JPH01500438A - A method for agglomerating latex, the resulting agglomerated latex, and the application of the latex to modify the thermoplastic matrix to impart impact resistance. - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Latex agglomeration method, modification of the obtained agglomerated latex and thermoplastic matrix Application of the latte to provide impact resistance The present invention is based on a polymer selected from elastomers and thermoplastics. A method for agglomerating latex with a base material, a latex obtained by this method, and an impact Application of said latex to modification of hard thermoplastic matrix to improve impact strength. It is related to For example, polybutadiene-based latex can be It can be applied to the production of ronitrile-butadiene-styrene (ABS) resin, and Acrylic latex or SBR latex with methyl methacrylate and styrene It can be applied to strengthen the base material, or multilayer acrylic latex can be used to strengthen the base material. Applications include strengthening styrene base materials.

The above latex is made using water as a medium with various additives such as emulsifiers and stabilizers added. most commonly obtained directly by emulsion polymerization. It is publicly known that The purpose of coagulating latex is to create such an emulsion. The aim is to increase the particle size of the polymer particles therein.

For example, if the monomer reaction rate is slow, energy and time losses can be eliminated. In order to increase the polymerization rate to produce small particles with a particle size of less than 200 nm, this is then to agglomerate the particles to a medium size and finally obtain particles of the desired size. C is particularly advantageous in industrial production.

That is, in order to obtain an ABS resin with excellent impact strength, the particle size force should be 300 to 700. It is necessary to use a latex based on polybutadiene. but, In traditional methods for emulsion polymerization of butadiene, the particle size is reduced at a rate of 10 nm per hour. First, the particle size of the polymer particles becomes small through polymerization. (approximately 80 to 200 nm) latex is made and then agglomerated. There is.

All known latex agglomeration methods involve the production of latex containing fine polymer particles. From a stable state, rough polymers are – Based on the principle of transitioning the latex containing particles to another stable state. and, in some cases, post-stabilization of the latex to its final stable state. Sometimes.

The flocculation methods that have been proposed so far are ones that do not use chemical agents, as shown below. It can be roughly divided into two types: those that use chemical agents, and those that use chemical agents.

Examples of the former include methods using cooling and methods that create a pressure gradient. Such a method does not contaminate the latex and therefore the obtained latex Processing (e.g., graph for producing ABS from polybutadiene latex) It does not interfere with the process (conversion) or impair the properties of the resulting product.

In the latter method, as a chemical agent or solvent, it exerts a destabilizing and swelling effect. benzene, toluene, acetone and benzene-alcohol type mixtures, Electrolytes such as salts or acids that partially destroy the protective effect of emulsifiers, or are polyvinyl alcohol, polyvinyl methyl ether, polyoxyethylene, Acrylic polymer electrolyte, polyurethane, polyethylene glycol [carbamat CARBAMAX 20M], carboxymethylcellulose and polyester A hydrophilic polymer such as vinyl acetal is used.

However, all of these conventional methods have the following problems. i.e. , - Significant consumption of energy; - formation of significant amounts of coagulum; - Particle size of agglomerated particles is limited and often too small; - Agglomeration is dependent on temperature and time. - It is difficult to control the particle size distribution of agglomerated particles, and it is difficult to reproduce. etc.

In order to solve the above problems, European Patent No. 29.613 A latex agglomeration method based on sticky polymers has been proposed, and this method is the latex to be agglomerated (latex to be agglomerated), (1) Unlike the polymer contained in the coagulated latex, it has lower lipophilicity. A polymer comprising: (a) a C, to C12 alkyl acrylate and methacrylate; a homopolymer of an alkyl acid, and (b) a homopolymer that is insoluble in water. Polymer selected from copolymers of ethylenically unsaturated monomers that can be formed and, (2) Obtained by adding ethylene oxide to an organic compound having a reactive hydrogen atom in its molecule. A nonionic surfactant consisting of a product that (referred to as flocculating latex).

However, the above method also had some problems and limitations.

First, in the above method, the polymer in the latex to be agglomerated is The main latex to be flocculated must be different from the polymer in the If the latex is polybutadiene, use polybutadiene as the coagulating latex. Tex cannot be used.

Second, a flocculating surfactant is adsorbed onto the initial latex to form a flocculating latex. Upon synthesis, anionic surfactant effects occur in the initial latex. This results in The particle size of the flocculated latex decreases and enters a pre-flocculation state, causing the flocculation latex to precipitate. happens.

