聚丙烯酸盐的助洗性能研究

研究了聚丙烯酸盐（PAA）及其改性聚合物（马来酸酐-丙烯酸甲酯-丙烯酸的三元共聚物）的组成，结构及相对分子质量对钙束缚力，分散力，絮凝性的影响。以两种商品PAA为参照，通过正交实验筛选出了无磷洗衣粉的最佳配方。实验结果表明，Ca^2 束缚值随着聚合物相对分子质量的增加而增大，其聚物中单体组成对Ca^2 束缚值影响不大。以聚合物与CaCl2的螯合物的沉淀量表征及其絮凝剂，发现聚合物加入量和Ca^2 总量相同时，沉淀量随着聚合物相对分子质量的增大而增大，饱和沉淀量只与CaV有关而与聚合物类型无关，达到饱和沉淀量时所应对应的聚合物加入量也近似正比与相应聚合物的CaV，实验条件下PAA对碳黑的分散力均优于STPP，均聚PAA对碳黑的分散力随相对分子质量增大而下降，改性PAA且增相对分子质量的增大而分散力仅略有下降，改性聚合物的相对分子质量对洗涤性能具有更广泛的适用性。     

聚羧酸盐类高分子洗涤助剂结构与性能的关系

主要讨论了用于洗涤助剂的聚羧酸盐类高分子聚合物的结构与性能的关系。结构主要包括高分子的相对分子质量与链上电荷密度 ;高分子本身性能包括无机盐结晶抑制力 ,颗粒分散力及碱土金属离子螯合力 ;应用性能包括织物纤维抗板结能力、污垢去除及抗污垢再沉积能力     

A realistic soil cloth and test procedure for detergent evaluation

The preparation of a uniformly soiled cloth for detergency studies is described. The soil, chosen for its realistic nature, consists of a colored clay as the particulate portion and triolein as the fatty or oily portion. The particulate portion of the soil is applied by tumbling the fabric in a horizontal axis washing machine containing a suspension of clay. The fatty portion is then applied by allowing the fabric to adsorb a known quantity of solvent-dissolved triolein with subsequent evaporation of the solvent. An evaluation test procedure for measuring the relative efficiencies of proprietary detergents is also described. Using this procedure, soil removal, soil redeposition and optical brightener effectiveness of a detergent are determined simultaneously. Detergents can thus be given a numerical rating according to their over-all performance. This rating is calculated from the equation: Overall Performance=Soil Removal−Soil Redeposition + Optical Brightener. Typical detergent evaluation data obtained with this soil cloth and test procedure are given, along with a statistical treatment of the data.     

Improvement of cotton cloth soil removal by inclusion of alkaline cellulase from Bacillus sp. KSM-635 in detergents

Alkaline cellulase from Bacillus sp. KSM-635 (EC 3.2.1.4) had reproducible detergent effects on cotton cloth that was artificially or naturally soiled with oily and/or particulate matter, under European washing conditions. The detergent effects of the cellulase, in combination with surfactants, apparently were the result of enzymatic action on amorphous regions of cotton fibers in which soil was trapped. The contribution of cellulase to soil removal increased as (i) the amount of soil in the amorphous regions of fibers in test fabrics was increased and (ii) the inhibition, by soil that adhered to the fibers' surfaces, of the action of the cellulase on fibers was reduced. Alkaline cellulase had the potential to replace, in part, both surfactants and zeolite in detergents, and it reduced washing time and allowed washing at lower temperatures under European washing conditions. The marked detergent effect of cellulase on naturally soiled cotton fabric was visually apparent, and it inhibited the accumulation of ash, calcium, and other inorganic components on cotton fibers during wash-and-wear cycles. These contributions of cellulase to the cleanliness of cotton fabrics were clearly increased by repeated wash-and-wear cycles. Cotton fabrics were not degraded by washing with the cellulase because effective hydrolysis by the cellulase occurred only in the amorphous regions of cotton fibers.     

