阅读说明：本技术 一种速溶活氧洗涤颗粒组合物及其制备方法 (Instant active oxygen washing particle composition and preparation method thereof ) 是由 陈文福 李林 赵顺祥 丁泳锋 宗蔚 沈兵兵 张利萍 于 2021-09-15 设计创作，主要内容包括：本发明公开了一种速溶活氧洗涤颗粒组合物及其制备方法,所述组合物分为包裹层和内层活氧洗涤颗粒。包裹层的组分由硫酸钠、氯化钠、硅酸钠、成膜剂和十二烷基苯磺酸钠构成,其中硫酸钠、氯化钠、硅酸钠、十二烷基苯磺酸钠和成膜剂在包裹层中的重量占比分别为38-55％、3-15％、5-25％、2-10％和2-20％。内层活氧洗涤颗粒各组分含量以重量份计包括：脂肪酸甲酯磺酸钠3～11份,α-烯基磺酸钠0.5～5份,非离子表面活性剂0.5～8份,碳酸钠10～55份,双氧水溶液7～38份,硫酸钠1～30份,五水偏硅酸钠1～5份,崩解剂1～8份,羧甲基纤维素钠0.1～2份。本发明为速溶配方体系,活氧洗涤颗粒的溶解效果好,活氧稳定性能好,颗粒包裹层水溶性能好,产品储运过程颗粒不易破碎。(The invention discloses an instant active oxygen washing particle composition and a preparation method thereof. The components of the coating layer are composed of sodium sulfate, sodium chloride, sodium silicate, a film forming agent and sodium dodecyl benzene sulfonate, wherein the weight percentage of the sodium sulfate, the sodium chloride, the sodium silicate, the sodium dodecyl benzene sulfonate and the film forming agent in the coating layer is respectively 38-55%, 3-15%, 5-25%, 2-10% and 2-20%. The active oxygen washing particle at the inner layer comprises the following components in parts by weight: 3-11 parts of fatty acid methyl ester sodium sulfonate, 0.5-5 parts of alpha-alkenyl sodium sulfonate, 0.5-8 parts of non-ionic surfactant, 10-55 parts of sodium carbonate, 7-38 parts of hydrogen peroxide solution, 1-30 parts of sodium sulfate, 1-5 parts of sodium metasilicate pentahydrate, 1-8 parts of disintegrant and 0.1-2 parts of sodium carboxymethylcellulose. The invention is an instant formula system, the dissolution effect of the active oxygen washing particles is good, the active oxygen stability is good, the water solubility of the particle coating layer is good, and the particles are not easy to break in the product storage and transportation process.)

1. The composition of the instant active oxygen washing particles comprises inner active oxygen washing particles and a coating layer coated on the surfaces of the inner active oxygen washing particles, and is characterized in that the coating layer comprises sodium sulfate, sodium chloride, sodium silicate, sodium dodecyl benzene sulfonate and a film forming agent, wherein the sodium sulfate, the sodium chloride, the sodium silicate, the sodium dodecyl benzene sulfonate and the film forming agent respectively account for 38-55%, 3-15%, 5-25%, 2-10% and 2-20% of the coating layer by weight.

2. The instant reactive oxygen species scrubbing particle composition of claim 1, wherein said inner reactive oxygen species scrubbing particle comprises in component amounts: the composition comprises, by weight, 3-11 parts of fatty acid methyl ester sodium sulfonate, 0.5-5 parts of alpha-alkenyl sodium sulfonate, 0.5-8 parts of a nonionic surfactant, 10-55 parts of sodium carbonate, 7-38 parts of a hydrogen peroxide solution, 1-30 parts of sodium sulfate, 1-5 parts of sodium metasilicate pentahydrate, 1-8 parts of a disintegrating agent and 0.1-2 parts of sodium carboxymethylcellulose.

