JPH0689084B2 - Emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention provides a film-forming property and rigidity obtained by seed-polymerizing an ethylene / vinyl chloride / vinyl ester copolymer emulsion with a styrene monomer. And an emulsion composition having characteristics of flame retardancy. The emulsion obtained by the present invention can be used in a wide range of application fields of emulsions such as a hard type fiber processing agent represented by a carpet backing agent, a non-woven fabric binder and the like, a paper processing agent, an adhesive and a paint.

<Prior art> Conventionally, vinyl chloride copolymer emulsions represented by ethylene / vinyl chloride copolymers and ethylene / vinyl chloride / vinyl ester copolymer emulsions are flame retardant as the vinyl chloride content increases. It is known that the hardness and rigidity are improved.

For example, Japanese Examined Patent Publication (Kokoku) No. 58-31432 proposes a method of shaping a rug using a vinyl chloride / vinyl acetate / ethylene (30 to 75/10 to 35/5 to 30% by weight each) copolymer. .

Further, JP-A-55-40844 discloses a flame-retardant backing composition for rugs, which comprises a combination of a vinyl chloride / vinyl acetate / ethylene terpolymer and a flame retardant.

In addition, JP-A-57-73037, JP-A-58-41972, JP-A-58-104935, JP-A-58-152037, and JP-A-58-1646.
No. 31 and the like also show that the ethylene / vinyl chloride / vinyl acetate copolymer emulsion is suitable as a shaped rug or a flame-retardant backing agent for rugs.

In addition, various proposals have been made for so-called seed polymerization in which a monomer, a catalyst and the like are additionally added and polymerized in the presence of a synthetic resin emulsion.

For example, Japanese Examined Patent Publication No. 54-44034 discloses an aqueous emulsion obtained by emulsion polymerization of a simple substance mixture of ethylene and vinyl acetate, or ethylene, vinyl acetate and vinyl chloride, and 0.1 to 100 parts by weight of solid content in the aqueous emulsion. One or two or more kinds of ethylenically unsaturated compounds corresponding to 150 parts by weight are added, and the polymerization is performed in the presence of an oil-soluble radical polymerization initiator.

Examples of the ethylenically unsaturated compound used here include olefins such as ethylene and propylene, acrylic acid esters such as methyl acrylate and ethyl acrylate, methacrylic acid esters such as ethyl methacrylate, halogenated vinyl chloride, vinyl bromide and the like. Unsaturated carboxylic acids such as vinyl, styrene, acrylic acid, maleic acid and its monoesters, acrylonitrile, acrylamide,
Numerous substances such as nitrogen-containing unsaturated compounds such as N-methylol acrylamide are exemplified. Further, as a method for producing ethylene, styrene, vinyl ester or vinyl ester and vinyl chloride emulsion, JP-B-58-
In the first step of 39164, ethylene and styrene-based monomer or ethylene, a monomer copolymerizable with ethylene and styrene-based monomer is emulsion-polymerized, and in the presence of the aqueous emulsion obtained in the second step, ethylene is added. And a vinyl ester or ethylene, a vinyl ester and vinyl chloride are emulsion polymerized.

On the other hand, in recent years, there has been a demand for development of an emulsion having higher rigidity and good film-forming temperature for various purposes and further having flame retardancy.

By the way, as a general technique, it can be achieved by increasing the copolymerization amount of monomers such as vinyl chloride, styrene, and methyl methacrylate in the polymer composition as a means for increasing the rigidity. Along with this, the film forming temperature rises, and an excessive heat source is required during processing, resulting in a markedly poor workability.

In the above ethylene / vinyl chloride copolymer and ethylene / vinyl chloride / vinyl acetate copolymer emulsion,
By further increasing the vinyl chloride content, the flame retardancy and rigidity are further improved, but the minimum film-forming temperature, which is an important function of the emulsion, is significantly increased, which deteriorates the workability and makes it unusable. Will be things.

In addition, the method of quaternary copolymerizing ethylene, vinyl chloride, vinyl ester and styrene at the same time has poor copolymerizability of styrene.
A styrene quaternary copolymer emulsion cannot be easily obtained.

An ethylene / vinyl chloride / vinyl ester / methyl methacrylate quaternary copolymer emulsion can be easily obtained, but with an increase in the copolymerization amount of methyl methacrylate,
Although the rigidity is improved, the flame retardancy and the film-forming property are deteriorated, so that the physical properties cannot be balanced.

Therefore, ethylene-vinyl chloride copolymer, ethylene
It is possible to seed polymerize methyl methacrylate with a vinyl chloride / vinyl acetate copolymer emulsion.
Further, the film forming temperature becomes higher and the film forming property cannot be improved.

Further, a method of seed-polymerizing styrene on an ethylene / vinyl chloride / vinyl acetate terpolymer is presented in the above-mentioned Japanese Patent Publication No. 54-44034, but the operation is complicated and an oil-based catalyst is used. Since it is used, it is necessary to raise the polymerization temperature, and the polymerization controllability is remarkably inferior, and there is a problem that coarse particles are generated in the produced emulsion.