An improved method for evaluating detergent builders for water hardness control

Commercial detergent additives to control water hardness may act through sequestration, crystal growth inhibition, precipitation, or ion exchange. These builders lower the free hardness (Ca⁺⁺, Mg⁺⁺ concentration by different mechanisms. A full factorially designed experiment has been developed to evaluate builders functioning by the sequestration or crystal growth inhibition of calcium carbonate or magnesium hydroxide. The builder’s performance is determined by its ability to prevent precipitation while in the presence of carbonate and hardness ions. The tests are based on incubation followed by filtration and determination of calcium and magnesium in the filtrate by Inductively Coupled Plasma (ICP). Variables in the design include builder concentration, temperature, pH and time. Regression equations and response surfaces for tripolyphosphate and several polyacrylates and phosphonates are included.     

Thermal behaviour of films of partially neutralized poly(acrylic acid). 3: Effect of magnesium and calcium ions

Partially neutralized polyacrylates of calcium and magnesium have unexpectedly been found not to undergo thermal decarboxylation at 250°C, unlike partial polyacrylates of lithium, sodium or potassium. Reflectance infrared spectroscopy has confirmed that the partial polyacrylate of calcium is predominantly ionic but as with the magnesium compound, this does not promote decarboxylation. Further study of the partial lithium salt of poly(acrylic acid) has confirmed that lithium ions exhibit some degree of covalency, and hence are probably site-bound. Despite this, they succeed in promoting decarboxylation. It is concluded that the main factor which prevents calcium and magnesium facilitating decarboxylation is their divalency, rather than any inherent tendency to become site-bound. Reasons for this are discussed.     

Protease and Amylase Stability in the Presence of Chelators Used in Laundry Detergent Applications: Correlation Between Chelator Properties and Enzyme Stability in Liquid Detergents

Chelators are a common ingredient in most laundry detergents. They have a number of different functions such as reducing water hardness, assisting in keeping particulate soil in suspension and the removal of certain stains, thus complementing the action of the anionic surfactants. Another important group of components in a modern liquid detergent is enzymes, mainly proteases and amylases. As the most commonly used enzymes within the detergent industry are dependent on bound calcium ions to maintain conformational stability and function, the presence of both chelators and enzymes in a liquid detergent presents a challenge. The three commonly used Ca²⁺ chelators: citrate, DTPA (diethylene triamine pentaacetic acid) and HEDP (1-hydroxyethane-1,1-diyl)bis(phosphonic acid), were studied with regard to their impact on protease and amylase stability in buffer and in a model liquid detergent. Enzyme stability was characterized by differential scanning calorimetry (DSC) and activity studies, and correlated to the chelator-Ca²⁺ interaction properties. The results show that a chelator’s ability to reduce water hardness and its Ca²⁺ affinity are in reality two separate aspects in the context of their use in liquid detergents. In the presence of DTPA, stoichiometric surplus of free Ca²⁺ is required to maintain sufficient amylase and protease stability. In the presence of the weaker chelators, HEDP and citrate, the total Ca²⁺ concentration is more important to protein stability than stoichiometric balancing between chelator and Ca²⁺. Thus, for these chelators their total concentration only has a minor impact on the Ca²⁺ concentration required to maintain or improve enzyme storage stability. The results underline the importance of Ca²⁺ in liquid detergent formulations, and suggest how proper balancing of chelators and Ca²⁺ can be used to improve overall enzyme stability.     

Test method utilizing dry natural dirt for evaluating laundry detergents

A laboratory test has been developed for screening detergent compositions with respect to the removal of natural dry particulate soil (dirt). The fabrics are soiled uniformly with dirt obtained from a suitable area and then laundered under controlled conditions in a Tergotometer. The total soil removal is determined instrumentally. The test enables the researcher to check the effects of many variables, such as temperature, water hardness, builders, fabric, etc., with a minimum amount of preparation and time. The soil removal data is analyzed by a suitable statistical method, and the results are good indicators of practical performance.     

