TW473480B - Latex systems that have a tendency to flocculate because of grafting, the preparation processes and the latex paint of composition made thereof - Google Patents

Abstract

A process is provided for preparing an acrylic copolymer latex having improved mechanical and shear stability comprising emulsion polymerizing at least one ethylenically unsaturated monomer having up to 23 carbons in the presence of, by weight based on the total monomer content, (a) from about 0.05% to about 5.0% of a protective colloid with a molecular weight of less than 75,000, and (b) from about 0.01% to about 1.5% of at least one water soluble free radical polymerization initiator. This latex provides coating manufacturers the flexibility of either eliminating surfactants altogether from coating or to use small amounts thereof.

Description

473480 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (1) 1 1 This case is filed in U.S. Patent Application 08 / 542,269 1 filed on October 20, 1995 Case t This case is a continuation of the US patent application No. 08/333697 filed on November 3, 1994. The latter S has asked K to give up first. The entire case is listed here as reference C » Read about the present invention about aqueous polymer dispersions »Derived from an ethylenically unsaturated single-backed M 1 I 1 body in the presence of a water-soluble protective colloid and related to its preparation method 0 '意 1 I in the industrial emulsion polymerization method »Surfactant 9 is often used alone or Matter 1 1 is used together to protect the carcass. The disadvantage is that surfactant must be used.» Fill | Shear Stability Lattice > This method is uneconomical and has adverse side effects 1 I Action 0 For example »Surfactants are present in the latex system« Have a negative effect on water sensitivity 1 1 * and cause the final product Foaming. In addition, the conventional level 1 | > Surfactants can not give sufficient mechanical stability to the final product. 1 It is known in the prior art. * Unsaturated vinyl monomers (including vinyl monomers, vinyl monomers and Acrylic monomers such as acrylate Λ methyl 1 I-based acrylates or mixtures thereof) Emulsion polymerization includes hydroxyethyl fiber 1 | Protective colloids such as HEC and PVOH as co-stabilizers. 1 Time > Can provide a sub-micron-sized lattice to improve its rheological stability and performance characteristics. These aqueous polymer dispersions 9 can be used to produce emulsion 1 1 rubber paint non-woven Adhesives for water-based ink paper coatings and aquatic adhesives 1 1 Adhesives t such as pressure-sensitive adhesives 0Ί 1 In monomer (including acrylic or styrene or other monomer combinations alone) 1% \ in the emulsion polymerization method 9 It does not start with the protection of cellulose or P V0H, etc. 1 I colloids are co-stabilizers. 0 In acrylic or styrenic latex systems 1 I »When using protective colloids of the prior art» High flocculation occurs 1 1 1 1 1 1 1 This paper size applies the Chinese National Standard (CNS) Λ4 specification (21 OX 297 gong) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 473480 A7 B7 V. Description of the invention (2) It shows that it lacks itself Mechanical stability. This flocculation is the result of a high tendency for the protective colloid to be incorporated directly into the reactive polymer chain. This gauge is often called grafting. It should be noted that grafting in or by itself is not completely eliminated. A small amount of grafting does not cause flocculation; in addition, migration can improve the stability of latex systems, such as the vinyl acetate copolymer lattice, has long been known. The combination of the possibility of excessive grafting and intergranular bridging is the cause of coagulation; intergranular bridging is determined not only by the amount of grafting material or particle size, but also by the amount of water-soluble polymers present in the aqueous phase and the molecular weight of the protective colloid. Depending on the solids content and so on. In any case, depending on the particular latex system *, the use of high levels of surfactants alone or in combination with protective colloids, M gram eyes lack mechanical stability. For example, in vinyl acetate systems, highly protective child colloids can be used with surfactants, while in acrylic systems, high levels of surfactants are used alone. However, a crystal lattice made of such a high content of a surfactant has the above-mentioned efficacy problem. Therefore, there is an urgent need in the industry to overcome the shortcomings of conventional latex systems that use high levels of surfactants, or conventional protective colloids.

Craig's strategy in U.S. Patent No. 4,684,704 is to use hydrophobic modified hydroxyethyl cellulose (HMHEC) with a weight of about 0.0U to about 1.7¾ based on the total amount of monomers. It can be easily and successfully added to the dispersion or crystal lattice by using emulsion polymerization. The resulting lattice has a particle size of 1.0 micrometer or less and has excellent mechanical stability. Another strategy for the polymerization of acrylic monomer systems is disclosed in US Patent No. 4845 1 75 of Lo, which uses 0.02 to 2.0¾ weight of hydrophobic modified hydroxyethyl-4- This paper standard is applicable to Chinese National Standard (CNS) Λ4 Specifications (210 × 7mm) (Please read the notes on the back before filling in this page)-# Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Clothing and Economics 473480 Μ B7 V. Description of the invention (3) Base fiber as protective colloid . Another strategy for the systemic polymerization of acrylic monomers is contained in Craig's U.S. Pat. Acids, styrene mineral acids, M and hydrazones such as metal, amine, ammonium and quaternary salts of C4-C36 acids. The present invention is directed to a method for preparing latex with improved mechanical stability, which includes emulsification polymerization of at least one ethylenic unsaturated monomer in the presence of a polymer based on the total content of the ethylenic unsaturated monomer in an effective amount ratio * The compound is a protective colloid with a molecular weight of less than about 75,000, and is selected from the group consisting of polysaccharides, polyacrylic acid and its salts, partially and fully hydrolyzed polyvinyl alcohol, polypropylene ammonium, polyvinyl pyrrolidine, polyvinyl ether, A group consisting of gelatin, tick protein, and its derivatives, and a mixture of that group. The present invention is also directed to a latex system, an aqueous emulsion including a polymer of at least one ethylenically unsaturated monomer, and the protective colloid. It has been unexpectedly discovered today that in the emulsion polymerization of ethylenically unsaturated monomers, the use of a low molecular weight protective colloid can give the resulting polymer excellent mechanical stability. The upper limit of the molecular weight of the protective colloid is about 7500, K is preferably about 50,000, and M is about 20,000. The lower limit of the molecular weight of the protective colloid is about 5000, M is preferably about 10,000, and M is about 15,000. The invention is particularly useful in acrylic or styrene latex systems. As mentioned above > Acrylic or styrenic latex systems with respect to prior art techniques * The use of commercially required levels of protective colloids is impractical because of high flocculation. Use a high content of surfactant to overcome this problem. For water sensitivity -5- This paper size applies Chinese National Standard (CNS) Λ4 specification (210 × 297 male f) (Please read the precautions on the back before filling in this page. Order 473480 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (4) It has negative effects and causes foaming of the final product. In addition, when surfactants are used, the final product will not be sufficient. Mechanical stability. It was unexpectedly discovered today that the use of low molecular weight protective colloids in acrylic or styrenic latex systems can reduce the surfactant content or even omit it completely. When the final product is compared with the previous case, it is generally found Low water sensitivity, less foaming, and higher mechanical stability. Mechanical stability can be shown to be longer in its useful life. In addition, in paint applications, it will reduce the tendency to relax and change the homogenization. Better polysaccharides Protective colloids are water-soluble cellulose ethers derived from ethylene oxide, methyl chloride, propylene oxide, monochloroacetic acid, and the like, or mixtures thereof. Particularly preferred is carboxyl Cellulose (CMC) and its derivatives have a degree of substitution of carboxyl groups (DS > about 0.7 to about 2.9, preferably about 0.7 to about 1.5, and more preferably about 1.0 to about 1.4. Suitable carboxymethyl cellulose derivatives, including carboxymethyl cellulose methyl ether, carboxymethyl cellulose, carboxymethyl cellulose hydroxyethyl ether, carboxymethyl cellulose hydroxypropyl ether, carboxymethyl cellulose methoxy Diethyl ether, carboxymethylcellulose oxyethyl ether, M and aminocarboxymethylcellulose diethyl ether. Hydroxyethyl cellulose (HEC) can also be used, and hydroxyethyl mol instead of (MS) M is about 1.6 to about 4 0 is better, and M is about 1.8 to about 3.5, and M is most preferably about 1.8 to about 2.9. In addition, hydrophobically modified isovitamin ethers can be used. Hydrophobic modification is used Cellulose ethers are azorex ethers substituted with KC4 ~ C25 hydrocarbons, and the amount is about 0.1¾ to about 3. (U, Μ about 0, 1S: to about 2) 0% is better. Better hydrophobically modified cellulose ether is hydrophobically modified hydroxyethyl-6-(Please read the precautions on the back before filling in this page.