3. An instant active oxygen detergent granule composition according to claim 1 or 2 wherein the coating layer is present in an amount of from 10 to 20% by weight of the total instant active oxygen detergent granule composition.

4. The instant active oxygen detergent granule composition according to claim 1 or 2, wherein the film forming agent is one or more of sodium polyacrylate, sodium carboxymethyl cellulose, polyvinyl alcohol.

5. The instant reactive oxygen detergent granule composition of claim 2, wherein the nonionic surfactant is one or more of C12-C14 alkyl glycoside, C12-C18 fatty alcohol polyoxyethylene ether, C12-C18 alcohol condensate with ethylene oxide/propylene oxide block copolymer, coconut oil fatty acid diethanolamide, coconut oil fatty acid monoethanolamide.

6. A process for preparing an instant, live oxygen detergent granule composition, the process comprising the steps of:

(1) adding 0.5-3.0 parts by weight of stabilizer into 30-70% hydrogen peroxide, and uniformly stirring and mixing to obtain a hydrogen peroxide solution;

(2) adding a raw material composition of fatty acid methyl ester sodium sulfonate, alpha-alkenyl sodium sulfonate, a nonionic surfactant, sodium carbonate, sodium sulfate, sodium metasilicate pentahydrate, a disintegrating agent and sodium carboxymethyl cellulose into a reactor, and uniformly stirring and mixing;

(3) spraying the hydrogen peroxide solution prepared in the step (1) into a reactor, controlling the reaction temperature in the reactor to be 30-50 ℃, and forming and drying a product after the reaction is finished to obtain spherical active oxygen washing particles;

(4) and (4) uniformly mixing the active oxygen washing particles obtained in the step (3) with a coating solution with the concentration of 30-45% in a mixer, drying by a fluidized bed, and screening out particles of 20-12 meshes, namely the required coated active oxygen washing particles.

7. The method of claim 6, wherein the stabilizer is preferably one or more of diethylenetriamine pentamethylenephosphonic acid and sodium salts thereof, hydroxyethylenediphosphonic acid and sodium salts thereof.

8. The method according to claim 6, wherein the concentration of hydrogen peroxide in step (1) is 50-70%; the adding time of the hydrogen peroxide solution in the step (3) is controlled to be completed within 30-60 minutes; in the step (4), the air supply temperature of the fluidized bed dryer is controlled to be 80-100 ℃, and the air outlet temperature is controlled to be 55-60 ℃.

Technical Field

The invention relates to the technical field of daily chemical products, in particular to an instant active oxygen washing particle composition and a preparation method thereof.

Background

With the increasing demand of people on the sterilization and cleaning of detergents, an oxygen bleaching agent, namely sodium percarbonate, is added into more and more washing powders. Sodium percarbonate is used as a novel efficient active oxygen washing assistant, has strong functions of stain removal, bleaching and sterilization, has no destructive effect on an organic additive and a whitening agent with aromatic flavor in a detergent, and can keep the original flavor of a matrix. Compared with the traditional phosphorus-series and boron-series washing auxiliaries, the sodium percarbonate has strong detergency, does not destroy the ecological environment, has the characteristics of no odor, no toxicity and no pollution, is an important additive of high-grade detergents, and is a washing auxiliary widely applied in the washing industry at present.