Third, such a method always yields a particle group with a bimodal distribution. .

The inventors of the present invention have discovered that instead of the surfactant (2) in the flocculating latex, a small amount of At least one polyethylene repeating unit and vinyl, diene, or acrylic varnish. containing repeating units of at least one polymer based on methacrylic esters and methacrylic esters. and in the presence of this multicomponent repeating unit polymer. The problems of conventional methods can be solved by producing latex for aggregation. I found out. That is, - First, the latex to be agglomerated and the latex for agglomeration are the same. In general, the agglomerated polymer can be extended to thermoplastic polymers. can. In addition, the European patent, which can only be used for rubber-based coagulated polymers, As in the method described in No. 29.613, a temperature higher than the glass transition temperature of the polymer to be aggregated is There is no need to perform agglomeration at temperature.

-Secondly, agglomerated particles with a large particle size can be easily produced, -Thirdly, the choice between a unimodal or bimodal distribution depends on the final latent Coagulation in 100 g of final latex for amount of coagulated polymer in 100 g of latex This can be done by adjusting the ratio to the amount of polymer used (this point was completely unexpected in the present invention).

Furthermore, by using a copolymer having the aforementioned multicomponent repeating units, the following There are also additional benefits such as: That is, - Can be carried out over a wide range of temperatures and can be used for both coagulation and coagulation latex. The amount of dry extraction can be selected from a wide range. In particular, dry extraction in latex for flocculation It is possible to work with much smaller quantities than with conventional methods.

- The particles can be agglomerated 100%.

That is, the object of the present invention is a material selected from elastomers and thermoplastics. In a method for agglomerating latex of a coagulated polymer, the latex to be agglomerated and , (A) a polymer selected from elastomers and thermoplastic resins; (B) At least one polyethylene repeating unit and a vinyl polymer, diene polymers, acrylic ester polymers and methacrylic ester polymers repeating unit of at least one polymer selected from a nonionic surfactant consisting of a mixing with a flocculating latex constituted by, and The above-mentioned coagulation latex uses the above-mentioned (A) as a surfactant while using the above-mentioned (B) as a surfactant. , ) is obtained by synthesizing the polymer defined in be.

As the polymer for the above-mentioned latex to be agglomerated and latex for agglomeration, butyl ene, isoprene, styrene, α-methylstyrene, vinyltoluene, acrylic Nitrile homopolymers and copolymers; alkyl groups having 1 to 12 carbon atoms Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid and List homopolymers and copolymers of each alkyl ester of itaconic acid The latex to be agglomerated is SBR latex or “core”. Multilayer (2 or 3 layer) acrylic latex with a structure called “shell” You can also use

The nonionic surfactant (B) is made from a polymer having three repeating units. It is preferable to select a polyoxyethylene repeating unit at both ends. Preferably, it is made of a polymer having Also, a polyester with two repeating units It is also possible to use nonionic surfactants (B) consisting of mer.

Polymers having repeating units other than polyoxyethylene repeating units include Select a polymer consisting of polystyrene. Therefore, polyoxyethylene Three types of listyrene-polyoxyethylene (hereinafter referred to as POE-PS-POE) Mention may be made of surfactants (B) consisting of copolymers with repeating units. .

Furthermore, it is desirable that the surfactant (B) has the following characteristics. - Number average molecular weight is 1000 to 1.000.000.

- polyoxyethylene content from 5 to 95% by weight.

The surfactant (B) used in the method according to the invention is generally in an anionic state. This has the advantage that an almost pure product is obtained. POE- When producing PS-POE copolymers, the repeating unit PS is heated to a temperature of -80°C. In tetrahydrofuran, the “tetramer of α-methylstyrene” type bifunctional made with a functional initiator and then the repeating unit POE is polymerized at a temperature of 30°C.

According to a preferred embodiment of the present invention, the latex to be agglomerated is potassium laurate. and anionic surfactants such as sodium dodecyl sulfate (SDS) and persulfuric acid. Free radical initiators such as potassium and linked compounds such as tertiary dodecyl mercaptan Latex produced by emulsion polymerization at temperatures between 40 and 90°C in the presence of a chain transfer agent Use The particle size of the polymer in the coagulated latex is between 50 and 300 nm. The solid content of the latex is preferably 5 to 50% by weight.

Similarly, the particle size of the polymer (A> is 60 to 500 nm, and the solid content ratio is 1 to 40 nm. Particularly used is a coagulating latex that is % by weight.