.tT Λ IV— This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) 473480 A7 B7 V. Description of the invention Hydrocarbon application 25 * ~ c can be used with C. Also) is CE, MH element Η. • Vitamin fiber base fiber B is preferably about M to 10% J. 1 B 3 Q hydroxyl is about about The amount of C 9 is 2 times the amount of lysin. To Weijia and fiber more, the base 0% Jiayi 2 is the range of the hydroxyl group to the standard quality uo ο 4 sex about water to sparse and 9 is the amount of 2 about. 3 in the example base, the propion hydroxyl gel ,.保 C)}. MC protects {Ρ as a vegetarian ingredient 丨 using vitamins in the fiber BenQ fiber hair methyl, C in hydroxycollamine and Ε also {with etheroids), brewing ethyl C stripe 33 element vitamin {vitamin Κ betayl betaine and its hydroxyvitamins such as polyethylenimide and polyacrylamide, polyamines, amines, alkenes, and ethylene-polysaccharides), multiple solutions 丨 all other components and gels The salt protection is under the protection of gold, alkaloids, acid-derived alkene, and sodium propylene oxide, etc. (Please read the precautions on the back before filling this page) # 衣. 0 olefin Ethyl methyl polyacrylamide powder), Qiongzui, alkaloid, pyridyl, alkenyl acetate, alginic acid), soluble anhydride, water soluble horse, This effect can be used in the best amount. The body glue will form a protection, protection, and convergence, as well as an occasional gathering. The stability of water in milk is generally referred to as the effect of rubber milk, so that the success of the milk can be achieved. The order is printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. The energetic ethylenic gels in the strip need to be internally protected in the warranty product. The final reaction method is to gather the milk on the restricted base, which is clearly limited. The range of sports equipment is wide and there is a good single and 5 full 2. It is not about ene and B, which is the lower limit of 5 3 better to better 5% is ο% · ο ο 5 is about the limit of content The lower total body weight is better than the single one. The sole weight is 5 A oW ο The weight of the reducible body is guaranteed. The total amount is included with the body weight, while the limited body TP best protection is the best. Or this paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 mm) Printed by the Central Consumers Bureau of Ministry of Economic Affairs, Consumer Cooperatives 473480 A7 B7 V. Description of Invention (6) or surfactant. For example, CMC derivatives can be used as a single stabilizer or in combination with one or more surfactants. The CMC used in the present invention is a water-soluble polymer of Arabe "gum 1221 and 3021 types sold by Aqualon Corporation, Wilmington, Delaware, USA. Suitable hydrophobically modified hydroxyethyl cellulose is Delaware, USA A trademark sold by the Hercules Company of Minton, Natroso 丨 Plus. According to the present invention, the monomer used in the present invention is at least one ethylenically unsaturated monomer, such as vinyl vinegar or ether, stupid vinyl, and others. The acrylate used in the present invention is acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, M, and other acrylic or methacrylic acids. Generally speaking, any ethylenically unsaturated monomer can be cyclic type as required, and can be used freely. Anyone who initiates polymerization by radical can be used to implement the present invention. Preferred ethylenically unsaturated monomers include those below C23K. Examples of suitable monomers include vinyl esters, vinyl ethers, vinyl halides and vinylidene halides, and N-ethylene. Pyrrolidine, ethylene, α-olefins on C3 or M, allylamines, allyl esters of saturated monocarboxylic acids, and their salts, amines, dienes, and derivatives. Suitable vinyl esters class Contains aliphatic vinyl esters, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methacrylate, vinyl valerate, vinyl hexanoate, vinyl versatate ° Typical vinyl ethers include methyl vinyl ether, ethyl vinyl ether, and n-butyl vinyl ether. Applicable α-olefins of C3 or above, including propylene, 1-butene, 1- CNS) Λ4 specification (210 X 297 Gongchu) (Please read the precautions on the back before filling out this page)-clothing. 〆 5 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 473480 A7 B7 5. Description of the invention ( 7) pentene, cyclopentene, 1-hexene, cyclohexene and 1-decene. Allylamine and N-substituted allylamine are examples of typical allylamines. Classes include butadiene, cyclopentadiene, and dicyclopentadiene. Suitable saturated monocarboxylic allyl esters, especially allyl acetate, allyl propionate, allyl lactate, and 醯Amines. The polymers of the invention may be made from one or more ethylenically unsaturated monomers. In this regard Notes "polymer" also refers to the term homopolymer, and copolymers of [mu] and two or more different of monomers. For acrylic and stupid vinyl lattices, low molecular weight CMC is preferred. For the ethyl acetate-acrylate system, low molecular weight HMHEC is preferred, but low molecular weight HEC and low molecular weight CMC can also be used. If acrylic acid or methacrylic acid is used in the polymerization, the amount is preferably about 0.005¾ to about 2! 总, and more preferably about 0.05% to about 1¾ by weight. The polymer of the present invention has a higher glass transition temperature, for example, about 501C to about 150 ° C, and can be tested as "hard", while a lower glass transition temperature, for example, about 100 ° to about -3C, can be tested as " Soft. " The factor that affects the degree of rigidity and softness is the identity of the vinyl fluorene unsaturated monomers used. Different ethylene / unsaturated monomers cause different degrees of rigidity or softness, so they are called "hard" and "soft" monomers. The relative rigidity and softness of different monomers are known in the art. The degree of rigidity or softness of a polymer is therefore affected by the rigidity or softness of the monomers including the polymer, M and the relative ratio of these monomers. This paper size applies to China National Standard (CNS) Λ4 specification (210 × 297 male; |) (Please read the precautions on the back before filling this page)

473480 A7 B7 V. Description of the invention (8 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-Heavy olefin rubber, lacquer two bases and hard C0, Class II need not be ligandene acrylate to emulsion paint _ and. Alkane such as -5-5 alcohol butan end W, is a softened 70 /: 3 facial milk, 44 high-grade alkanesulfene starter batches are increased by 70%, the flatness is high, the C4 position is 50 The base and non-ethyl are added to the pair. To the olefinic system and the child's version, the mono-octyl salt is salted and the J film 5¾ in the half body can be compared with the paint and separated from the hydrocarbyl alkane. 00 acid 1 'This bright, is not really gold oxyethyl He Ruwu nothing 2 batches of hard milk ο 0: 0: from the light, alkane alkali ethoxylate ί 诸 Zhu Kezhong to the point of polymerization, renewed in Λ1 contains half of the acid, ring, and half of the method i. If there is a connection, it is about 50%, and the sulfones such as U ester can be made. Fatty acid esters are based on the following: contact, shape, olefin 1: loose rubber in cation, ether, acid, ¾ dihydration, use it or ο from time to time, about the degree of lactation, alcohol ester sulfur b Butyl milk through ο can be obtained in the agent-system acid. Concentrated mellow acid alcohol ί ' The amount of sulfonate or amount of 5 is all. The oxygen strips are warmed up by polyenes. The sub-mixed ethyl sulfide fat-generating agent has been modified from the copolyester ratio of the modified acrylic resin to survive the gelation. .1 Heyuan is made by adding milk. The ratio of yin and gui, containing sulphur, sulfonate, live, and G-poly is added in the form of thinning & brightening, and covering the surface of the moon. The polymer is heavy. Some of the 50 known agents such as acid and ο amount of lactic acid are used to co-exist, and the lacquer in the benzene is about the nature of the oil, -2, etc. to make the general knowledge or comparison The system can be modified in terms of the amount of glue, and the class 10 is based on the acid batch of the heat-accepted acid formula. Sodium phenol is a sulphur-resistant surface, but the mono-one is added in the body. According to the brightening technology world, the acid and acid groups are good, and the acid can be monoacrylic acid 9: lacquering sex, when the thioalkane and acid are full, (please read the precautions on the back before filling in this Page) This paper size is in accordance with Chinese National Standard (CNS) Λ4 specification (2 丨 0X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 473480 A7 B7 V. The description of the invention (9) can also use the circulation anti- The reactor M carries out the reaction. In the initial feeding of the reactor, it is preferable to add about 5% of ethylene fluorene unsaturated monomer to about 40%, preferably about U to about 25¾, and most preferably about 5¾ to about 15¾. In the reactor It is suitable to add about 0% to 60% of the initiator in the initial charge, preferably about 50¾ to about 60¾. Add any reaction ingredients or ingredients continuously, usually for about 2 to about 5 hours. The initiator can be added in batches or delayed The catalyst, although these changes are not indispensable for the success of the present invention. Generally speaking, the monomer is using aqueous emulsification technology, at about 20 " 0 to about 1 2 0 Ό, to about 4 5 t: to about 9 5 t Preferably, it is polymerized in the presence of a free-radical polymerization initiator, especially a water-soluble peroxide, such as hydrogen peroxide, a persulfate, such as potassium peroxoate, sodium, ammonium, or in some cases, a perborate. Other methods known in the art can also be used to polymerize the monomers, for example, using a system of proton polymerization catalysts such as potassium persulfate, sodium bisulfite. The initiator is used at a concentration of 0.2 to 2.0X by weight, preferably M0.3 to 1.0%. The product obtained by the present invention is a latex system and contains polymer particles thus prepared, dispersed in a continuous aqueous phase as a non-connected phase, and also includes a protective colloid. The average size of the particles shown is better at about 500 nm, more preferably at about 300 nm, and even better at about 200 nm. The latex system of the present invention has excellent shear stability. Consistent with the foregoing, it can be used in latex paint compositions. These paint compositions should preferably contain at least one of pigments and extenders; in addition, other ingredients conventionally used in latex paint formulations, including thickeners, can be used. In addition, the latex system of the present invention can be used for water-based ink products and paper coating. 11- The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) (Please read the precautions on the back before filling in this page)