At present, two main modes of producing the washing products containing sodium percarbonate are available, one mode is to simply mix or agglomerate sodium percarbonate with other components of a washing agent for forming, for example, patent CN103131552A discloses a washing agent composition containing a low-temperature bleaching activation system, anionic surfactant, softening water auxiliary agent, whitening agent, polymer, filler and the like are prepared into slurry, spray drying is carried out to prepare base powder, and the base powder is mixed with nonionic surfactant, peroxide (sodium percarbonate or sodium perborate monohydrate and the like), enzyme preparation, essence, decorative particles and the like to prepare the washing agent composition. The method has the problems that the dissolution speed of the added sodium percarbonate particles is slow, and the dissolution performance of the product is influenced. Patent CN1131185A discloses an oxygen-containing bleaching compound soap powder, which is prepared by agglomerating and molding a bleaching oxidant (sodium perborate and sodium percarbonate), a bleaching activator, embedded manganese sulfate, modified protease, soap base powder and the like as main agents, polyacrylic acid, acrylic acid-maleic acid copolymer as an auxiliary agent and other auxiliary agents. The method has the advantages that the components are different in particle size and density, so that the components are difficult to mix uniformly in the mixing process, and even after being mixed uniformly, the components are easy to layer in the packaging and transportation processes, and the uneven distribution of the components is caused again. And the other is that sodium carbonate is mixed with other washing raw materials and then reacts with hydrogen peroxide solution to prepare an oxygen-containing detergent, for example, patent CN108753485A discloses an active oxygen laundry composition and a preparation method thereof, wherein the composition raw materials comprise sodium carbonate, sodium bicarbonate, sodium dodecyl benzene sulfonate, hydrogen peroxide aqueous solution and the like, and the active oxygen laundry composition is prepared by adding the sodium carbonate, the sodium dodecyl benzene sulfonate and the like into a reaction kettle for mixing, then adding the hydrogen peroxide aqueous solution for mixing reaction, granulating and drying. The active oxygen laundry composition prepared by the method has good solubility, but the particles are loose and are easy to break in the processes of packaging, transportation and storage, so that the granular appearance of the product is influenced.

Disclosure of Invention

Aiming at the problems of slow dissolution speed, uneven components and easy breakage of particles of the existing washing product containing active oxygen, the invention provides an active oxygen washing particle composition which is instant, stable in active oxygen and difficult in breakage of particles, and a preparation method of the composition.

The following is a technical solution given by the present invention.

The instant active oxygen washing particle composition provided by the invention is a coated active oxygen washing particle which is divided into a coating layer and an inner active oxygen washing particle. The coating layer is composed of sodium sulfate, sodium chloride, sodium silicate, sodium dodecyl benzene sulfonate and a film forming agent, wherein the weight percentages of the sodium sulfate, the sodium chloride, the sodium silicate, the sodium dodecyl benzene sulfonate and the film forming agent in the coating layer are respectively 38-55%, 3-15%, 5-25%, 2-10% and 2-20%. The active oxygen washing particle at the inner layer comprises the following components in parts by weight: 3-11 parts of fatty acid methyl ester sodium sulfonate, 0.5-5 parts of alpha-alkenyl sodium sulfonate, 0.5-8 parts of non-ionic surfactant, 10-55 parts of sodium carbonate, 7-38 parts of hydrogen peroxide solution, 1-30 parts of sodium sulfate, 1-5 parts of sodium metasilicate pentahydrate, 1-8 parts of disintegrant and 0.1-2 parts of sodium carboxymethylcellulose.

3-11 parts of fatty acid methyl ester sodium sulfonate and 0.5-5 parts of alpha-alkenyl sodium sulfonate are compounded with 0.5-8 parts of nonionic surfactant, so that the problem that the prepared high-surfactant-content particles are gelatinized when meeting water can be solved, and the solubility of the particle composition is improved. The wrapping layer contains sodium sulfate and sodium chloride, and because the sodium sulfate and sodium chloride form pane type intercalation compound according to a certain proportion, after the water content is fed into its crystal lattice, its binding force is stronger than that of general crystal water, and in the course of storing active oxygen washing granules, if there is H₂0₂When released, the active oxygen can be captured by the crystal lattice, thereby avoiding the loss of active oxygen and effectively improving the stability of active oxygen washing particles. The sodium silicate in the coating layer can play a role of an anti-friction agent, and the sodium dodecyl benzene sulfonate can reduce the interfacial tension of the coating layer, so that the coating layer has the characteristics of dispersion and emulsification, and the coating layer is favorable for accelerating the dissolution speed of the coated active oxygen washing particles. The organic film forming agent is flexible, so that the coating layer is not easy to peel off, and the integrity of the particles is kept.

