A fabric whitening and brightening additive composition and a detergent containing the composition

Abstract

The present invention relates to the field of detergents, and discloses a fabric whitening and brightening additive composition and a detergent containing the composition. The fabric whitening and brightening additive composition comprises the following components in weight percentage: 1-70% of a polycarboxylic acid with an unsaturated carbon ring, 1-20% of an anionic fluorescent brightener, and 1-70% of an alcohol solvent. The fabric whitening and brightening additive composition of the present invention contains a polycarboxylic acid with an unsaturated carbon ring, which can greatly improve the whitening and brightening effect of the anionic fluorescent brightener on the fabric, thereby reducing the addition amount of the anionic fluorescent brightener, and can effectively solve the problems of high viscosity and easy gelation in the detergent system of high active substances; in addition, the preparation operation of the whitening and brightening additive composition of the present invention is simple, easy to add, and can be stably used in fabric detergents.

Description

Technical Field

[0001] The invention relates to the field of detergents, in particular to a fabric whitening and brightening additive composition and a detergent containing the composition. Background Art

[0002] When clothes are worn, they absorb blue light in the visible light, which causes the whiteness of the fabric to be affected by the lack of blue light. Therefore, the clothes will turn yellow and become old. For this reason, people often use chemical bleaching, bluing, and fluorescent whitening agents to improve this phenomenon. Among them, the chemical structure of fluorescent whitening agents is generally a conjugated system containing π electrons. Common ones include benzene rings, naphthalene rings, triazine rings, vinyl and five-membered heterocycles. The higher the degree of conjugation, the larger the wavelength of light that can be absorbed, the easier it is for electrons to be excited, and the higher the fluorescence efficiency; the structure is -C=CC=CC=C- or -N=CC=NC=C-. This structure determines its spectral performance, which can absorb invisible ultraviolet light (wavelength of about 340-370nm) and reflect visible blue-violet fluorescence (wavelength of about 410-470nm). It uses the principle of complementary colors in optics, that is, the emitted blue-violet light and yellow are complementary colors to each other, eliminating yellowing and visually improving the whiteness of the fabric.

[0003] However, the existing fluorescent whitening agents have the disadvantage that the fluorescent whitening agent molecules are attached to the fibers in the form of single molecules, the fluorescence intensity of the single color system is limited, and the affinity to clothing fibers is lacking, and the whitening effect is not ideal. Therefore, in order to achieve a better whitening effect, it is usually necessary to add a large amount of fluorescent whitening agents, but the price of fluorescent whitening agents is generally high, and the economic benefit problem caused by the cost after adding a large amount cannot be ignored. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a fabric whitening and brightening additive composition and a detergent containing the composition. The fabric whitening and brightening additive composition of the present invention contains a polycarboxylic acid with an unsaturated carbon ring, which can greatly improve the whitening and brightening effect of anionic fluorescent whitening agents on fabrics, thereby reducing the amount of anionic fluorescent whitening agents added, and can effectively solve the problems of high viscosity and easy gelation in detergent systems with high active substances; in addition. The whitening and brightening additive composition of the present invention is simple to prepare and easy to add, and can be stably used in fabric detergents.

[0005] The specific technical scheme of the present invention is:

[0006] In a first aspect, the present invention provides a fabric whitening and brightening additive composition, comprising the following components in weight percentage: 1-70% of a polycarboxylic acid having an unsaturated carbon ring, 1-20% of an anionic fluorescent brightener, and 1-70% of an alcohol solvent.

[0007] The present invention finds that the introduction of a polycarboxylic acid having an unsaturated carbon ring into a fabric whitening and brightening additive composition can improve the deposition effect of anionic fluorescent whitening agents on fabric fibers, thereby improving the utilization rate of fluorescent whitening agents, having good stability in detergents, and being significantly better than the effect of anionic fluorescent whitening agents when used alone. After further research and analysis, the present invention speculates that its synergistic mechanism is as follows: the structure of anionic fluorescent whitening agents is a planar conjugated system containing aromatic rings, which absorbs ultraviolet rays to cause electrons to transition from a singlet ground state to an excited state, and return to the ground state to emit fluorescence, and the substituents on the conjugated system can change the fluorescence characteristics. When anionic fluorescent whitening agents are used alone, they are attached to fibers in the form of a single molecule, and the fluorescence intensity of a single color system is limited, and they lack affinity for clothing fibers. (1) Anionic fluorescent whitening agents contain electron-donating groups but no electron-withdrawing groups. The multiple carboxyl groups in the polycarboxylic acids with unsaturated carbon rings may act as color-adjusting groups as electron-withdrawing groups, changing the fluorescence properties and intensity of the anionic fluorescent whitening agents, broadening the wavelength of the radiation spectrum of light, and improving the overall fluorescence intensity, thereby changing the whitening performance, making it better than the whitening effect when using only anionic fluorescent whitening agents. (2) Electron-withdrawing groups can increase water solubility. At the same time, the unique unsaturated carbon ring structure of polycarboxylic acids enables the system to maintain good stability at low temperatures, thereby making the entire detergent system more stable. (3) The long carbon chain structure of polycarboxylic acids increases the intermolecular force between the anionic fluorescent whitening agent and the fabric fiber, namely the van der Waals force, making the anionic fluorescent whitening agent more adsorbed on the fabric, improving the fabric whiteness and the stability of the entire system. Under the condition of using the same amount of anionic fluorescent brightener, the whitening and brightening effect is better, or the amount of anionic fluorescent brightener can be reduced while maintaining the excellent whitening effect, thus saving costs and improving efficiency.