473480 A7 B7 V. Description of the invention (Its special composition grouping agent is sticky and used. Compound sticking material composition agent is not woven, and the substance is refined into paste group. It is not except that -1BT is weighed to equalize the soil. Hundreds and Quantitative Points-Ί The user clearly stated that 0 This means that there is an explicit statement for the purpose of the implementation of the example, plus + 0 examples of the application of the example below the example of the present invention is not limited to the law Analysis 01 layer 5 analysis an decoration VI can be highly effective: it is installed and installed as a test equipment (please read the precautions on the back before filling this page) and the difference between the dj body Recording type of My, Kasama Teruyuki line washing and flushing, 1 2 = Η Π advance schedule fixed parameters can be combined, mouth valve out style elbow test pass 30 type 2 analysis ο 53 C of Ε Θ S Π VV line d into e0 K since when 10 purchase analysis # Column points 5 C In the preparation of SE, install: and use column Ran to analyze. 槽 layer phase 811 ^ transfer stable path with needles with side illumination Back sample

The depositor's injection safety valve is printed in the country _ β, _ h ί, R c IN. The printing group number of the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. FtMX4 Approved by the number D ffl I 5 • ra2 o D (.6 phase I .column 4 in m analysis-1 X junction .m min 1 ± ΓΊ it chemical base propylene glycol has a diameter C} LO upper hole G§ # 2 silicon cell 0148 chemical A (two 92 Oxygen 00, 4 batches of s4 3D c ο 3., Ρ 9 0 1) G 7 2-2 2m tablets are separated and protected by 2 2ra column

X 歹 indicates that the columns are grouped into phase shifts, and the sons of phase shifting are used in phase shifting. The two of the phase shifting from the public Λ 4 1 are 2 liters of Q, and the smallest is ο 7 method. B is the water P liter of MC4 0 3. Million deionized liquid 6 De-fragmented slowly-distilled salt, distilled in 1 «2 bottles of Boiled and Measured, high capacity acid liter B'-ΐ This paper size applies Chinese National Standard (CNS) A4 specification (210X 297) (%) 473480 A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (11) Sub-strength 锾 liquid. The ionic strength of this solution was increased to 1.44 M by the addition of 0.4 mol sodium sulfate to 1 liter of a 0.24 M acetate solution. In the sample preparation, 1.44M ionic strength solution was used to reduce mobile phase mismatch. The final mobile phase was prepared by diluting 1.44M ionic strength solution with distilled deionized water 1: 1 and filtering through a 0.22wm type GS Millipore membrane. Sample preparation: All samples are prepared by dissolving 0.150 g of polymer (solid basis, corrected water content) in distilled deionized water to a total volume of 25 ml, resulting in an initial hysteresis of 6 mg / ml. These aqueous solutions were diluted 1: 1 with M1.4M double-strength acetate solution to a concentration of 3 kg / ml, approximately matching the mobile phase composition. All sample solutions were filtered through a 0.45 UB M i 1 le X -HV consumable unit (Millipore product) before injection. Analytical conditions Column set: gpc ιοοχ protection, looL loot ιοοοχ (Synchropak) mobile phase: 0.7 M, pH 3.7 Acetate buffer flow rate: 0.5Bl / min (measured 0.51el / ®in) Pressure: ~ 135 to 140ATM Graph speed: lcm / ΐΒίη Sample concentration: 1.5 ~ 2. 0 mg / m 1 DR I attenuation: 2X Each sample was injected multiple times using the above conditions. The obtained SEC chromatogram was coated with transparent paper and compared with the standard Mw. Calibration: Various M w series of American Polymer Standard Corporation (D X T K I T) -13- (Please read the precautions on the back before filling this page)

" -11 This paper size applies to China National Standard (CNS) Λ4 specification (2! 0 × M7). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 473480 A7 B7 5. Description of the invention (12) Dextran standard, used The aforementioned capacity (distance) analysis. Basically, the minimum molecular weight standard (DXT 180MW) for the total permeation limit elution is also used as the internal standard. Inquiry on the method of measuring the amount of Mw of the earth. Example 1 Using the low score to obtain the earth's energy. ≫ Acrylic acid preparation This example illustrates the specific example of the aqueous dispersion of the present invention and how to prepare it. Polymerization was performed in a 2 liter glass reaction vessel equipped with a thermocouple, a reflux condenser, a monomer inlet, an initiator inlet, and a half-moon agitator. In 461 grams of demineralized water, 16.6 grams of protective colloid (carboxymethylcellulose (CMC), sold under the trademark M Ambergum302 1 with a weight average molecular weight (Mw) of about 7,000 to 11,000, a degree of carboxy substitution of about 1.2, A qua 1 ο Available from company η with a solution concentration of 29.6 I, its B r ο κfie 1 d viscosity (630 mPais) * at 2.5 and 1.6 grams of sodium bicarbonate. After completely dissolving, the temperature was raised to 85C in a water bath. Next, add 40¾ initiator solution (1.5 g of potassium perrhenate dissolved in 50 g of demineralized water) evenly over 30 seconds. After one minute, monomer addition was started. Μ was added to measure the monomer mixture (248.6 g of butyl acrylate, 248.6 g of methacrylic acid methyl ester, and 2.8 g of methacrylic acid), initially at 54.5 g per hour, and this speed gradually increased to 1 6 3 per hour in the first hour of the reaction. 5 grams. When the temperature returned to 8 5 t, the remaining approximately 95¾ of the initiator was metered, and 5¾ of the initiator solution remained, which was added after the monomers had all been metered. Add the remaining 95¾ of the initiator shown in the same time period of the monomer. Adjust the initiator addition speed to the monomer addition speed so that the monomer addition and the addition of the remaining 95¾ of the initiator are completed at the same time. Add monomer and initiator for 3.5 to 4 hours, respectively 1-4. This paper size applies Chinese National Standard (CNS) Λ4 specification (21〇X 297 cm) (Please read the precautions on the back before filling in this Page) clothing. 1 ^^, 473480 A7 B7 V. Description of the invention (octyl succinate; Aerosol 0T-75, 75% of live physical properties < :: Fang Rong inside. Examples of dehydration of water and minerals旃 richest sub-item is low with benzene agent tongue * Yt and bounded with arsenic acid allyl I allyl 迺 2 scoop, -Jn 3m oxw hot mix electric stir-up preparation in half, 口 口 S 隹There is a single case of the agent, another one is the bow, the one is the mouth, and the second is the hidden bone.

