleaning composition according to claim 1 which comprises one or more alkyl hydrocarbons selected from the group consisting of n-heptane, isoheptane, octane, nonane, decane, undecane and dodecane. The cleaning composition of claim 1, wherein the alkyl hydrocarbon is used in an amount of from about 50 to 92% by weight. The cleaning composition of claim 1, wherein the nonionic surfactant has an HLB value of from 0 to 11. The cleaning composition of claim 8, wherein the nonionic surfactant is an ethoxylated alcohol. The cleaning composition of claim 1, wherein the nonionic surfactant The amount used is 0.05-8 wt%. The cleaning composition of claim 1, wherein the alcohol is isopropanol. A cleaning composition according to claim 1 or 11, wherein the amount of the alcohol is from about 1 to 25% by weight. A method of making a cleaning composition according to any one of claims 1 to 12, which comprises substantially having from about 40 to 99% by weight of a TWA value of greater than or equal to 150 ppm and at least 5 and up to 18 carbon atoms One or more alkyl hydrocarbons; from about 0.01 to 10% by weight of a nonionic surfactant having an HLB value of less than or equal to 12; and a composition of from about 1 to 30% by weight of the alcohol. A method of removing a stain and/or an adhesive from a surface of a substrate, comprising: applying a cleaning composition according to any one of claims 1 to 12 to the stain and/or adhesive on a surface of the substrate; The cleaning composition is contacted with the stain and/or adhesive for a sufficient period of time to form a conjugate; and the conjugate is removed from the substrate.