[0008] Preferably, the polycarboxylic acid having an unsaturated carbocyclic ring is C 21 Dicarboxylic acids and / or C 22 Tricarboxylic acid.

[0009] C 21 The structural formula of dicarboxylic acid is:

[0010]

[0011] wherein X+Y=12, X≥0, Y≥0; one of R1 and R2 is a carboxyl group, and the other is hydrogen;

[0012] C 22 The structural formula of tricarboxylic acid is:

[0013]

[0014] Where X+Y=12, X≥0, Y≥0.

[0015] Preferably, the mass ratio of the polycarboxylic acid having an unsaturated carbon ring to the anionic fluorescent whitening agent is 10 to 40:1.

[0016] The present invention has found in the research process that the mass ratio of the polycarboxylic acid with unsaturated carbon ring and the anionic fluorescent whitening agent has a great influence on the whitening and brightening effect. When the mass ratio of the two is controlled within the range of 10 to 40:1, a better whitening and brightening effect can be produced. When the amount of the anionic fluorescent whitening agent is too large, the whitening effect on the fabric is reduced instead of increased. The whitening effect of the anionic fluorescent whitening agent is only proportional to the concentration within a certain range, because when the concentration of the anionic fluorescent whitening agent reaches the "yellowing point", the anionic fluorescent whitening agent molecules aggregate and present multi-molecular layer adsorption. The distribution of the anionic fluorescent whitening agent molecules should be a single molecular layer. Excessive aggregation of the anionic fluorescent whitening agent molecules will reduce the fluorescence quantum efficiency, and the wavelengths of the absorbed and reflected light will change, resulting in a sudden decrease in the whitening effect. When the amount of polycarboxylic acid with unsaturated carbon ring is too large, the solution viscosity is extremely low, which is inconvenient to use. Consumers cannot actually and intuitively feel the performance of the product. When this component reaches a certain concentration, the whitening effect reaches an extreme value and the whiteness difference will no longer increase, so excessive addition has no practical significance.

[0017] Preferably, the anionic fluorescent brightener is one or more of a bis(vinylbenzene) biphenyl type brightener (such as CBS, FP, etc.), a bis(triazine) aminostilbene type brightener (such as VBL, CXT, etc.), a pyrazoline type fluorescent brightener (such as DCB, NSM, etc.) and a coumarin type fluorescent brightener (such as SWN, WS, etc.).

[0018] Preferably, the alcohol solvent is one or more of ethanol, ethylene glycol, propylene glycol, isopropanol, sorbitol, glycerol and isohexanediol.

[0019] In a second aspect, the present invention provides a method for preparing a fabric whitening and brightening additive composition: adding a polycarboxylic acid having an unsaturated carbon ring to an alcohol solvent, stirring at 30 to 35° C. until completely dissolved, and then adding an anionic fluorescent brightener to obtain the fabric whitening and brightening additive composition after complete dissolution.

[0020] In a third aspect, the present invention provides a fabric detergent comprising a fabric whitening and brightening additive composition in an amount of 0.1 to 10% by weight of the total detergent.

[0021] The present invention also found in the research process that the fabric whitening and brightening additive composition, when used in conjunction with concentrated fabric detergent, has not only obvious whitening and brightening effects, but also has a greater impact on solution viscosity, and has stable performance. The reason is inferred as follows: under the solvent preparation condition, the interaction between the polycarboxylic acid and the fluorescent whitening agent is strengthened, and when used in conjunction with the concentrated fabric detergent, the solubilization of the composition components by the surfactant is reduced, the whitening agent can be more firmly attached to the surface of the fabric fiber, the unsaturated carbon ring structure of the polycarboxylic acid can also play a more full role, and the solution is not easy to produce gel phenomenon, so as to achieve the effect of the joint action. The composition solution not only has good stability in the concentrated formula, but also significantly reduces the solution viscosity, effectively avoids the gel area, and can solve the common problems in concentrated detergents, such as concentrated detergents are prone to gel phenomenon due to high active substances, or have high viscosity and poor water-soluble dispersibility.