U ⑪. C ί Take 2. Concentrated polymer solution dissolves, and the body gel protects it, which contains 63 water. It has low-quality slime and its liquid minerals. Add sodium sulphate and sodium sulphate, dissolve in a spoon, remove β oc ° c 5 8 to 5 high 1. Raise the temperature of the solution, cite the agent bath hair water% υ ο He 4, add the solution and add a solution After the second is over, the addition of ethyl benzene and benzophenone? 5 minutes after 24 minutes, the esters are separated. (Acid) lactone water gram 5 substance 24 ore 5 dehydrate gram 5 mixed potassium monoacid thiol reaction in polygram 5 5 4 ο 5 hours S 3 every 16 Degree to speed, increase and increase gradually) acid by acid, but after the isobutylene is a small gram a 1st Ding An cut pieces live and bound pieces apart 10. TTV. And the same phase, the description is from the Yin Yin 1 use case, application D example and comparison bh: ¾ acid is propylene-ethyl benzene (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

According to the description of the subscript 2 the low case needs to be applied, and when used, the agent 0 character live crystal plane delimitation of the degree of stability ii to obtain a low value, the indicator table example is more like this C Yin E grams A 5] Yes .0η in SP • 1 water D gram · purpose 3 S 6 § 4 S. thio modified ether-based rubber aromatic protective base alkoxylate gram 33 agent, the sequence sequence boundary and sexual formula match the isolated physical tongue '7— The city of Fudosedou has state-of-the-art properties, tongue * vt facet character proton gram 5 and) ¾ Si Yuan Gong Ru Jun 1 ej k k k G G G G r 纸张 ring paper size applicable to Chinese national standards (CNS) Λ4 specification (210X297 mm) 473480 A7 B7 V. Description of the invention (15) Ethyl oxide: Intrasol NP10, 100¾ active substance). In this case, the monomer mixture was 248.6 g of butyl acrylate, 248.6 g of styrene, and 2.8 g of methacrylic acid. Tracheostomy case 3: Combined use and living parts _ and Pseudo-Fraction CMC Porcene Zene Zene-Acrylic Strip Use the formula and procedure described in Example 2, except that in addition to the Ambregun® solution, 15 grams of anionic Surfactant (alkyl aryl ether sulfate: Disponil AES 60; 33¾ active substance), and 5 grams of nonionic surfactant (nonylphenol ethoxylate with 10 ethylene oxide units: Intrasol HP10, 100¾ active Substance), in 450 g of water, M for stabilization. g Example 4 Bacterial active ingredients and cooking agents CMC glycosides, chemical compounds 7, ene-acrylic acid were prepared using the formula and procedure described in Example 2, except that AmbregUIn® 3021 products were changed to 16.6 grams, together with 5.9 grams of anionic surfactant (sodium dicyclohexylsulfosuccinate: Aerosol A 196, 85¾ active substance), 5 grams of nonionic surfactant (nonylphenol ethoxylate with 4 ethylene oxide units: Surfonic NP40, 100¾ active substance), used for 463 grams of printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) in water. In this case, the monomer mixture was 248.6 g of butyl acrylate, 248.6 g of styrene, and 2.8 g of methyl acrylate. Increasing the initiation dose Μ improves monomer conversion, but still at low levels. The initiator solution contained 3 g of potassium persulfate in 100 g of water. Tube pus example 5 contains cooking ingredients, most of which are CMC 7, acid zinc-propylene. This example shows that in the monomer composition, a relatively high amount of butyl acrylate, -17- This paper size applies to Chinese national standards (CNS) Λ4 specification (210 × 29?) 473480 A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (K) Possibility of preparing vinyl acrylic dispersion without surfactant. Polymerization was carried out in a 2 liter glass reaction vessel equipped with a thermocouple, a reflux condenser, a monomer inlet, an initiator inlet, and a half-month stirrer. Take 33 grams of protective colloid (Ambergum ^ SOSl CMC solution, solution 澹 29. 6¾, Brook's fied 1 viscosity 630 mPa. S at 25), together with 2.0 grams of sodium bicarbonate, dissolve into 397 grams of demineralized water. After the 俟 is completely dissolved, raise the temperature to 8010 using a water bath. Secondly, the initiator solution (1.5 g of potassium persulfate in 50 g of demineralized water) was added uniformly over 30 seconds. After one minute, start adding monomer. The monomer mixture (350 grams of vinyl acetate and 150 grams of butyl acrylate) was added at a rate of 54.5 grams per hour initially and gradually increased to 163.5 grams per hour during the first hour of the reaction. When the temperature reached 80 ° C, the remaining 95% of the initiator solution was then metered. Retain the 5% initiator solution and add all the monomers after metering. The initiator is added in the same time as the monomer, and the initiator addition speed is adjusted to the monomer addition speed. Monomers and initiators were added for 3.5 to 4 hours with the plunger and peristaltic pumps, respectively. The reaction temperature was maintained at 80 ° C. After the initiator and monomer were added, the polymerization was terminated at 80 t: the temperature was maintained for 1 hour. The lattice is then cooled to room temperature. The stirring speed during the reaction was 200 rpm. Honey fi Example fi fi contains bounded and live castration and low scores. The most CMC 7, acid 7, ene-acrylic acid. The formula and procedures used in this example are the same as in Example 5. The changes are as follows: 33 grams戍 11 ^ 6 「8 1111） | ^ 3021 0 materials 〇 Use 67g / ^ 1! ^ 6「 811111® 1 5 2 1 product (14.7% solution Mae degree, at 2 5 υ B r ο 〇kfie 1 d Viscosity: -1 8- (Please read the precautions on the back before filling this page). Order # This paper size is applicable to China National Standard (CNS) Λ4 specification (210 / i 297 mm) Central Ministry of Economic Affairs Printed by the Consumer Bureau of Standards Bureau 473480 A7 B7 V. Description of the invention (π) 1 5 4 0 m P a. S, M w about 3 5, 0 0 0 to 5 0, 0 0 0, the degree of substitution of carboxyl group is about 1 · 2), together with 17 g of anionic surfactant (sulfated nonylphenol ethanide with 30 ethylene oxide units: F e η ο ρ ο η Ε Ρ 1 2 Q; 3 (U active substance), and 7 1 gram of non-ionic (any phenol ethoxylate, A 111 ar ο XC 0 8 9 7 70¾ active substance), dissolved in 3 6 3 grams of demineralized water. The rest of the formula is the same as in Example 4. Fen Shi 7 Both bound and active agent and low The most CMC of Ethyl Cool 7 and Ethylene-Propylene Preparation The formula and procedures used in this example are the same as those used in Example 5, except that a surfactant is also added in this example: the protective colloid and the buffer solution are dissolved in 397 g. In water, together with 5 grams of nonionic surfactant (nonylphenol ethoxide with 20 cycloethane units: Tergit ο 1 Ν Ρ 4 0; 1 D 0% active substance), and U grams of anionic interface Active agent (sulfated ethoxylated ethoxylate, with 30 ethylene oxide units: Fe η 〇p ο η EP 1 2 0; 30% active substance). Fenxi Example 8 Contains bounds and live castration And low tiller amount of HFC ^ 7,7, ene-propylene casein The formula and procedure used in this example are the same as described in Example 1, except that the changes are as follows: 12.5 grams of mixed anionic surfactant (D is ρ ο ni 1 MGS 1 5 6, active substance 4 Q%), together with 7.1 grams of anionic (Anytar ethoxylate, Antar ο XC 0 8 9 7, 70% active substance), 3.3 G of low molecular weight ΗEC (29.1% solution concentration, B r 〇, 〇kfie 1 d viscosity at 2 5 ° C 2 60 m P a. S), M w about 7, f) [) 0 to About 1 1, 0 G 0, and 2.8 g of sodium bicarbonate were dissolved in 397 g of deionized water. Reaction temperature 8 (TC, monomer mixture includes 350 grams of vinyl acetate and 150 grams of butyl acrylate. -1 9-This paper size applies to Chinese National Standard (CNS) Λ4 specification (210X 297 mm) (please (Read the precautions on the back before filling out this page.)