Soap-based detergent formulations: X. Nature of detergent deposits

The cumulative deposition of detergent residue on unsoiled cotton and polyester-cotton permanent press finish cloth was determined for a variety of detergent formulations after washing 25 consecutive times in 300 ppm hard water in a laboratory Tergotometer. Included in this study were: a phosphate-built laundry detergent, two carbonate-built detergents, tallow soap and various tallow soap formulations with anionic and amphoteric lime soap dispersing agents, and a glassy sodium silicate. Sample swatches washed with each formulation were analyzed for calcium, magnesium, and organic acid content. Fabric washed with the carbonate detergents showed the highest calcium and magnesium content, while those washed with the phosphate detergent and the soap-lime soap dispersant-builder formulations had the lowest. Fabric washed with soap alone had a much higher fatty acid residue than those washed with the other detergent formulations. However, the amount of organic acids left on the fabric after washing with a soap-lime soap dispersing agent formulation was no greater than that produced by phosphate- and carbonate-built detergents. The presence or absence of deposits also was verified visually with a scanning electron microscope. Each formulation also was tested for detergency by measuring the soil buildup in a multiwash procedure. Generally, the buildup of soil paralleled the deposit of detergent residue on the unsoiled cloths.     

Building action of various types of inorganic electrolytes

The builder effects of a series of condensed phosphates and other types of electrolytes on the detergency for standard soiled cloth have been measured. The detergency highly depends on the type of electrolytes and, in general, increases with increasing pH of detergent solutions. The building action of phosphates is greater than that of other electrolytes when it is compared at the same pH. The alkalinity, including alkali buffering capacity, of various electrolytes and the sequesteration capacity of phosphates for calcium ion have also been determined. From the results, the building action of inorganic electrolytes in a detersive system has been discussed in connection with the suspension stability of colloidal particles reported in previous papers. The following factors are at least important in the building action of inorganic compounds: (a) the suspension of soil particles in a detergent solution, (b) the sequesteration of heavy metal ions, and (c) the alkalinity including buffering action to keep the solution alkaline. Condensed phosphates, in particular sodium tripolyphophate, have an ability to satisfy these three factors although their alkalinity is not so strong.     

A detergency test based on rapid aging of unremoved sebum

A laboratory test has been developed for screening detergent compositions with respect to the removal of sebum soil in the absence of particulate soil. The fabrics are uniformly soiled with an aqueous emulsion of synthetic sebum and are then laundered under controlled conditions in a Tergo-Tometer. The unremoved soil is rapidly aged, and the resulting yellowness is measured instrumentally. This test can be run in a minimum amount of time and with a minimum amount of equipment. It enables one to check many variables (such as sequentering capacity, temperature effects, brightener build-up under soiled conditions, etc.) on various fabrics, with or without special treatments. The results are in terms of yellowness, which is recognized by the housewife, and are not a measurement of total soil removal. These values, when combined with grayness values derived from the sebum airborne test, are good prognosticators of practical performance.     

Water-based poly(2-ethylhexyl acrylate-itaconic acid) removable adhesives with frost resistance for digital inkjet printing

Adhesives are nonmetallic materials used to bond each layer in many applications for its flexibility. For digital inkjet printing, the requirements of adhesives performance are demanding as they must be able to adhere well to adherend, be removable without leaving adhesive residue, or even causing any damage. Water-based polyacrylates have been widely used for backing adhesive layer in application of digital inkjet printing, due to their various advantages. While the application has been limited on account of the weak frost resistance of common polyacrylates, which could not be used directly under low temperature storage. To improve the weak frost resistance, water-based poly(2-ethylhexyl acrylate-itaconic acid) was synthesized. Itaconic acid (ITA) could be greatly beneficial to improve the frost resistance. The polyacrylates could still be used directly, even after being frozen below at −18°C for 16 hr. The adhesion properties of polyacrylates could also be enhanced by moderate ITA. The results show that the optimal amount of ITA was 2 mass%. The overall properties of the resulting polyacrylates with the 180° peel strength of 2.73 N/25 mm, the tack of 23 #, and the shear holding power of more than 24 hr are suitable for practical applications on removable adhesives for digital inkjet printing.     