[0022] Preferably, the fabric detergent further comprises an anionic surfactant and a nonionic surfactant.

[0023] Anionic fluorescent whitening agents tend to aggregate into molecular clusters in systems with high concentrations of nonionic surfactants, reducing the whitening effect. The polycarboxylic acid with unsaturated carbon rings in the fabric whitening and brightening additive composition can increase the cloud point of nonionic surfactants, while providing a synergistic effect for anionic surfactants, improving the detergency, and acting as a cosolvent, effectively solving the crystallization problem of fluorescent whitening agents. In a system of nonionic surfactants and anionic surfactants, the polycarboxylic acid with unsaturated carbon rings can reduce the Krafft point of the system, and its unsaturated carbon structure enables the system to maintain good stability at low temperatures.

[0024] Furthermore, the anionic surfactant includes one or more selected from saturated fatty acid salts, alkylbenzene sulfonates, sodium polyoxyethylene fatty alcohol ether sulfates, fatty acid methyl ester sulfonates, dodecyl sulfates, modified oil ethoxylate sulfonates, N-fatty acyl amino acid salts and sodium α-olefin sulfonates; the nonionic surfactant is selected from one or more selected from natural alcohol polyoxyethylene ethers, alkyl glycosides, isomeric alcohol polyoxyethylene ethers, fatty alcohol polyoxyethylene polyoxypropylene ethers, fatty acid ester ethoxylates, fatty acid methyl monoethanolamide, fatty acid monoethanolamide and modified oil ethoxylates.

[0025] Preferably, the detergent further comprises one or more of a chelating agent, an acid-base regulator, an anti-redeposition agent, an inorganic salt, a sunscreen, a preservative, a defoaming agent, an antibacterial agent, an enzyme preparation, a flavor and a pigment.

[0026] Compared with the prior art, the present invention has the following technical effects:

[0027] (1) The fabric whitening and brightening additive composition of the present invention contains a polycarboxylic acid having an unsaturated carbon ring, which can greatly improve the whitening and brightening effect of the anionic fluorescent brightener on the fabric, thereby reducing the amount of the anionic fluorescent brightener added.

[0028] (2) The fabric whitening and brightening additive composition of the present invention can effectively solve the problems of high viscosity and easy gelation in detergent systems with high active ingredients.

[0029] (3) The whitening and brightening additive composition of the present invention is simple to prepare and easy to add, and can be stably used in fabric detergents. DETAILED DESCRIPTION

[0030] The present invention is further described in the following examples, but the protection scope of the present invention is not limited thereto.

[0031] The professional terms and technical means used in the present invention have the same meanings as those generally understood by those skilled in the art. Unless otherwise specified, the various reagents, raw materials, equipment, etc. in the present invention are commonly used reagents, raw materials, equipment understood by those skilled in the art and are all commercially available.

[0032] Overall embodiment

[0033] A fabric whitening and brightening additive composition comprises the following components in weight percentage: 1-70% of a polycarboxylic acid having an unsaturated carbon ring, 1-20% of an anionic fluorescent whitening agent, and 1-70% of an alcohol solvent (selected from one or more of ethanol, ethylene glycol, propylene glycol, isopropanol, sorbitol, glycerol, and isohexanediol). Preferably, the mass ratio of the polycarboxylic acid having an unsaturated carbon ring to the anionic fluorescent whitening agent is 10-40:1.

[0034] Preferably, the polycarboxylic acid having an unsaturated carbocyclic ring is C 21 Dicarboxylic acids and / or C 22 Tricarboxylic acid. 21 The structural formula of dicarboxylic acid is:

[0035]

[0036] wherein X+Y=12, X≥0, Y≥0; one of R1 and R2 is a carboxyl group, and the other is hydrogen;

[0037] Furthermore, C 21 The dicarboxylic acid has X=5, Y=7, and the structural formula is:

[0038]

[0039] or

[0040]

[0041] C 22 The structural formula of tricarboxylic acid is:

[0042]

[0043] Where X+Y=12, X≥0, Y≥0. Furthermore, C 22 The tricarboxylic acid has X=5, Y=7, and the structural formula is:

[0044]

[0045] Preferably, the anionic fluorescent brightener is one or more of a bis(vinylbenzene) biphenyl type brightener (such as CBS, FP, etc.), a bis(triazine) aminostilbene type brightener (such as VBL, CXT, etc.), a pyrazoline type fluorescent brightener (such as DCB, NSM, etc.) and a coumarin type fluorescent brightener (such as SWN, WS, etc.).