In the present invention, the flocculating latex is emulsified in the presence of a nonionic surfactant (B). It is therefore possible to obtain it directly. Also, this polymerization is It is carried out in the presence of a free radical initiator such as potassium sulfate. Third dodecylme It turns out that the presence of chain transfer agents like lucaptan is indeed essential. ing. This migration agent limits the chain length and also acts as an initiator in the organic phase. do. Furthermore, it acts as a co-surfactant and significantly reduces the particle-solvent interfacial tension. Reduce the particle size by adding alcohol such as methanol to the mixture. It is also possible to adjust the particle size of the latex by adding it to for this same purpose Other surfactants can also be used, such as sodium lauryl sulfate. This polymerization is carried out batchwise or semi-continuously at a temperature of about 40-90°C (e.g. 70°C).

The resulting conversion rate is very high and can reach 100%.

The particle size of the polymer in the flocculation latex depends on the monomers used (and therefore the acrylic). When using butyl sulfate, the particle size is smaller than when using butadiene or styrene. ), the concentration of the alcohol acting as a co-surfactant (as described above), and the (The particle size of semi-continuous methods is much lower than that of batch methods. In addition, the copolymer (B), as a co-surfactant, As the alcohol and initiator concentrations increase, the particle size decreases, while the copolymer decreases in size. As the molecular weight Mn of (B) increases, the particle size increases.

Coagulation can be carried out by adding a coagulating latex to the latex to be coagulated, or by adding a coagulating latex to the latex to be coagulated. This can be done by adding latex to be agglomerated to latex. In fact, agglomeration Unless there are special circumstances, the mixing methods used for It has been found that it has little effect on the diameter. Generally, agglomeration latte Latex (in principle, the volume is very small) is mixed with the latex to be agglomerated (in principle, the volume is very small). It is preferable to follow the former method, as it is easier to add the

Mixing for flocculation according to the invention is generally carried out at 10°C to 10°C for a period of 1 minute to 48 hours. It can be carried out at a temperature of 0°C.

According to the invention, a small amount of at least 0.05 parts by weight of solid polymer (A) and at least 0.0001 parts by weight A predetermined amount of coagulating latex consisting of part surfactant (B) is introduced. In particular, 0.05 to 20 parts by weight per 100 parts by weight of polymer present in the agglomerated latex of solid polymer (A) and 0.0001 to 0.2 parts by weight of surfactant. Introduce an amount of flocculating latex. However, the above amounts are by no means limiting. Please note that.

Particularly noteworthy of this invention is that the flocculating polymer in 100 g of final latex The curve representing the particle size of the particles after agglomeration as a function of the ratio between the amount of and the amount of polymer to be agglomerated is Generally passes through a maximum value, and is obtained depending on whether the ratio R is smaller or larger than this maximum value. It has been clarified that the particle groups generated can be divided into bimodal distribution type and single mode distribution type. ing. In this regard, the method described in the aforementioned European Patent No. 29.613 A very interesting observation has been made by comparing the aggregates obtained in .

The morphology of the aggregated particles is generally spherical, and the surface of the particles is smooth. moreover , the obtained agglomerated particles were heated (freeze-thaw cycle), ultrasonic waves, and latex for agglomeration. Stable to post-addition and shear stress.

In this way, it was possible to obtain agglomerated particles having a particle size of up to 1700 nm.

The present invention further provides an agglomerated latex obtained by the above method and improved impact strength. The present invention relates to the application of this latex to the modification of thermoplastic matrix materials in order to improve the properties of the latex. child These base materials are particularly suitable for alkaline methacrylates in which the alkyl group has 1 to 4 carbon atoms. styrene, substituted styrene, acrylonitrile, methacrylonitrile Rigid thermoplastic polymer obtained from at least one kind of polymer selected from -, or at least 50% by weight of at least one of these monomers and at least one other unsaturated polymer copolymerizable with the polymer. Consists of. Specific examples of applications of the present invention are given at the beginning of this specification. There are some things I have already mentioned. The manufacturing method of the reinforced base material as described above is known to those skilled in the art. This is the traditional method of knowledge. Generally, flocculation particles are coated and then flocculated. washed, dried and dispersed in the matrix in the next step. The method according to the invention Examples of various latex agglomeration methods based on However, the present invention is not limited thereto. In addition, used in the following examples Among latex, those indicated by LPB, LS, , LPBA and LSBR are , polybutadiene, polystyrene, poly(butyl acrylate) and butyl acrylate, respectively. LPBCop , LPSCop, LPBACop and LPBA-3Cop are: Polybutadiene, polystyrene, poly(butyl acrylate) and aluminum respectively. Cop represents a coagulating latex of butyl acrylate-styrene copolymer; Represents a copolymer with three repeating units of OE-PS-POE, which is a non-isolated On-based surfactants, in the presence of which flocculating latexes are produced. Also, below The percentages given in the examples below are by weight.