1T 473480 A7 B7 V. Description of the invention (θ) Economy '郅 Central Standards Bureau employee consumption cooperation Du printed case 9; combined with interface active agent and low molecular halo H Μ Η EC vinyl acetate ft-propyl t Greek Cool preparation (invention) uses the same formula and procedure as described in Example 8 except that low molecular weight CMC is used instead »4 7 .4 g low molecular weight N atr 0 S ο 1 P 1 u S HM HE C (solution concentration 2 1.1 Br 〇〇kfi el d viscosity at 2 5. 2 8.5 m Pa S) 0 The weight average molecular weight of this protective colloid is about 25, 0 0 0 0 So> the amount of water must be adjusted to achieve latex Same solid content. Surfactant, buffer (1.0 g in this example) and protective colloid J dissolved in 38 3 g of demineralized water. Example 10 Both surfactant and low molecular halo HMHEC The formula and procedure of Pinene Cool-Acrylic Preparation are the same as those described in Example 8. Instead of low molecular weight CM C 1, use 10 grams of low molecular weight Nat. Γ 0 S 〇 1 P 1 u S HM HE C (2% solution viscosity at 2 5 4 Π) Pa .S »M w about 2 5 ， 0 0 0） 〇 So »the amount of water must be adjusted 〇 surfactant, 2.0 grams of buffer protective colloid dissolved in 3 8 3 grams of demineralized water 0 bu bu | comparative example R Ethylene glycol m-acrylic strip The formula and procedures used in this comparative example are identical to those used in Example 5 except that the protective colloid is not used, so the surfactant mixture and buffer 1 are dissolved in 4 20 grams of water. C30 military conversion rate is poor and latex viscosity is very low when only surfactant is used. Example 1 1 Use of active agent and low-molecular-weight halo CMC to audit vinyl acetate m-, ene in the thermocouple early body equipment Π Initiator into Π m mixer 2 -20- (Please read the back Precautions to fill out this page)

This paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 473480 A7 B7 V. Description of the invention () Polymerization in a liter stainless steel reaction vessel. Take 33 grams of protective colloid (Ant bergu in ® 3 0 2 1 CMC, solution concentration 29.6%, solution viscosity at 25 ° C 6 3 Q m P a. S), and 1.2 5 grams Sodium hydrogen sulfonate was dissolved in 3 37 grams of demineralized water. Next add 2 1.5 grams of 100% active EHSS (bis (ethylhexyl) sodium succinate), and 3.6 grams of An n.ar ο XC 0 8 9 7 material (nonylphenol 4 0 E 0). After the 俟 is completely dissolved, the temperature rises to 8 ° C. Secondly, a 15% initiator solution (2.5 g of potassium persulfate in 100 g of demineralized water) is added uniformly within 30 seconds. After one minute, Start adding the monomer and the remaining initiator solution. Gradually add 445 g of vinyl acetate for 120 minutes, keeping the pressure of ethyl acetate on the reaction vessel 21 bar. Add the initiator during the same period as the monomer The reaction temperature was maintained at 8 D ° C. After the initiator and monomer were completely added, the temperature was maintained at 8 ° C for 1 hour to terminate the polymerization. Then, the lattice was cooled to room temperature. Rich Example 1 Cutting and low tillering amount CMC Anzao 7, 7, 7-ene-propylene-butadiene; at high frying force This example shows the possibility of using a high shear force in the reaction when a low molecular weight protective colloid is applied. The formula and procedure used in this example are the same as those described in Example 5, but in this example, 12.5 grams of anionic surfactant (D is ρ ο n il MGS) 5 6, active substance: 4 0 %), 7.1 grams of nonionic surfactant (nonylphenol ethoxide, Ari tar ο XC 0 8 9 7, 7 0% Active substance), 33 g of protective colloid (A mbergum ® 3 () 2 1 CMC, solution concentration 2 3 · 6%, B r okokie 1 d viscosity at 25 ° C 6 3 0 m P a. S) , And a mixture of 2.0 grams of sodium hydrogen sulfonate, dissolved in 397 grams of demineralized water. Hh mm F Use the active and active tincture An Zhouhua 7, cool ethylene ft purpose-propylene cool work-version " ——Agglomeration with high strength_- 9 1 ............. This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210X 297 mm) (please first (Read the notes on the back and fill out this page)

473480 A7 B7 V. Description of the invention (20) This comparative example shows that when high shear force is applied, a protective colloid is needed during polymerization. The formulation and procedure used in this comparative example are the same as those described in Example 5, except that in this comparative example, 12.5 grams of anionic surfactant (Disponil MGS 156, active substance 40¾) was taken > 7.1 grams of nonionic surfactant Agent (nonanol ethoxylate, Antarox CO 897, 70¾ active substance), and 2.0 g of sodium bicarbonate, dissolved in 420 g of demineralized water. The mixing speed in this comparative example was 400 rpm (tip speed 2.72ia / s). When Example 1 3 was prepared, all the acrylic acid-based latexes that had been stabilized with ΠΜΠ were polymerized as described in Example 1, except that the changes were as follows. 16.6 grams of Amber gum® 3021 CMC instead of 33 grams of Ambergui »® 3021 CMC, along with 6.25 grams of dihexylsulfosuccinate (D isp ο ni 1 SUSIC 6 8 0, 80¾ active substance) with 4 瓖5 grams of ethoxylated ethoxylate (Surfonic N40, 100¾ active substance) and 1.6 grams of sodium bicarbonate are dissolved in 450 grams of demineralized water. The monomer mixture used included 200 grams of methyl methacrylate, 300 grams of butyl acrylate, and 2.8 grams of methacrylate. hb. Age example G Crystals are low, and they are low in daily life. _ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China (Please read the precautions on the back before filling this page) The polymerization of this comparative example was carried out as described in Example 13, except that the Amber gum polymer was not used for stabilization. All the surfactants and buffers were dissolved in 473 grams of water. When the bottle example 1 4 Jie Low Cheng _ warm hemp low daily ultra-high-temperature dehumidification most HMHRC An Zhou Hua Xi 7, acid Z-ene cool-acrylic acid preparation, 睽 -22- This paper size applies to the Chinese national standard (CNS) Specification Λ4 (210 X 297 g) 473480 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7. V. Description of Invention (2i) Polymerization was performed as described in Example 10, with the following changes: Take 12.7 grams of mixed anionic interfacial activity Agent (Disponil MGS 156 active substance 40¾), 7.7 grams of ethoxylated fatty acid (Disponii APE 257, 65¾ active substance), 1.6 grams of sodium bicarbonate, and 10 grams of low molecular weight "" 0505 卩 11 ^ 01 ^ ( :, Soluble in 4 22 g of demineralized water. The monomer mixture contains 200 g of vinyl acetate and 300 g of butyl acrylate. The particle size distribution is measured by a MJoyce Loeb 丨 disc centrifuge. G pus example 1 5 Summer low strontium strontium hemp medium daily CMC stabilization chemical ether 7, ether 7, μ my νρον ^ -ioa, m 2 liters equipped with thermocouple, reflux condenser, monomer inlet, initiator inlet, half-moon agitator Polymerize in a glass reaction vessel. Take 40 g of protective colloid (AmbergUm® 3021 CMC, solution concentrated 2 9. 6%, at 2 5 its B r okokie 1 d viscosity 6 3 0 b P a · s > together with 1.6 g of sodium bicarbonate and 7.5 g of dihexylsulfosuccinate ( D isp ο η 1 1 SUS IC680, 80¾ active substance), and 6 grams of non-ionic surfactant (ATP0L E 5720) dissolved in 432 grams of demineralized water. After the mixture is completely dissolved, the temperature is raised to 801 in a water bath Secondly, add 5% of the total monomer in one minute. After 2 minutes, add 2 5 S of the initiator solution (1.8 g of potassium pertellurate in 60 g of demineralized water). At 721, monomer addition was started. The monomer mixture was measured (300 grams of vinyl acetate, 300 grams of VeoVa-10 monomer) at a rate of 180 grams per hour. Ve〇Va is a Koch acid vinyl ester product sold by the Shell Chemical Company After five minutes, the temperature rose to 80 ° C and maintained at this temperature. The initiator solution meteor was adjusted to the monomer flow rate. The stirring speed of the stirrer during the reaction was 200 -23- (Please read the precautions on the back before filling this page)