[0046] A method for preparing a fabric whitening and brightening additive composition comprises the following steps: adding a polycarboxylic acid having an unsaturated carbon ring into an alcohol solvent, stirring at 30-35°C until completely dissolved, and then adding an anionic fluorescent brightener to obtain the fabric whitening and brightening additive composition after complete dissolution.

[0047] A fabric detergent: containing 0.1-10% of the total mass of the detergent as a fabric whitening and brightening additive composition, anionic surfactant, nonionic surfactant, and selectively including one or more of chelating agent, acid-base regulator, anti-redeposition agent, inorganic salt, sunscreen, preservative, defoamer, antibacterial agent, enzyme preparation, essence and pigment.

[0048] Furthermore, the anionic surfactant includes one or more selected from saturated fatty acid salts, alkylbenzene sulfonates, sodium polyoxyethylene fatty alcohol ether sulfates, fatty acid methyl ester sulfonates, dodecyl sulfates, modified oil ethoxylate sulfonates, N-fatty acyl amino acid salts and sodium α-olefin sulfonates; the nonionic surfactant is selected from one or more selected from natural alcohol polyoxyethylene ethers, alkyl glycosides, isomeric alcohol polyoxyethylene ethers, fatty alcohol polyoxyethylene polyoxypropylene ethers, fatty acid ester ethoxylates, fatty acid methyl monoethanolamide, fatty acid monoethanolamide and modified oil ethoxylates.

[0049] Test Method

[0050] (I) Test method for anionic fluorescent whitening agent content on fabrics and calculation method for deposition rate Experimental method: High performance liquid chromatography fluorescence method HPLC-FLD was used to determine the content of anionic fluorescent whitening agent on fabrics. Dimethylformamide (DMF) and water with a volume ratio of 7:3 were used as the extraction solvent. Ultrasonic extraction was performed at 50°C for 20 min, and repeated twice. A ZORBAX Eclipse XDB-Phenyl column (4.6 mm×250 mm, 5 μm) was used as the separation chromatographic column. The column temperature was 30°C, and 20 mmol / L ammonium acetate solution, acetonitrile, and methanol were used as the mobile phases for gradient elution, which can effectively separate the fluorescent whitening agent.

[0051] Step a: Use a vertical detergent (RHLQ II, manufactured by China Daily Chemical Industry Research Institute) to wash the cotton white cloth (in compliance with the provisions of HG / T 2609-1994), the washing conditions are water hardness 250ppm, water temperature 30°C, time 20 minutes, rotation speed 120rpm, concentration 2.0g / L (concentrated detergent is reduced according to the active content), rinse 3 times after washing, and dry naturally after rinsing.

[0052] Step b: After cutting the sample treated in step a into 5 mm×5 mm pieces, weigh 1.0 g of the sample and place it in 20 mL of a dimethylformamide-water mixed solution (volume ratio 7:3) as an extraction solvent. After ultrasonic extraction at 50°C for 20 min, centrifuge it in a high-speed centrifuge for 5 min, filter the filtrate with a 0.45 μm PTFE filter membrane, and measure it by HPLC-FLD. The fluorescent whitening agent in the sample is quantified by the external standard method according to the chromatographic peak area.

[0053] Anionic fluorescent brightener content calculation formula:

[0054]

[0055] Where:

[0056] X: Fluorescent brightener content (mg / Kg)

[0057] c: Fluorescent whitening agent solution concentration obtained from the standard curve (mg / mL)

[0058] V: Volume (mL)

[0059] m: mass (kg)

[0060] Anionic fluorescent brightener deposition rate calculation formula:

[0061]

[0062] Where:

[0063] X: Fluorescent brightener content (mg / Kg)

[0064] A 总 : Total fluorescent brightener content in detergent solution (mg / Kg)

[0065] Whitening effect test method

[0066] Experimental method: Cut cotton white cloth (in accordance with the provisions of HG / T 2609-1994) into 6cm×6cm size, and form a group of 6 pieces. The concentration of the test solution is 2.0g / L (the amount of concentrated detergent is reduced according to the content of active ingredients). Put the cotton white cloth into the test solution, stir continuously for 10 minutes, take out the cloth, rinse twice, 3 minutes each time. After taking out, spread it flat and arrange it on a plate to dry. After drying, use a whiteness meter to measure the whitening effect.