After starting the stirring gradually to a speed of 500 revolutions/min, 0 g of water, 6.3 g of lauric acid pre-dissolved in 200 g of water, and 1.75 g of potassium hydroxide, and 2.10 g of tertiary dodecyl mercaptan (TDM). 1.40 g of potassium hydroxide dissolved in 50 g of water was charged in sequence, and 500 g of water was added. Rinse. The reaction was carried out by creating a vacuum in the reactor and introducing nitrogen at a pressure of 3 bar. Remove oxygen from the reactor. Heat to 70°C.

2.8 g of potassium persulfate, pre-dissolved in 100 g of water, is passed through a mouth strainer with nitrogen. Add by pressure and rinse with 50 g of water.

Thus, by varying the pressure, the polybutadiene latex LPB1~L PB6 was obtained. The characteristics of each latex are shown in Table 2 below.

(2) Production of latex to be agglomerated other than the above Stirring and nitrogen reflux at a constant temperature of 70℃ Water, the above-mentioned surfactant and IJ hydroxide are charged downstream. surfactant After the agent is completely dissolved, the monomer-TDM mixture is added. After 10 minutes, temperature is brought back to a constant level and potassium persulfate, previously dissolved in water, is added.

Following the general operating method above, each latex as shown in Table 1 below was produced. Ta. The characteristics of each latex are shown in Table 2 below.

(3) Characteristics of the agglomerated latex produced by (1) and (2) *Strength latex cross-linked to ** is a surfactant consisting of a latexmer that is hardly cross-linked. The characteristics of these surfactants are shown in Table 3 below.

M number average molecular weight (2) 70°C by bifurcation or water bath for producing latex for flocculation by batch method. Water, surfactants Cop and and methanol are introduced; residual air is removed by continuous nitrogen gas blowing.

Stirring is carried out at a constant speed of 250 revolutions/min. The surfactant Cop is completely dissolved and heated After the temperature reaches 70° C., the monomer mixture-TDk is added. After 10 minutes, check the temperature The reaction was brought to a constant level and the reaction was started by adding potassium persulfate dissolved in 15 g of water. Let it start.

First, perform the same operation as the method shown in (2). However, 30 tons of monomer mixture - Add the TDM and after 5 minutes add all the pre-soaked initiator. next , polymerization is carried out until the conversion is less than 100%, forming a "core" of latex. So Afterwards, the remaining 70% of the monomer mixture - TDM was charged at a rate of 0.3 mA/min (continuously Add to.

(4) Production of other latex for aggregation Various latexes were prepared according to the general operating method described above. Table 4 shows each latte. The characteristics of cous were shown.

■-Agglomeration method (1) General operating method Agglomerating lattices with different concentrations are added to various latexes to be agglomerated while mechanically stirring. Add the mixture in various proportions using a billet. Unless otherwise specified, The initial mass of the agglomerated latex was kept constant at 30 g. During the addition of latex for flocculation, Maintain slow stirring with a magnetic bar. This agitation will cause the latex to coagulate. The addition continues for a few minutes and then stops.

(2) Selected concentration unit In the following, R is relative to the mass of polymer to be agglomerated in 100 g of final latex. The ratio of the mass of coagulating polymer in 100 g of final latex is shown.

m+ = mass of polymer for aggregation xl = Solid content ratio of latex for flocculation m2 = mass of polymer to be aggregated X2 = Solid content ratio of latex to be agglomerated holds true.

Let C be the final dry extraction amount expressed as the total mass of polymer in 100 g of latex. and, holds true.

[Cop] is the amount of FOE added to 100 g of dry extracted latex to be coagulated. - Surfactant quality consisting of a copolymer with three repeating units of PS-POE It's the amount. Further, the ratio 1=Ds. /D. defined. Here, Dso and Dl.

denote the cumulative diameters that constitute 90% and 10% by volume of the particles, respectively.