Role of detergent builders in fabric washing formulations

The role of a detergent builder in fabric washing formulations is complex because the builder is multifunctional. The primary function of a builder is to counteract the detrimental effects of hardness ions (Ca²⁺ and Mg²⁺) which arise in the wash solution not only from the tap water but also from the washload. The need to control the free hardness ion level to 0.1 °FH is well established and is mainly required to release calcium bound soil and prevent further calcium soil interaction during the wash process. The most elegant way of doing this is with a sequestrant. Sodium triphosphate is the preferred material. Measurement of the equilibrium constants of sequestrants with Ca²⁺/Mg²⁺/Na⁺/H⁺ as a function of temperature and ionic strength allows prediction of free hardness ion levels over a wide range of conditions such as temperature, pH, water hardness, and dosage. Secondary functions such as specific adsorption effects are important, and a true builder will aid not only soil removal but alleviate soil redeposition.     

Enzymes in detergents

Factors affecting the performance of proteolytic and amylolytic enzymes in an anionic and nonionic detergent formulation have been studied using stain removal from EMPA blood-milk-ink and cocoa-milk-sugar soil test cloths as a measure of enzyme activity in the detergent solution. Factors considered include enzyme concentration, and temperature and pH of the wash solution. Results on stability of these enzymes in the two detergent formulations under accelerated storage conditions are also given. Presented at the AOCS Meeting, New York, October, 1968.     

Formulation and Evaluation of an Automatic Dishwashing Detergent Containing T1 Lipase

The use of enzymes in detergent formulations is becoming popular due to the concerns about the environment. T1 lipase (E.C. 3.1.1.3) was evaluated for its stability and performance in dishwashing along with other common components of an automatic dishwashing detergent. Therefore, the process of formulating the detergent would depend on the stability of T1 lipase, which may also reflect the performance during the washing. T1 lipase was mostly stable in nonionic surfactants, especially those that were made of polyhydric alcohols. T1 lipase was also stable in a mixture of sodium carbonate and glycine. However, sodium carbonate alone destabilized T1 lipase possibly due to the interaction between carbonates and Ca²⁺. These results indicated that polyhydric alcohols and glycine had stabilizing effects on T1 lipase. The dishwashing performance was evaluated in term of percent soil removed. The dishwashing performance of the formulated detergent was positively affected by the increase in temperature but negatively affected by the presence of hard water, specifically Ca²⁺ and Mg²⁺. However, T1 lipase was not negatively affected by the presence of hard water, and this enzyme was enhanced by the presence of polyacrylates. The presence of Ca²⁺ improved the structural integrity of T1 lipase. It is generally known that most enzymes that depend on Ca²⁺ for their structural integrity would be greatly destabilized in the presence of metal chelators; thus, stabilizing strategies such as adding glycine would be essential to maintain enzyme activity during the wash.     

Properties of detergent phosphates and their effects on detergent processing

Phosphates are usually key ingredients in detergent formulations ranging from liquids to free-flowing powdery material to hard cakes. Their functional properties, which contribute to the over-all detergency by controlling the alkalinity, lowering the critical micelle concentration, sequestering metal ions, and decreasing soil redeposition, are generally considered to be the reason for their wide use. Another important but less recognized reason is their versatile role in improving the handling properties and lowering the cost of the finished products. The sophistication of the phosphate manufacturing processes makes it possible to turn out a large number of phosphates with different properties and physical forms. Trisodium orthophosphate, tetrapotassium pyrophosphate, and sodium phosphate glass are for the specialties. Sodium tripolyphosphate, the work-horse of the detergent phosphates, has many grades. Some are designed to give the desired hydration properties for different detergent-processing conditions. Size and density are varied for granular grades to reduce segregation and degradation in dry-blended detergents. Sodium trimetaphosphate, which converts rapidly into tripolyphosphate, offers a new detergent-processing technology. Effervescent phosphate is an intriguing new detergent phosphate with many possible new applications. The properties of these phosphates and their effect on the detergent products and processes are discussed in detail.     