[0067] (II) Whitening effect evaluation method and calculation formula

[0068] (1) The whitening effect is expressed by the whitening value Z before and after washing. The larger the whitening value, the better the whitening effect.

[0069] (2) Whiteness value WI (CIE) before washing: measure at the center of the front and back sides of the cloth before washing, and take the average of the two measurements as the whiteness of the cloth before washing. Whiteness value WI (CIE) after washing: take four points on the front and back sides of the cloth after washing, two points on each side and measure symmetrically, and take the average of the four measurements as the whiteness of the cloth after washing.

[0070] (3) Calculation formula:

[0071]

[0072] Where:

[0073] Z: The whitening value of the fabric by the fluorescent brightener sample

[0074] ΔWI(CIE)=WI(CIE) 洗后 -WI(CIE) 洗前

[0075] (III) Test method for brightening effect

[0076] Experimental method: Cut the pure cotton blue cloth into 8cm×8cm size, and each 6 pieces form a group. Use a vertical decontamination machine (RHLQ II, manufactured by China Daily Chemical Industry Research Institute) to wash the cotton blue cloth according to the method specified in GB / T 13174-2008. The washing conditions are water hardness 250ppm, water temperature 30℃, time 20 minutes, speed 120rpm, concentration 4.0g / L (concentrated detergent is reduced according to the active content), rinse twice after washing, and dry naturally after rinsing. Use a whiteness meter to test the brightening effect of the cotton blue cloth.

[0077] Evaluation method of brightening effect:

[0078] The brightening effect is expressed by the saturation difference of ΔC*(D65) of blue cloth washed with different detergents, where ΔC*(D65)=C*(D65) 洗涤剂A -C*(D65) 洗涤剂B If ΔC*(D65)>0, it means that the fabric sample washed by detergent A is brighter than the fabric sample washed by detergent B, and the brightening effect of the colored fabric is better. Specific embodiments

[0080] Examples 1 to 4, Comparative Example 1 and Test Examples 1 to 6

[0081] In Table 1, the contents of each component of the fabric whitening and brightening additive composition are all in parts, and the amount not filled in means 0.

[0082] Table 1

[0083] Components Example 1 Example 2 Example 3 Example 4 Comparative Example 1 <![CDATA[C 21 Dicarboxylic Acids]]> 6 12 10 6 <![CDATA[C 22 Tricarboxylic Acid]]> 8 15 Anionic light extinguishing brightener CBS-X 0.5 1 1 0.5 0.5 Propylene glycol 4 5 10 Ethylene glycol 5 Deionized water 4

[0084] In Table 1, C 21 The dicarboxylic acid is C 22 Tricarboxylic acid is

[0085] The preparation steps of Example 1 are as follows: using propylene glycol as solvent, mixing C 21 The dicarboxylic acid is prepared into a solution with a mass fraction of 60%. 10 g of the above solution is taken, and 0.50 g of CBS-X is added thereto. The mixture is stirred evenly to make it completely dissolved, thereby obtaining a composition.

[0086] The preparation steps of Example 2 are as follows: using propylene glycol as solvent, mixing C 21 Dicarboxylic acids and C 22 The tricarboxylic acid (mass ratio 3:2) was prepared into a solution with a mass fraction of 80%. 10 g of the above solution was taken, and 1.00 g of CBS-X was added thereto. The mixture was stirred evenly to make it completely dissolved, thereby obtaining a composition.

[0087] The preparation steps of Example 3 are as follows: using propylene glycol as solvent, mixing C 21 The dicarboxylic acid is prepared into a solution with a mass fraction of 50%. 10 g of the above solution is taken, and 1.00 g of CBS-X is added thereto. The mixture is stirred evenly to make it completely dissolved, thereby obtaining a composition.

[0088] The preparation steps of Example 4 are as follows: using ethylene glycol as solvent, heating C 21The dicarboxylic acid is prepared into a solution with a mass fraction of 75%. 20 g of the above solution is taken, and 0.50 g of CBS-X is added thereto. The mixture is stirred evenly to make it completely dissolved, thereby obtaining a composition.

[0089] The preparation steps of comparative example 1 are as follows: in room temperature, C 21 The dicarboxylic acid is prepared into an aqueous solution with a mass fraction of 60%. 10 g of the above solution is taken, and 0.50 g of CBS-X is added thereto. The mixture is stirred evenly to make it completely dissolved, thereby obtaining a composition.