Latex to be agglomerated by polybutadiene using latex for aggregation of lyle-based copolymer: LP BA, (φ=104 nm; x2=32.2%) Latex for 'u'J: LPBACop4a (φ-135nm; x+=4.5 2%) Table 5 *Agglomeration temperature: 17℃ **tt: 25℃ VB = very large In Experiment 1, the latex for agglomeration was added to the latex to be agglomerated, and in Experiment 2, the latex to be agglomerated was added to the latex to be agglomerated. The latex was added to the flocculating latex.

The mixing method used for agglomeration has a particular influence here on the particle size of the agglomerated particles. I found out that it wasn't.

et al.) Effect of time on agglomeration methods Latex to be agglomerated: LPB3 (x-=31.0%) Latex for aggregation: LPBACop3 Table 6 *Final dry extract: c=28.40**”: c=28.61 Time 1 = 0, that is, the point at which aggregation starts is when the aggregation latex is added to the polybutadiene latex. The time was determined at the end of the addition of the mixture.

This type of latex agglomeration can achieve final particle size in a few minutes to about an hour, depending on the system. It's fast because you can

Latex to be aggregated: LPB5 Latex for coagulation: LPBACop4a Coagulation temperature: 25°C Table 7 Latex to be aggregated: LPB3 (x2=31%) Latex for aggregation: LP BACop3 agglomeration temperature: 17℃ Table 8 Latex to be aggregated: LPB4 or LPB5 Latex for aggregation: LPBC op4a (xt = 4.5%) Coagulation temperature: 25℃ 4-Consideration The particle size of the agglomerated particles is highly dependent on the agglomeration time, R and C.

In all cases, the higher the C, the shorter the aggregation time, which is almost instantaneous.

(d) Temperature effect Latex to be aggregated: LP B3 (X2 = 31.0%) RX 10”+2 =3.10 C (g/100 g) = 26.63 As the agglomeration temperature increases, the agglomerated particles The particle size becomes considerably smaller. In fact, when the agglomeration temperature T = 17°C, the maximum particle size is 480 nm, but when T=65°C, it is only 300 nm. On the other hand, if the particle size is 30 When it reaches 0 nm, stop heating and lower the agglomeration temperature T to <11°C as quickly as possible. If this is maintained, aggregation continues further and reaches a final particle size of 490 nm. This value is , close to the particle size obtained by agglomeration at low temperatures (T=17°C).

(e) Functional agglomeration temperature depending on the characteristics of the latex for aggregation: 17°C Agglomeration time: 24h 2-The molecular weight of the repeating unit POE is polybutadiene latex FBI (x2=30 ．． 6%; φ-203nm) agglomeration temperature = 17℃ Agglomeration time: 24h 3-POE-PS-POE copolymerized latex with 3 repeating units: LPB4 (x2=32.2%; φ=104nm) Coagulation temperature = 17℃ Agglomeration time = 24h Table 13 VB = very large Particle size due to agglomeration has three repeating units used: POE-PS-POE It is recognized that it varies depending on the type and concentration of surfactant. Repeat unit PO It can be seen that as the Mn of E increases, the particle size of the agglomerated particles also increases.

4- Influence of particle size of latex for coagulation Latex for coagulation: LPBACop4b (φ=197nm) Coagulation temperature: 17℃ Agglomeration time: 24h The particle size of the agglomerated particles is largely related to the particle size of the agglomerating latex. aggregated This effect is small for particles with a small particle size, but when the particle size is large, it is extremely becomes important.

(4) Pig for agglomeration of copolymers with three repeating units POE-PS-POE Polybutadiene agglomerated latex by Genlatex: LPB5 (φ-10 00nm; X2=32.3%) Latex for aggregation: LPBcop5 (φ-225nm; x, = 2.5%) Latex for aggregation: LPBCop6 (φ=277nm; X2=3.6%) Coagulation temperature = 25℃ et al.) Effect of polybutadiene particle size Latex to be aggregated: LPB5 (φ = 100 nm + X2 = 32.3%) Latex to be aggregated: LPB2 (φ-181nm; X2=30.7%) Latex for coagulation: LPBCop5 (φ = 225 nm; X, = 2.5% ) Coagulation temperature = 25℃ From the obtained results, the U collection using the above latex is a method of mixing two latexes. method (the method of adding the latex to be agglomerated to the latex for coagulation must be selected) ), concentration of surfactant, initial particle size of polybutadiene latex, It is recognized that the molecular weight of the repeating unit POE varies depending on the particle size of the coagulating latex. I can't stand it.