Principles of performance testing of laundry detergents

Summary Laboratory performance tests for laundry detergents can fill important needs in laboratory development programs and in control testing, in which cases full scale practical testing is inapplicable. It has been found to be unnecessary and undesirable to attempt close simulation of practice conditions. In order to be most useful to the experimental investigator or the manufacturer of detergents the soil removal and whiteness retention properties should be measured by separate tests. A soil removal test has been devised in which the soil, which consists essentially of carbon black, is applied to the test fabric from aqueous medium. Soiling from aqueous medium has advantages with respect to reproducibility in tenacity and in variation and susceptibility to removal by detergents having different degrees of effectiveness. The quantity of soil removed is measured directly by means of light transmission measurements on the soiled detergent solution. This eliminates uncertainties and limitations inherent in the reflectance method and permits the use of high soil loads in the test cloth, which minimizes redeposition effects. Multiple wash tests are not required. The whiteness retention property is determined by agitating unsoiled swatches in the detergent solution containing carbon black dispersion and measuring the reflectance change of the swatches. The results of both tests are expressed in relative terms, reference detergents being used as controls. The precision of the soil removal tests is approximately ±3.4% in terms of mean deviation and that of the whiteness retention test approximately ±5.1%. Both tests have been used over a period of several years for research and control purposes and have been successfully correlated with actual results in commercial laundries. Presented at the fall meeting of the American Oil Chemists' Society, Chicago, Oct. 31-Nov. 2, 1949.     

晶态层状结构二硅酸钠机理性能研究

阐述了新型助洗剂－晶态层状结构二硅酸钠的物化性能与特征,它具有室温快速软化水能力、碱性缓冲能力、去污能力、抗再沉积能力等功能特点,它是粉状洗涤剂中功能好、不污染环境、价格低廉的新一代助洗剂。     

Detergency study of the synergism between oily and particulate soil on polyester/cotton fabric

The removal of multiphase, multicomponent soils from fibrous substrates depends upon the nature of the soil mixture, the order of application, wash temperature, and type of detergent formulation. By studying these factors, we investigated the synergism between residual oil (triolein) and particulate soil (clay) on a durable press polyester/cotton fabric after laundering with four different detergents at wash temperatures of 27 and 49 C. To probe the interaction between clay and oil, fabric specimens were soiled with clay only, triolein only, clay followed by an application of triolein, and triolein followed by an application of clay. Four detergent formulations were used to launder the soiled fabrics, including one unbuilt liquid and three powdered detergents with different builder systems. The amount of residual oil (triolein) was determined by radiotracer technique, and the quantities of clay were determined by measuring aluminum by neutron activation. Reflectance measurements were used to calculate fabric whiteness. The soil distributions on and within the textile structure were obtained by scanning electron microscopy using backscattered electron images, secondary electron images and X-ray mapping. Osmium tetroxide was used to tag the oil, while silicon was the elemental tag for clay in the microscopic analysis. Results of the four factors studied can be summarized as follows. (i) In agreement with observations by previous researchers, a mixture of clay and oil is more difficult to remove than either the oil or the clay applied singly. It appears that oil acts as a matrix to bind clay, forming a composite soil. (ii) The specimens that were soiled first with oil and then clay had more soil removed by laundering than the specimens soiled with clay and then oil. Detergency was limited by the encapsulation of clay by the oil and adsorbtion of oil by the clay. (iii) The built powdered detergents were temperature sensitive, while the unbuilt liquid detergent was not. (iv) The built powdered detergents removed more soil (oily and clay) than the unbuilt liquid detergent.     

CO2 dry cleaning: Acoustic cavitation and other mechanisms to induce mechanical action

High pressure carbon dioxide (CO₂) is a potential solvent for textile dry cleaning. However, the particulate soil (e.g. clay, sand) removal in CO₂ is generally insufficient. Since cavitation has been proven to be beneficial in other CO₂ cleaning applications, this study aims to investigate the possibility of improving the performance of CO₂ textile dry cleaning by using ultrasound or other mechanisms to induce the mechanical action such as bubble spray and jet spray. In the experiments, several types of textiles soiled with a mixture of motor oil and soot were cleaned using 1 L and 90 L CO₂ dry cleaning set-ups. Using either ultrasound, stirring, liquid spray or bubble spray does not give a significant improvement on particulate soil removal from textile. It was also found that the additional use of ClipCOO detergent does not give a significant improvement on particulate soil removal either. The cleaning performance of CO₂ is 50% lower than that of PER and thus another method to increase the particulate soil removal in CO₂ textile dry cleaning still needs to be developed.