The film forming agent is preferably one or more of sodium polyacrylate, sodium carboxymethyl cellulose and polyvinyl alcohol, and is preferably sodium polyacrylate or sodium carboxymethyl cellulose with the average molecular weight of 3000-7000. The film forming agent is a matrix adhered to the wrapping material and can adhere the inorganic salt and the surfactant together, so that the wrapping layer has certain tensile strength, and the film forming property, the solubility and the storage stability need to be comprehensively considered in the selection of the film forming agent.

The disintegrant is preferably one or more of croscarmellose sodium, sodium carboxymethyl starch, hydroxypropyl starch, crospovidone, and low-substituted hydroxypropyl cellulose. The disintegrating agent is swelling disintegrating agent, has strong capillary/water content, large specific surface area, strong hydration ability and strong water absorption and expansion ability, and can promote the rapid disintegration of the granule through water absorption and expansion.

The nonionic surfactant is preferably one or more of C12-C14 alkyl glycoside, C12-C18 fatty alcohol-polyoxyethylene ether, C12-C18 alcohol-ethylene oxide/propylene oxide block copolymer condensate, coconut oil fatty acid diethanolamide and coconut oil fatty acid monoethanolamide.

According to the invention, the auxiliary agent can be added into the coated active oxygen washing particle composition according to actual needs to improve the product performance, for example, the enzyme preparation is added to improve the decontamination performance of the product, and the whitening agent is added to realize the visual whitening effect. Because the active oxygen washing particles are wrapped particles and have good active oxygen stability, the auxiliary agent can be selectively added with a sodium percarbonate low-temperature activating agent such as tetraacetylethylenediamine, and the sodium percarbonate low-temperature activating agent is mixed with the active oxygen washing particles, so that the bleaching activity of the sodium percarbonate at low temperature can be effectively improved, and the use effect of the active oxygen detergent in the low-temperature environment can be improved.

A process for preparing an instant oxygenated detergent granule composition comprising the steps of:

(a) adding 0.5-3.0 parts by weight of stabilizer into 30-70% hydrogen peroxide, and uniformly stirring and mixing to obtain a hydrogen peroxide solution.

(b) Adding a raw material composition of fatty acid methyl ester sodium sulfonate, alpha-alkenyl sodium sulfonate, a nonionic surfactant, sodium carbonate, sodium sulfate, sodium metasilicate pentahydrate, a disintegrating agent and sodium carboxymethyl cellulose into a reactor, and stirring and mixing uniformly.

(c) Spraying the hydrogen peroxide solution prepared in the step (a) into a reactor, controlling the reaction temperature in the reactor to be 30-50 ℃, and forming and drying a product after the reaction is finished to obtain the spherical active oxygen washing particles. In the invention, the reaction is started after the hydrogen peroxide solution is added, if the reaction temperature is higher than 55 ℃, the decomposition speed of the hydrogen peroxide solution is increased quickly, so that the yield of the active oxygen of the product is influenced, and when the reaction temperature is lower than 0 ℃, the reaction speed of the hydrogen peroxide and the sodium carbonate is slow and the reaction time is overlong. Therefore, in order to make the reaction between the hydrogen peroxide and the sodium carbonate smoothly proceed and improve the utilization rate of the hydrogen peroxide, the invention strictly controls the reaction temperature in the reactor to be 30-50 ℃, preferably 45-50 ℃.

(d) And (c) uniformly mixing the active oxygen washing particles obtained in the step (c) with a coating solution with the concentration of 30-45% in a mixer, drying by a fluidized bed, and screening out particles of 20-12 meshes, namely the required coated active oxygen washing particles.

(e) And (3) selective step: adding the coated active oxygen washing particles obtained in the step (d) and an auxiliary agent into a mixer, and fully mixing to obtain the instant active oxygen washing particle composition with various characteristics.