Latex to be aggregated: LPBA1 (φ = 139 nm; X, = 23.1%) Latex for aggregation: LPBACop4a (φ = 135 nm; X, = 4.5%) Coagulation temperature: 25℃ *LPBAI prepared in the presence of potassium laurate as a surfactant Coagulation of polybutadiene latex Latex to be aggregated: LPB4 (φ-104nm; X2=32.2% ) Latex for coagulation: LPBA-3Cop6 (φ-138nm; X, = 4.68%) Coagulation temperature = 25℃ Agglomeration time: 24h -Poly(butyl acrylate) latex with butadiene-based coagulation latex agglomeration of Latex to be aggregated: LPBA1 (φ=139nm; X2=33.1%) Or LPBA2 (φ=125nm; X2=32.9%) Latex for aggregation: LPBCop5 (φ-225nm; X, = 2.5%) Coagulation temperature: 25℃ Agglomeration time: 48h Table 19 *LPBAI: Surfactant: Potassium laurate **LPBA2: Surfactant agent: 5DSVB = very large The present invention will be explained in more detail with reference to the following examples.

In order to produce latex for agglomeration, two types of 3 types having the characteristics shown in Table 21 A polymer having two repeating units POE-PS-POE was used.

*Measured by gel permeation chromatography: ＊＊＊＊Ethylene is 258 Based on the fact that it does not absorb at nm wavelengths and only PS units are detectable, Measured by ultraviolet light method.

A series of latex LPBACop for flocculation is manufactured according to the following general operating method: did.

(In a reactor with a capacity of 21% by weight of water and as shown in Table 22 below) methanol and 23% by weight of butyl acrylate for this monomer. 6% by weight of a polymer with 3 repeating units and 0.6% by weight of TDM. I entered.

Heat to 70° C. while stirring at 250 rpm. The temperature reached 70℃ Then, 0.15% by weight of K2520a was added to the above monomer. When compositing The duration will be 4 hours. ) According to the above operating method, various types as shown in Table 22 below. latex LPBACop was manufactured. The characteristics of these latexes are shown in the same table. vinegar.

Table 22 also shows the characteristics of polystyrene latex produced in batch mode. child The latex was prepared using raw materials (91% water + Cop 8.9% by weight % styrene and 1 wt. % TDM) and a stirring speed of 200 revolutions/min. After heating to 90°C while holding, potassium persulfate was added and heated for 3 hours. It can be obtained by performing the synthesis using

The characteristics of the latex to be agglomerated used in the above series of Examples are shown in Table 23 below.

*Latex containing 10-2 moles of SDS per 100g of latex **Synthesized with SDS, a surfactant.

To perform agglomeration, the latex to be agglomerated is added with the surfactant SDS, if necessary. Add the flocculating latex in batch mode with mechanical stirring. temperature, coagulation time, as well as the total particle size (measured with a turbidimeter) of the agglomerated particles, which affects the growth of the particles. The parameters were investigated.

(a) Effect of aggregation time Latex to be aggregated: LPB6 Latex for coagulation: LPBACop9a Simulation conditions: Temperature: 20°C; R = 2 After agglomeration for 2 hours, the particle size stabilized.

Latex to be aggregated: LPB8 Latex for coagulation: LPBACop8a Operating conditions: Temperature 20°C; R=2X1 0-'; pH=i2 Table 25 Latex to be aggregated: LPB8 Latex for coagulation: LPBACop8a Operating conditions: Temperature 20°C; Time 24h; pH-12 Latex to be aggregated: LPB8 Operating conditions: temperature 20℃; : Time 24h; pH=8 Table 27 *Addition of 1.5 Xl0-' mol of SDS per 100 g of latex to be agglomerated Effect of molecular weight of POE unit of mer Latex to be aggregated: LPB8 + 1.5 Xl0-' per 100g of latex Mole SDS Operating conditions: temperature 20℃; Time 24 hours (d) Influenced by the characteristics of the latex to be agglomerated: Latex to be agglomerated: LPB8 Latex for coagulation: LPBACop8a Operating conditions: Temperature 20°C; Time 24 hours 2- Influence of coating ratio of latex to be agglomerated Coagulation latex: LPBCop8 a Operating conditions: temperature 20℃; Time 24 hours Latex with a smaller coverage ratio has greater aggregation.