" if this paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 473480 A7 B7 V. Description of invention (22) rpm. After the addition of the initiator and the monomer, the polymerization was terminated by maintaining the temperature at 80 ° for 1 hour. The polymeric substance is then cooled to room temperature. Comparative Example Η: Vinyl Acetate / Veoova-10 Latex Stabilized with a Surfactant at a Lowest Medium Film Formation Temperature This comparative example was polymerized according to Example 15 except that the protective colloid was not used. Therefore, the amount of water should be adjusted to 460 grams. Example 16 Stabilized methacrylic acid methyl ester / VeoVa-9 butyl latex using CMC and surfactant was polymerized according to Example 13, except that the monomer mixture contained 100 g of methyl methacrylate and 100 g of VeoVa-9 monomer , 300 grams of butyl acrylate, and 2.8 grams of methacrylic acid. Example 7 Methyl methacrylate / VeoVa-9 / butyl acrylate latex stabilized with CMC without using a surfactant. Polymerization was carried out according to Example 16, except that the surfactant was omitted. Example 18 Stabilized methyl methacrylate / butyl acrylate latex with ultra-low molecular weight hydroxypropyl cellulose was polymerized using the procedure described in Example 1. For the protective colloid, 16.5 grams of ultra-low molecular weight hydroxypropyl cellulose (Mw6500) 30¾ solution with a cloud point of 90CM was used in place of 16.6 grams of Arabberguim® 3021 CMC. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). The lattice performance of the foregoing examples and comparative examples is shown in Tables 1 and 2 below. This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 473480 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (23) Table 1 Example solids (% by weight) Coarse grain PM pH PS 1 (n ra) Shear stability (min) 1 48.8 200 6. 4 310 > 5 A Cohesion B 46.2 70 6.3 η. d. > 5 C 48.0 80 6.5 < 100 < 1 2 46.9 9900 5.8 220 < 1 D agglomeration 3 47.0 100 5.7 740 > 5 4 48.0 130 5.4 230 > 5 5 49.9 11000 4.8 830 > 5 6 49.9 380 5.1 240 > 5 7 48.9 670 5.. 1 230 > 5 8 49.7 406 4.9 200 3 9 50.8 130 4.7 220 3 10 50.6 610 3.7 350 4 E 49.1 170 5.0 170 < 1 11 52.2 190 4.9 320 > 5 12 50.0 20 5.5 590 > 5 F 45.4 400 5.4 210 < 3 13 45.1 80 5. 9 230 N. D. G precipitation 14 49.7 180 4.7 280 N. D. 15 52.3 70 4.8 480 N. D. Plutonium condensate 16 44. 9 60 6.4 215 N. D. 17 44.3 40 6.2 170 N. D. 18 46.2 90 6.0 345 N. D. Note. The performance is determined by the grain size and the average force. The flat shears are counted and the speed is measured. Between the heart and the clock, the time is 5 and the circle is condensed. bl 机 生 宝 oe 料 发 _ ”Mixed display elng table ίκ ycrl word Jowa number D mm, n (Please read the precautions on the back before filling this page. Order

This paper scale is applicable to China National Standard (CNS) Λ4 specification (210X 297 male f) -25- 473480 A7 B7 V. Description of the invention (24) Table 2 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Example viscosity mPa. s Film gloss FDT201C, -45¾. Film spot FDT20O, -45¾. MFT 3) 1 200 78 82 8 9 ND A agglomeration B 20 25 61 9 9 ND C 480 63 65 10 10 ND 2 1050 76 90 8 9 ND D agglomeration 3 3000 79 84 8 9 ND 4 940 49 89 9 9 ND 5 40 73 79 4 4 HD 6 2625 79 82 9 9 ND 7 680 78 80 9 9 ND 8 365 79 81 9 9 ND 9 485 80 81 9 9 ND 10 960 81 81 10 10 ND E 50 80 81 10 9 HD 11 90 77 82 6 8 ND 12 50 79 82 8 9 ND F 30 76 82 10 10 HD 13 600 83 83 9 9 < 〇G precipitation 14 2325 81 82 9 9 < 0 15 420 77 83 8 9 11 Η Coacervation 16 2100 82 82 9 9 12 17 1200 81 81 9 9 HD 18 20 30 33 9 9 ND Note: 1. Brookfield viscosity at 20 rpm at 20 rpm. 2. FDT is the English abbreviation of film drying temperature. 3. MFT is the minimum film forming temperature. 4. N.D. is an abbreviation that has not been determined. (Please read the notes on the back before filling this page)

This paper scale applies Chinese National Standard (CNS) Λ4 specification (2 丨 〇X 297 | ^ —) 473480 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (25) Determination of solid content by K gravity method, scale The amount of latex was dried at 120o, and then the amount was dried, and the dry weight and wet weight were divided. Coarse grain content is measured by weighing the latex on a No. 200 sieve, and the part exceeding the No. 200. Membrane Performance For the water tank test, it is on a glass substrate. For wet-thickness 200Wm latex film measurement, M film gloss measurement was performed on Leneta sheet. The latex film was dried at 2010 and 451C, and the film gloss was measured with a MByk gloss head at a 60 ° angle. Water resistance is measured by putting a few drops of water on the film. After five minutes, the appearance of the film was judged. The evaluation is as follows: 10 clear 8 slightly turbid 6 turbid 4 opal 2 white 0 film re-emulsification The particle size distribution is measured by a M Joyce Loebl disc centrifuge. When Example 1 9 is used in the world, it is the most acidic Z-Hydroxy-Z-acid 7, alkenyl-butyl-acrylic acid, and it is made of pigment. Hemp (PVC) 65 paint is used in this example. The protective colloid stabilization emulsion of the non-mineral polymer phase, which is characterized by a small particle size (approximately 200 nm in this example), exhibits excellent properties of the paint due to its good film-forming ability. Due to its fine particle size, the paint can be made more stable. High filling system formulation. The latex of Example 9 was used in the PVC 65 paint, as shown in Table 3. -27- (Please read the precautions on the back before filling in this page) The size of the paper used in the edition is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 473480 A7 B7 V. Description of the invention (26) hh comparative example T 7 , 6 Nu 7, enecool- ^ 〇 ^ commercially available rolled (M owi 1 ΐ th ΠM21) m PVC lacquer PVC 65 formulation using commercially available latex (Mowilith DM21), also listed in Table 3. Surfactant for paint and Natrosol Plus low molecular weight Η M H E C stabilized. Example 20 of the vial, using the active agent and low-molecular-weight suspension HMHRC, Zyrene, Zinc Cool-Acrylic Butyl Ester, rubber, PVC 80 paint, PVC 80 paint, use Example 9 latex, as shown in Table 3 As shown. Vial Example 21 The most stable CMC glycosylated styrene-acrylic sg was used in the vial case. $ Apv [80 lacquer uses the latex described in Example 4, but uses 33 g (instead of 16.6 g). ) A mbergum ® 3 0 2 1 solution, as a protective colloid, used as a latex in PVC 80 paint, is also listed in Table 3. Comparative Example J: Use commercially available styrene-acrylic latex (Acronai 29 0D) to make PVC 80 lacquer and PVC 80 formula. Use commercially available latex (Acronal 290D), also listed in Table 3. 0 Bottle example 2?畐 CM An Zhou 丨 h acrylic strip 3, Jiao Dan PVC 1 印 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of lacquer (please read the precautions on the back before filling this page)