Wherein the stabilizer is preferably one or more of diethylenetriamine pentamethylenephosphonic acid (DTPMP) and a sodium salt thereof, hydroxyethylidene diphosphonic acid (HEDP) and a sodium salt thereof.

The concentration of the hydrogen peroxide in the step (a) is preferably 50-70%.

The adding time of the hydrogen peroxide solution in the step (c) is preferably controlled within 30-60 minutes, the air supply temperature of the fluidized bed dryer in the step (d) is preferably controlled within 80-100 ℃, and the air outlet temperature is preferably controlled within 55-60 ℃.

By properly selecting the adding speed of the hydrogen peroxide solution in the step (c), the heat production quantity of the reaction system in unit time is enabled to have small fluctuation in the whole reaction stage, and the cooling medium is favorable for taking away the heat quantity in time.

Detailed Description

The data for 14 examples and 2 comparative examples are presented below in tabular form, wherein 2 comparative examples select uncoated, aerobic detergent granule compositions having the same composition of the aerobic detergent granules and the adjunct as in examples 1 and 8.

TABLE 1 EXAMPLES 1-7 moderate speed oxygen-dissolved detergent granule compositions

TABLE 2 compositions of moderate speed oxygen-dissolved detergent granules compositions of examples 8-14

TABLE 3 composition of active oxygen scrubbing granule compositions of comparative examples 1-2

Performance test experiment

1) Dissolution rate test method: 10 g of sample to be tested is put into a beaker filled with 1000ml of deionized water, the temperature is kept constant at 20 ℃, a magnetic stirrer is started, the rotating speed is 300 revolutions per minute, and the dissolution speed of the sample is measured by a conductivity method.

2) The thermal stability test method comprises the following steps: the sample was left at a constant temperature of 45 ℃ for 1 week, and the retention of active oxygen in the sample was measured.

3) Wet stability test method: the samples were placed in an open petri dish at 40 ℃ and 70% relative humidity for 48 hours, and the retention of active oxygen of the samples was calculated.

4) The crushing condition test method comprises the following steps: and packaging 10 parts of samples (1 kg/part) in the same way, uniformly and quickly sending the samples to a receiving place 1000 kilometers away, and sending the samples back again, wherein the increase ratio of the particles and the fine powder is less than or equal to 20 meshes in a piece removal test.

TABLE 4 results of testing the performance of examples 1-14, comparative examples 1-2 and commercial active oxygen laundry powder

Remarking: the commercially available active oxygen washing powder is formed by directly mixing sodium percarbonate particles, washing powder base powder and other components.

As can be seen from Table 4, the compositions of the active oxygen scrubbing particles of examples 1 to 14 of the present invention have good dissolution performance, dissolution rate within 60S, good active oxygen stability under humid and hot environment, and good particle integrity, and the active oxygen scrubbing particles are not easy to break during transportation. While comparative examples 1-2 are superior to examples 1-14 in solubility, they are inferior in waterproof and heat insulating properties because of no coating layer, and the stability of the active oxygen particles under wet and hot conditions is significantly lower than that of examples 1-14, and the particles are broken more seriously during transportation, which affects the granular appearance of the product. The commercial active oxygen washing powder has poor overall dissolution performance due to the slow dissolution rate of sodium percarbonate particles therein, and also has poorer heat and humidity stability than examples 1 to 14.

In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.

The invention has the advantages of

The invention is an instant formula system, the preparation of active oxygen washing particles adopts a puffing granulation method that sodium carbonate is mixed with other washing raw materials and then reacts with hydrogen peroxide solution, and the obtained particles have good dissolving effect; the particle wrapping layer is composed of a surfactant, inorganic salt and a hydrophilic film forming agent, and has good water solubility; the active oxygen particles contain the wrapping layer, the active oxygen stability is good, and the particles are not easy to break in the process of storage and transportation of the product.