[0090] Stability of the whitening and brightening additive composition: The fabric whitening and brightening additive composition of Examples 1-4 was placed in a thermostat at 45°C ± 2°C and -18°C ± 2°C for 24 hours, taken out and restored to room temperature before observation. The results showed that the compositions of Examples 1-4 all had good stability, and the system had no precipitation and no stratification.

[0091] The fabric whitening and brightening additive compositions of Examples 1-4 and Comparative Example 1 were formulated into fabric detergents, and the compositions are shown in Table 2. The contents of the following components are all in weight percentage, and those not filled in are added in an amount of 0, and the remainder is deionized water.

[0092] Table 2

[0093]

[0094]

[0095] The evaluation of the whitening and brightening effect of the fabrics in Table 2 before and after washing is shown in Table 3.

[0096] Table 3

[0097] Whitening value (Z) Whitening value (Z) improvement rate ΔC*(D65) Test Example 1 29.33 206％ ＞0 Test Example 2 28.18 194％ ＞0 Test Example 3 28.34 195％ ＞0 Test Example 4 28.91 201％ ＞0 Test Example 5 20.38 113％ ＞0 Test Example 6 9.58

[0098] In Table 3, the whitening value (Z) improvement rate of test examples 1 to 5 is the improvement rate compared with test example 6. The ΔC*(D65) value of test examples 1 to 5 is the saturation difference compared with test example 6, that is, ΔC*(D65)=C*(D65) 测试例1～5 -C*(D65) 测试例6 .

[0099] The deposition rate of anionic fluorescent brightener after washing the fabric with the fabric detergent in Table 2 is shown in Table 4.

[0100] Table 4

[0101] Deposition rate / % Test Example 1 15.22 Test Example 2 14.30 Test Example 3 14.86 Test Example 4 15.04 Test Example 5 10.09 Test Example 6 6.51

[0102] From the data in Table 2-4, we can see that:

[0103] (1) The whitening and brightening additive compositions of Examples 1-4 have a significant improvement effect on the whitening effect of fabrics, with the improvement rate reaching about 200%. The viscosity change is more stable, which has the effect of reducing viscosity and resisting gelation. The content of anionic fluorescent brightener on the fabric is higher, indicating that the polycarboxylic acid with an unsaturated carbon ring structure can promote the deposition of fluorescent brightener on fabric fibers, making the adsorption of the brightener on the fibers stronger, so as to achieve the effect of whitening and brightening together.

[0104] (2) It can be seen from Test Example 5 that when the composition is prepared using only deionized water without using a solvent, the whitening effect is poor and it does not have a significant viscosity reducing effect in the detergent.

[0105] Examples 5 to 6 and Test Examples 7 to 9

[0106] In Table 5, the contents of each component of the whitening and brightening additive composition are in parts.

[0107] Table 5

[0108] Components Example 5 Example 6 <![CDATA[C 22 Tricarboxylic Acid]]> 1 5 CBS-X 1 0.1 Ethylene glycol 4 5

[0109] Table 5C 22 Tricarboxylic acid is

[0110] The preparation steps of Example 5 are as follows: using ethylene glycol as solvent, heating C 22 The tricarboxylic acid is prepared into a solution with a mass fraction of 20%. 5 g of the above solution is taken, and 1.00 g of CBS-X is added thereto. The mixture is stirred evenly to make it completely dissolved, thereby obtaining a composition.

[0111] The preparation steps of Example 6 are as follows: using ethylene glycol as solvent, heating C 22 The tricarboxylic acid is prepared into a solution with a mass fraction of 50%. 10 g of the above solution is taken, and 0.10 g of CBS-X is added thereto. The mixture is stirred evenly to make it completely dissolved, thereby obtaining a composition.

[0112] The fabric whitening and brightening additive compositions of Examples 5 and 6 were formulated into fabric detergents, and the compositions are shown in Table 6. The contents of the following components are all in weight percentage, and those not filled in are added in 0 amount, and the remainder is deionized water.

[0113] Table 6

[0114] Components Test Example 7 Test Case 8 Test Example 9 AES 20 20 20 LAS 6 6 6 AEO-9 8 8 8 Alkyl glycoside 1 1 1 Coconut oil fatty acids 1.8 1.8 1.8 EDTA 1 1 1 Sodium Citrate 1 1 1 HP 20 0.2 0.2 0.2 KOH / Citric Acid Monohydrate Adjust pH Adjust pH Adjust pH Whitening and brightening additive composition of Example 5 6 Whitening and brightening additive composition of Example 6 6 1% pH 8.4 8.3 8.4 Viscosity 1003 448 1288

[0115] The evaluation of the whitening effect of the fabrics in Table 6 before and after washing is shown in Table 7.