The latex described in Example 1 was used in the PVC 15 high-gloss paint, as shown in Table 3. hh Comparative Example K: Commercially available propylene brewed milk_ (Prinia) AC 5 07) Dan PVC L5Jf— P V C 1 5 uses a commercially available latex (P r i m a I A C 5 0 7), which is also listed in Table 3. -28- This paper size applies Chinese National Standard (CNS) Λ4 specification (2 丨 OX 297 mm) 473480 A7 B7 V. Description of the invention (27) Examples 19-21 and Comparative Examples J, 1 (paint properties, As shown in Tables 4 and 5. Among the weighting agents in Tables 4 and 5, Katrosol MBR and Hatrosol HBR are used as unrelated thickeners, while Natrosol Plus and Primal RM8 are used as related thickeners. Natrpsol MBR and Natrosol HBR, like Natrosol Plus, are products of Hercules, Wilmington, Delaware, and Prima 1 R Μ 8 is a product of Rohm and Haas, Philadelphia. (Please read the precautions on the back before (Fill in this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 473480 A7 B7 V. Description of the invention (28) Table 3 Printed by the Consumer Cooperatives of the Municipal Bureau of PVC 65 (grams) PVC 80 (grams) PVC 15 (grams) Water 197.0 230.0 49.7 Calgon N 1.0 1.5 2.02 Pigment Verteiler A 2.0 3.0-Tamol 731 A-0.69 CA 24 2.0 3.0 0.51 Agitan 280 1.0 5.0 10 increase Agent as needed ammonia (25¾) 0.4--Kronos RH57 159.0 198.0 210.9 Oroya Ii te 90 114.0 140.0-Durca I 5 159.0 198.0-Talcum AT 200 23.0 28.0-latex 167.0 93.0 671.9 butyl glycol 15.0 20.0-Texanol 4.0 5.0 12.1 Agitan 280 0.6--Water 150 71.5 52.1 Total 1000 1000 1000 — 30— (Please read the notes on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) Λ4 specification (2 丨 0X 297 male 473480 A7 B7 V. Description of the invention (29 Table 4 Performance of low molecular weight wesoxether ether stabilizer stabilized lattice lacquer printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics Cellular thickener wu Thickener Stormer viscosity ( KU) ICI viscosity (mPa.s) Homogenization (1eneta 1) 19 Hatroso 1 Plus 0.52 123 110 5 19 Natrosol HBR 0.51 102 110 7 1 Natroso 1 Plus 0.50 100 110 5 1 Natrosol mBR 0.50 104 110 5 20 Natrosol Plus 0.33 120 90 3 20 Natrosol HBR 0.31 112 100 3 21 Natrosol Plus 0.40 128 90 1 21 Natrosol HBR 0.32 112 120 4 J Natroso 1 Plus 0.43 109 110 3 J Natrosol HBR 0. 36 104 120 3 22 Natrosol Plus 0.11 96 100 5 22 Natrosol HBR 0.23 96 120 4 K Primal RM 8 0.03 95 100 5 K Natrosol HBR 0.24 94 98 2 1. Grades 1-10, M10 best — 31 — This paper size applies to China National Standard (CNS) Λ4 Specification (2 丨 〇 < 297 cm),-»^^ 1-Γ *-— ^ ― -I--II I — ^ 1. (Please read the precautions on the back first Fill out this page again) Order 473480 A7 B7 V. Description of the invention (30) Table 5 Example Thickener Splash Resistance 1 Washability 2 (cycles) Gloss (mPa) 19 Natroso 1 Plus 6 > 10000-19 Natrosol MBR 2 > 10000-1 Natrosol Plus 7 2300-1 Natroso I MBR 2 2000-20 Natrosol Plus 7 940-20 Natrosol HBR 2 850-21 Natroso 1 Plus 7 1010-21 Natroso l HBR 2 940 — J Natroso 1 Plus 7 --J Natroso 1 HBR 2-— 22 Natroso 1 Plus--59 22 Natroso 1 HBR--59 K Primal RM8 —-63 K Natroso 1 HBR--71 Printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read first Note on the back, please fill in this page again) 1. Level 1-10, Μ 10 is best. 2. DIN 53778. -32- This paper size applies Chinese National Standards (CNS) Λ4 specifications (210X 297 mm) 473480 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (31 It consists of the following ingredients, including Example 1 3 Latex to prepare solvent-free latex lacquer. Ingredients (g) Water 197 C a 1 g ο η Ν 1.0

Pigraentverteiler A 2.0 CA 24 2.0

Agitan 280 1.6

Hatrosol 250 MBR 5.0 Ammonia (25¾) 0.4

Kronos RN 57 159

Omyalite 90 114 D u r c a 1 5 15 9

Talcum AT200 23 Latex (Example 13) 167 Water 150 贲 The paint properties of Example 2 3 are listed in Table 6. -33- This paper size applies to Chinese National Standard (CNS) Λ4 specification (2 丨 0 乂 297 mm) (Please read the precautions on the back before filling this page)

473480 A7 B7 V. Description of the invention (32) Table 6 Evaluation of thickening efficiency without solvent paint Natrosol 250 MBR 0.57¾ Stormer viscosity (KU) 103 1C I viscosity 90 Finally, although the present invention has been referred to specific institutions, materials, and specific examples Adding the explanation, it should be noted that the present invention is not limited to the details, but extends to equivalents within the scope of patent application. (Please read the precautions on the back before filling this page), ya

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 1 34- This paper is over-sized; i] t threshold valve family mark $ (CNS, ι Λ4 specifications Ή Ο / 297 公 筇)

Claims (1)