(a) Other agglomerations Operating conditions: temperature 20C; Time 24 hours Table 31 *104 moles of SDS per 100 g of latex was added to the flocculating latex. thing.

The accompanying drawings illustrate the noteworthy aspects of the method according to the invention as described above. This is it Then, the curve representing the particle size of the aggregated particles varying with R passes through the maximum point, and R The particle group is divided into two models depending on whether it is smaller or larger than the value corresponding to this maximum point. mode distribution or unimodal distribution.

Figure 1 of the accompanying drawings shows the curve φ(nm)-F(RxlO'') corresponding to Experiment 1. vinegar. The particle morphology of the agglomeration latex was examined using a transmission electron microscope for five R values. It was measured. The five photographs corresponding to this are Figures 2 to 6, and the upper part of each figure The value of R corresponding to is shown. The magnification is 10.000. Figures 2 and 3 Since R is smaller than the maximum value, a bimodal distribution of particles is recognized, and the 4th to 6th particles In the figure, since R is larger than the maximum value, particles with a single mode distribution are recognized.

'E'XG, 2 Rm '0,46 x 102F engineering G, 3 R-0,92 x 1o2r engineering G, 4 R-1, 41x 102FIG, S FIG, 6 international search report ANNEX To’Lr, E INTERNAT 0 NAL 5 EARCHR EPORT　uNINTERNATIONAL　APPLICATION　No. , i’cT/TR87100210 (SA 17455)

Claims (12)

[Claims] (1) Lattes of polymers selected from elastomers and thermoplastics. In the method of coagulating latex, the latex to be agglomerated; (A) a polymer selected from elastomers and thermoplastic resins; (B) at least one polyethylene repeating unit, a vinyl polymer, a diene type polymers, acrylic ester polymers, and methacrylic polymers. at least one repeating unit of the selected polymer. A nonionic surfactant consisting of to do, and The above-mentioned coagulating latex is prepared by using the above-mentioned (A) using the above-mentioned (B) as a surfactant. A method characterized in that the method is obtained by synthesizing a defined polymer. (2) The polymer of the latex to be agglomerated and the latex for aggregation is Ene, isoprene, styrene, α-methylstyrene, vinyltoluene, acrylic Nitrile homopolymers and copolymers; alkyl groups having 1 to 12 carbon atoms Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, italic acid with selected from homopolymers and copolymers of each alkyl ester of conic acid. , the latex to be agglomerated may be SBR latex or multilayer acrylic latex. The method according to claim 1, characterized in that: (3) A polymer having three repeating units, more preferably polyoxygenated at both ends. Select a nonionic surfactant (B) consisting of a polymer with ethylene units 3. A method according to any one of claims 1 and 2, characterized in that: (4) Repeating units other than the above polyoxyethylene units are composed of polystyrene. The person according to any one of claims 1 to 3, characterized in that the polymer selected is Law. (5) A surfactant with a number average molecular weight between 1,000 and 1,000,000 ( 5. The method according to claim 1, characterized in that B) is used. (6) Using a surfactant (B) containing 5 to 95% by weight of polyoxyethylene The method according to any one of claims 1 to 5, characterized in that: (7) Emulsion polymerization in the presence of an anionic surfactant as the above-mentioned latex to be aggregated The particle size of the polymer in the latex is 50 to 3. 00nm, and the solid content ratio of the latex is 5 to 50% by weight. The method according to any one of claims 1 to 6. (8) As the agglomerating latex, the particle size of the polymer (A) is 60 to 500 nm. It is characterized by using a flocculating latex with a solid content ratio of 1 to 40% by weight. 8. The method according to any one of claims 1 to 7. (9) A claim characterized in that the mixing time for the aggregation is 1 minute to 48 hours. 9. The method according to any one of claims 1 to 8. (10) The above mixing for aggregation is performed at a temperature of 10 to 100°C. 10. The method according to claim 1, wherein: (11) Agglomerated latte obtained by the method according to any one of claims 1 to 10. x. (12) Alkyl methacrylate, styrene, in which the alkyl group contains 1 to 4 carbon atoms Select from a rigid thermoplastic polymer consisting of at least one monomer containing Copolymerizable with 50% by weight of at least one of these monomers and at least one other monoethylenically unsaturated monomer. Agglomerated according to claim 11 for a rigid thermoplastic matrix that increases the impact strength produced. An application characterized by the use of latex.