[0116] Table 7

[0117] Test Example 7 Test Case 8 Test Example 9 Whitening value (z) 11.39 17.30 12.03 Whitening value (Z) improvement rate -5.3％ 43％

[0118] The improvement rates of the whitening values ​​(Z) of Test Examples 7 to 8 are the improvement rates compared with Test Example 9.

[0119] From the data in Table 6 and Table 7, we can see that:

[0120] (1) When the mass ratio of the polycarboxylic acid having a carbocyclic structure to the anionic fluorescent whitening agent is less than 10-40:1, the viscosity does not change significantly, and the whitening effect decreases instead of increases.

[0121] (2) When the mass ratio of the polycarboxylic acid having a carbocyclic structure to the anionic fluorescent whitening agent is greater than 10 to 40:1, the viscosity is greatly reduced and the whitening value improvement rate is significantly lower than that of Examples 1 to 4.

[0122] Test cases 10 to 15

[0123] The whitening and brightening additive composition of Example 3 was used to study the whitening effect of different addition amounts in fabric detergents. The composition of the fabric detergent is shown in Table 8, and the content of each component below is weight percentage, and the amount not filled in is 0, and the balance is deionized water.

[0124] Table 8

[0125]

[0126] The evaluation of the whitening effect of the fabrics in Table 8 before and after washing is shown in Table 9.

[0127] Table 9

[0128] Test Example 10 Test Example 11 Test Example 12 Test Example 13 Test Case 14 Test Case 15 Whitening value (Z) 22.37 27.08 28.10 28.98 29.79 29.33

[0129] From the data in Table 8 and Table 9, we can see that:

[0130] In fabric detergents, the higher the content of the whitening and brightening additive composition, the better the whitening effect. However, when the content is greater than 10%, the whitening effect is no longer significantly improved and even has a downward trend. It can be seen that the whiteness limit has been reached and the solution viscosity is too low.

[0131] Comparative Examples 2 to 4 and Test Examples 16 to 19

[0132] In Table 10, the contents of each component of the whitening and brightening additive composition are in parts, and the amount not filled in is 0.

[0133] Table 10

[0134] Components Comparative Example 2 Comparative Example 3 Comparative Example 4 Oleic acid 10 Erucic acid 10 Succinic acid 10 VBL 1 1 1 Isopropyl alcohol 10 10 10

[0135] The preparation steps of Comparative Example 2 are as follows: using isopropanol as solvent, preparing oleic acid into a solution with a mass fraction of 50% at 30° C., taking 10 g of the above solution, adding 1.00 g of VBL thereto, stirring evenly to make it completely dissolved, and obtaining a composition.

[0136] The preparation steps of Comparative Example 3 are as follows: using isopropanol as solvent, preparing erucic acid into a solution with a mass fraction of 50% at 30° C., taking 10 g of the above solution, adding 1.00 g of VBL thereto, stirring evenly to make it completely dissolved, and obtaining a composition.

[0137] The preparation steps of Comparative Example 4 are as follows: using isopropanol as solvent, preparing succinic acid into a solution with a mass fraction of 50% at 30° C., taking 10 g of the above solution, adding 1.00 g of VBL thereto, stirring evenly to make it completely dissolved, and obtaining a composition.

[0138] The fabric whitening and brightening additive compositions of Comparative Examples 2-4 were formulated into fabric detergents, and the compositions were shown in Table 11. The contents of the following components are all in weight percentage, and those not filled in are added in an amount of 0, and the remainder is deionized water.

[0139] Table 11

[0140] Components Test Case 16 Test Case 17 Test Case 18 Test Case 19 AES 16 16 16 16 LAS 30 30 30 30 AEO-9 6 6 6 6 Coconut oil fatty acids 2 2 2 2 EDTA 0.5 0.5 0.5 0.5 Sodium Citrate 1 1 1 1 Cellulase 0.05 0.05 0.05 0.05 preservative 0.2 0.2 0.2 0.2 KOH / Citric Acid Monohydrate Adjust pH Adjust pH Adjust pH Adjust pH Whitening and brightening additive composition of comparative example 2 2 Whitening and brightening additive composition of comparative example 3 2 Whitening and brightening additive composition of comparative example 4 2 1% pH 8.5 8.4 8.4 8.3 Viscosity 1703 1889 1825 1920

[0141] The evaluation of the whitening effect of the fabrics in Table 11 before and after washing is shown in Table 12.

[0142] Table 12

[0143] Test Case 16 Test Case 17 Test Case 18 Test Case 19 Whitening value (Z) 20.84 21.17 17.82 10.71 Whitening value (Z) improvement rate 95％ 97％ 66％

[0144] The improvement rates of the whitening values ​​(Z) of Test Examples 15 to 17 are the improvement rates compared with Test Example 19.