4-¾473480 Patent Application Announcement B8 C8 D8 No. 85103 283 "Emulsion system with a tendency to flocculate due to grafting, its preparation method and latex paint composition" (Amended in October 1990) 1. A method for preparing a latex system having a tendency to flocculate due to grafting. The improvement includes the presence of a water-soluble protective colloid that stabilizes the latex system, although the molecular match is less than 75,000, and the presence of an initiator. Below 20 f. To 1 2 0 t: emulsification polymerization of at least one ethylenically unsaturated monomer from water, the monomer is selected from acrylic acid, methacrylic acid, butyl acrylate, methacrylic acid methyl, acrylic esters, benzene Ethylene, vinyl ethers, vinyl halides, vinylidene, N-ethoxylated noodles, Yican, C 3 or above α-Liyanol, allylamines, allyl saturated monocarboxylic acids Base esters and their amines, propylene, 1-butene, bupentene,! -Hexene, budecene, dipropyl acetate, allyl propionate, allyl lactate, and its amines 7 and its mixture, the water-soluble protective colloid is pseudo-selected from carboxymethyl fibers with a lower limit of carboxy substitution of 0.7 And its derivatives, hydroxyethyl cellulose, hydroxyethyl cellulose ether, methyl cellulose, hydroxypropyl cellulose methyl ether, hydroxypropyl cellulose, polyacrylic acid and its age metal salt, ethylated starch Derivatives, sodium salt of polyacrylates and other alkali metal salts, water-soluble powdery gelatin, gelatin, water-soluble alginate, casein, agar, natural and synthetic gums, partially and fully hydrolyzed polyvinyl alcohol, polypropylene Ammonium amine, polyvinylpyrrolidone, and poly (methyl vinyl ether-maleic anhydride): the effective latex system of water-soluble protective colloid is from 0 · 005¾ to 5.0 S: and the mother of the initiator is 0.2 to 2.0%; the above percentages are based on 1-this paper is applicable to Chinese National Standards (CNS) A4 (210X297 mm) (please read the precautions on the back before filling in, 1 write in the center of the Ministry of Economic Affairs) Printed by 473480 B8 C8 D8 of the Employees ’Cooperative of the Bureau of Standards, the scope of patent application is relatively high, and it is the same as in the electricity. The basic method is the system's total 1 S1 single circle and Fan full. Yeshen B such as 2 to weight total Tidan and saturate are not able to be bounded by their active properties. They are active in both active and active roles, and they are not in the real world. * \ The legal system of Li Xiangyang 2 and Di Ganggang. Fan Li Zhunli Yinyin Difficulty asks for _s ¾ Applicants include the legal system in the enveloping activity surface. Item 3 is a combination of the scope and benefits, and the application of sex is as fat as possible. Fatty acid groups, diethyl ethers, acid thioesters, high sulfur grades, fatty alcohols, sulfonates, fatty acids, sulfonates, metalloids, polyoxylated ethoxylates, biochemicals Sulfur and phenol-like alkane formation biochemical, its η and -alcohol C alkane and its type 1 ester acid dibutyl sulfonate and encapsulation active surface 4 its legal system 4 Is combined application such as 5 disodium, acidification of oils, dry and hard acetic acid phenolic esters, monoesters, alkylthioethyl gas, lauric acid ring 0 5 \ 4-sodium has acid Ji Yixin (Please read the notes on the back before filling out this ) Packing. The Central Government Bureau of Standards, Ministry of Economic Affairs, Employees ’Cooperatives’ Seal of Inclusion 0 includes the legal items in the packaged rubber protection insurance 11 'Art. Ethyl propionate hydroxyl, Ethyl vitamin B fiber base cellulose methyl, Ethyl hydroxyl vitamin, 0 Ethyl vinyl acetate fiber carboxyl ethyl 7 M0 self-limiting parts and sodium acid acid allene derived acrylic powder polymer 0, acid-based allyl propylene glycol, Λ-ol alcohol, vinyl ethyl ethyl propylene, hydroxylysis, water ether mecotin and anhydride to 1-ether allyl ethyl methyl / IV polyamine 0 allyl polymer, salt 0 The standard of Austin and other papers is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 473480 A8 B8 C8 D8 6. Application scope of patent, polyvinyl 4-pyrrolidine, water-soluble starch glue, gelatin, water-soluble Alginate, casein, agar, and Wuran and synthetic gum. (Please read the back " Note before filling in 7. If the method of applying for the scope of the first patent application, the upper limit of the molecular M of the protective colloid is 50,000. 8. If the method of applying for the scope of the patent, the first aspect, the molecular scenery of the protective colloid The upper limit is 20,000. 9. The production method according to item 1 of the patent application range, wherein the protective colloid includes cellulose ether, which is selected from the group consisting of hydroxyethyl cellulose, hydroxyethyl cellulose acetate, and carboxymethyl fiber with a lower limit of 0.7. , Methyl oryzanol, hydroxypropyl fervidin methyl ether, and hydroxypropyl cellulose. 10. 10. The method according to item 9 of the patent application scope, wherein the cellulose ether includes a degree of substitution of a carboxyl group of 0.7 to Carboxymethylcellulose of 2.9. 1 1. The production method according to item 10 of the patent application scope, wherein the cellulose acid includes hydroxyethylcellulose with an upper limit of 4.0 for substitution. 1 2. The manufacturing method of item 11 in the scope of patent application, in which the lower limit of hydroxyethylcellulose of hydroxyethylcellulose is replaced by 1.6. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 13. , Where the protective colloid includes hydrophobically modified fibers Vitamins_, Hydrophobic substances are C +-25 hydrocarbons, the scene of which is 0.1% to 3% of the weight of the hydrophobically modified euvitamin ether. 1 4. According to the production method of item 13 in the scope of patent application, where The hydrophobically modified cellulose ether includes hydrophobically modified hydroxyethyl cellulose. 15. The production method according to item 14 of the scope of patent application, wherein the upper limit of the hydroxyethyl moryl substitution of the hydrophobically modified hydroxyethyl cellulose is 4.0. -3- This paper size applies to Chinese National Standards (CNS) (210 × 297 mm) 80 34 7 A8 B8 C8 D8 Employees of the Central Bureau of Standards, Ministry of Economic Affairs, printed by cooperatives. 6. Scope of patent application '1 • 1 | 1 6. Rushen »;. <-Patent Fanpu y 15 Production Method t where the hydrophobically modified hydroxy 1 1 1 ethyl methanedin has a lower limit of hydroxyethyl moryl substitution 2. 9 Ο 1 1 1 * 17, as in y .: i: Patent m, Λ · — 1 m cracking method J, even if there is an initiator, please read -r first, including the choice of g of water-soluble supergas, persulfate and perylene. Acid 1 Read back 1 side μ "" 1! 1 8. For example, in the method of claim 17 of the patent scope of δ month, the initiator includes the selection of ψ 1, and item 1 is filled with potassium persulfate and ammonium hydrogen persulfate and sodium perborate. IS 1 9. If the master of the string seven: Ming patent en be—the method of producing item 1 of the formula j where the polymerization is based on the total amount of initiator 1 and 0% to 60¾ of initiator 1 and the amount of 0% to 4 0¾ at least--species Ethylene 1 Unsaturation σο Carbohydrate 1 Add j at the beginning of the reaction, and proceed according to the semi-continuous formula 1 and formula I. 〇20. For example, the application method of the patent A-Λ ^ w around item 1 wherein the polymerization is continuous 1. i way to perform 〇1 1 2 1. If the patent application w encircle 1 production method wherein the polymerization is carried out in the factory back 1 line J reactor 〇22. — a kind of flocculation due to grafting. Its improvements include 1 an aqueous emulsion ： 1 1 (a) At least-one kind of ethylene 糸 unsaturated αο polymer of early body 1 単 1 1 § § acrylic methacrylic acid butyl acrylate methacrylic acid i methyl ester N acrylate styrene vinyl ethers, vinyl halide \ #-Halovinylene, N-vinyl B than pyrrolidone ethylene C3 or more α-olefins, allylamines, allyl-4 of saturated monocarboxylic acids-this paper is suitable for t countries Ladder (CNS) A4 (210X297 mm) 473480 8 8 8 8 ABCD Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 6. Application for patents Esters and their cool amines, propylene, 1-butene, 1-pentene,]-hexene, 1-decene, allyl acetate, allyl propionate, allyl lactate, and their limbs, and mixtures thereof; and (b) latex strips are stable and effective t is a water-soluble protective colloid with a molecular weight of 75,000 or less, and is selected from the group consisting of fluorenylmethyl azorvin and its derivative with a lower limit of carboxy substitution of 0.7, hydroxyethyl cellulose, hydroxyethyl woven Retinyl ether, methyl cellulose, hydroxypropyl cellulose methyl ether, hydroxypropyl cellulose, polyacrylic acid and alkali metal salts thereof, ethoxylated starch derivatives, sodium polyacrylate ester and other alkali metals Salt, water-soluble starch gelatin, gelatin, water-soluble alginate, casein, agar, natural and synthetic gums, partially and fully hydrolyzed polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidine, and poly ( Methyl vinyl ether-maleic anhydride). 2 3. The latex system according to item 22 of the patent application, wherein the polymer is polymerized in the presence of a water-soluble protective colloid by an aqueous emulsion polymerization method. 24. For example, the latex system of item 22 of the scope of patent application, which also includes a surfactant, is 0.1 to 4.0% by weight of the total content of the unsaturated monomer in the ethylene strip. 25. The latex system according to item 22 of the patent application scope, wherein the molecular limit of the protective colloid is 50,000. 26. The latex system according to claim 22, wherein the polymer includes a discontinuous phase and is characterized by an average particle size of less than 300 n in. -5-丨 丨 /.lt— — Li (please read the precautions on the back before filling this page) ----- Order— --Line--%! This paper standard uses China National Standards (CNS) A4 specifications (210X297 mm) 473480 Λ8 B8 •, C8 D8 VI. Patent application scope 2J The latex paint composition made by the latex system of patent application No. 22, including: U) selected from the group consisting of pigments and supplements At least one of the agents; and (b) 5-7 0 ^ 11 Compared to the item 7 of the latex latex of the application for the Lifanpu, the item becomes the lacquer latex 7 2 " ^ Wai 0 Shenru δ 2 combined with 'α Ha, its content becomes a new compound ¾ latex item 7 2 Range 0 0 Dissolve the special agent, please include the application is not as good as the content of the paint 0 granule group under the paint with latex S C3- -: I. 0 item 0 7 5 2 In the first round of the grain Fan Junliping, please include the application material as the paint in the 0 group, paint with 0 L 5 Fu Fu in the degree of concentration 2 product volume Fan Yanli Λ special paint, please apply as bright as possible. 0 * The upper system is ¾ or glue 0 L 5? ί 2 Concentration 2 Jierongrong Fan Yanli, Special paint If Shen Ping, like other things, less α, to the composition and material can be painted, its paper and ink-formation system 糸 a · water glue s iu S " § $ Forms and items are grouped together. OJ Groups of the composition of the surrounding ingredients. Fan Niuchengli Material and ink special for oiling, please apply for paper types. As the central government bureau of the Ministry of Economic Affairs, the consumer co-operative society prints one. As little as possible, the essence and the paste can not be formed, and the form of a glue group. U ΠΡ Ψ ΨT is 2 2 away from the sect of the encircling sticky fan's essence. Μ can be a rule of latex item 2 2 Scope of profitable composition, please apply the application agent such as the grouping agent to stick together 缁 TT > s forming the M group phase separation agent to stick to other materials. Standards apply to China National Standards (CNS) A4 specifications (210 × 297 mm)