[0145] The stability evaluation in Table 11 is shown in Table 13.

[0146] Table 13

[0147] Test Case 16 Test Case 17 Test Case 18 Test Case 19 -5℃ stability Gel, unqualified Turbid, unqualified Turbid, unqualified qualified Freeze-thaw recovery Layered, unqualified Unable to recover, unqualified Unable to recover, unqualified qualified

[0148] From the data in Table 11-13, we can see that:

[0149] Oleic acid, erucic acid and succinic acid are used in the comparative example, and the structural formula of oleic acid is: The structural formula of erucic acid is: The structural formula of succinic acid is:

[0150] It can be seen that the three have either only one carboxyl group and no unsaturated carbocyclic structure, or have two carboxyl groups but no unsaturated carbocyclic structure. Not only is the whitening value improvement rate in the detergent significantly lower than that in Examples 1 to 4, but it also fails to achieve the effect of solubilizing and reducing viscosity, and cannot have good low-temperature stability in the detergent. It can be seen that the unsaturated carbocyclic structure and the polycarboxyl group conditions in the composition are indispensable.

[0151] The raw materials and equipment used in the present invention, unless otherwise specified, are all commonly used raw materials and equipment in the art; the methods used in the present invention, unless otherwise specified, are all conventional methods in the art.

[0152] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent transformation made to the above embodiment based on the technical essence of the present invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A fabric whitening and brightening additive composition, characterized in that: The following components are included in weight percentage: 1-70% C 21 Dicarboxylic acids and / or C 22 Tricarboxylic acid, 1-20% bis(diphenylethylene)biphenyl brightener, 1-70% alcohol solvent; C 21 The structural formula of dicarboxylic acid is: X=5, Y=7; one of R1 and R2 is carboxyl, and the other is hydrogen; C 22 The structural formula of tricarboxylic acid is: X=5, Y=7; C 21 Dicarboxylic acids and / or C 22 The mass ratio of tricarboxylic acid to bis(distyryl)biphenyl whitening agent is 10-40:1; The alcohol solvent is one or both of ethylene glycol and propylene glycol.

2. The fabric whitening and brightening additive composition according to claim 1, characterized in that: C 21 The structural formula of dicarboxylic acid is: X=5, Y=7; R1 is carboxyl, and R2 is hydrogen.

3. The fabric whitening and brightening additive composition according to claim 1, characterized in that: C 21 The structural formula of dicarboxylic acid is: X=5, Y=7; R1 is hydrogen, and R2 is carboxyl.

4. A method for preparing the fabric whitening and brightening additive composition as claimed in any one of claims 1 to 3, characterized in that: Add C to alcohol solvent 21 Dicarboxylic acids and / or C 22 The tricarboxylic acid is stirred at 30-35°C until it is completely dissolved, and then a bis(diphenylethylene)biphenyl type whitening agent is added. After the whitening agent is completely dissolved, a fabric whitening and brightening additive composition is obtained.

5. A detergent containing the fabric whitening and brightening additive composition as claimed in any one of claims 1 to 3, characterized in that: The invention discloses a fabric whitening and brightening additive composition containing 0.1 to 10% of the total mass of detergent.

6. The detergent according to claim 5, characterized in that: The detergent also includes an anionic surfactant.

7. The detergent according to claim 6, characterized in that: The anionic surfactant is selected from one or more of saturated fatty acid salts, alkylbenzene sulfonates, sodium fatty alcohol polyoxyethylene ether sulfates, fatty acid methyl ester sulfonates, dodecyl sulfates, modified oil ethoxylate sulfonates, N-fatty acyl amino acid salts and sodium α-olefin sulfonates.

8. The detergent according to claim 5, characterized in that: The detergent also includes a nonionic surfactant.

9. The detergent according to claim 8, characterized in that: The nonionic surfactant is selected from one or more of natural alcohol polyoxyethylene ethers, alkyl glycosides, isomeric alcohol polyoxyethylene ethers, fatty alcohol polyoxyethylene polyoxypropylene ethers, fatty acid ester ethoxylates, fatty acid methyl monoethanolamide, fatty acid monoethanolamide and modified oil ethoxylates.

10. The detergent according to claim 5, characterized in that: The detergent may further comprise one or more of a chelating agent, an acid-base regulator, an anti-redeposition agent, an inorganic salt, a sunscreen, a preservative, a defoaming agent, an antibacterial agent, an enzyme preparation, a fragrance and a pigment.

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