In addition, although it is recognized that ethylene / vinyl acetate copolymer emulsion is used as a seed and styrene is post-polymerized in the examples, when ethylene / vinyl acetate / vinyl chloride copolymer emulsion is used as a seed, ethyl acrylate, methyl Only the description of post-polymerization containing methacrylate as a main component is exemplified. Also, regarding the effect, although there is a description such as tensile strength and pencil hardness, there is no description regarding rigidity as in the present invention, and no effect regarding flame retardancy is described. Next, in Japanese Examined Patent Publication No. 58-39164, the styrene monomer is polymerized in the presence of ethylene in the first step emulsion polymerization. Therefore, even if it reaches the second stage, the polymerization of vinyl ester is significantly suppressed and a good emulsion cannot be obtained.

<Problems to be Solved by the Present Invention> The purpose of the present invention is that the technology of seed-polymerizing a styrene-based monomer into an ethylene / vinyl chloride / vinyl ester-based copolymer emulsion has not yet been established in these conventional technologies. In view of this, the emulsion has a good film-forming property with a minimum film-forming temperature of 60 ° C or less, and has a very high rigidity of 200 mm by the cantilever method, which is a characteristic of the vinyl chloride-based copolymer emulsion. It is to obtain an emulsion composition that does not impair the flammability.

That is, it is to improve the rigidity of the ethylene / vinyl chloride / vinyl ester copolymer without impairing the film-forming property and flame retardancy which are the characteristics of the ethylene / vinyl chloride / vinyl ester copolymer emulsion.

<Means for Solving the Problem> The inventors of the present invention have earnestly studied to develop an emulsion composition having physical properties such as film-forming property, flame retardancy, and rigidity, and as a result, ethylene-vinyl chloride was obtained. Solid content in the copolymer emulsion in the presence of vinyl ester copolymer
It was found that an emulsion meeting the above-mentioned purpose can be obtained by adding 10 to 150 parts by weight of styrene-based monomer per 100 parts by weight and polymerizing with a water-soluble radical initiator.

That is, the present invention is: ethylene: 5 to 40 wt% vinyl chloride: 30 to 80 wt% vinyl ester 65 wt% or less and, if necessary, copolymerizable modified monomer: 0 to 10 wt% ethylene Emulsion obtained by adding a styrene monomer corresponding to 10 to 150 parts by weight to 100 parts by weight of the solid content in the vinyl chloride / vinyl ester copolymer emulsion and polymerizing with an aqueous radical initiator. Which has a film-forming temperature of 60 ° C. or less, a rigidity by the cantilever method of 200 mm or more, and a vinyl chloride content in the polymer of 12 to 73% by weight. It is related to. In the present invention, the ethylene / vinyl chloride / vinyl ester copolymer emulsion (hereinafter referred to as a seed emulsion) has a flame retardancy and rigidity when the ethylene content is less than 5% by weight or the vinyl chloride content exceeds 80% by weight. The degree is not preferable because the film-forming temperature becomes high although it exhibits sufficient performance.

When the ethylene content exceeds 40% by weight, the vinyl chloride content is less than 30% by weight, or the vinyl ester content exceeds 65% by weight, the film forming temperature can be lowered, but the rigidity is low. However, the flame retardancy is poor and it cannot be used.

The vinyl ester used in the present invention is one or more of vinyl acetate, vinyl propionate, vinyl butyrate, and tertiary higher fatty acid vinyl ester.

Further, in the seed emulsion, in order to improve various other physical properties such as water resistance, solvent resistance, weather resistance, and heat resistance within a range that does not impair the characteristics of the present invention, in addition to the main monomer,
0 to 10% by weight of the copolymerizable modified monomer can be used.

Examples of the copolymerizable modified monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid, as well as esters of these unsaturated carboxylic acids, anhydrides, N-methylolacrylamide, N-
N-methylol derivative monomers such as methylol methacrylamide, N-butoxymethylol acrylamide, etc., hydroxyl group-containing monomers such as allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and monoallyl ethers of polyhydric alcohols. , Amino group-containing monomers such as dimethylaminoethyl methacrylate, vinyl pyridine and tert-butylaminoethyl methacrylate, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether, amide groups such as acrylamide, methacrylamide and maleamide Contained monomers, diacrylic phthalate, triacrylate, tetraacrylate, triallyl cyanurate, triacrylate Examples thereof include compounds having a polypolymerizable vinyl bond such as allyl isocyanurate and divinylbenzene.

It should be noted that the seed emulsion may be produced by any method as long as it can be obtained by emulsion polymerization according to a usual method, and the emulsion concentration is not particularly limited.

The styrene-based monomer used in the present invention, styrene,
α-Methylstyrene, vinyltoluene, 4-chlorostyrene, etc. are used.

It is preferable to select the optimum amount of the styrene-based monomer in consideration of the polymer composition of the seed emulsion. That is, when an ethylene content close to the lower limit of the scope of claims or a vinyl chloride content close to the upper limit of the scope of claims is used, the polymer itself of the seed emulsion has relatively high rigidity and flame retardance. The film forming temperature is relatively high, but the film forming temperature is relatively high. Therefore, it is preferable that the amount of the styrene-based monomer to be seed-polymerized is relatively small, but if the amount of the styrene-based monomer used is less than 10% by weight per 1000 parts by weight of the solid content in the seed emulsion, Although almost no increase in the film temperature is recognized, the effect of improving the rigidity is not sufficiently exerted, which is not preferable. Therefore, in such a case, the optimum amount is 10 to 50 parts by weight of the styrene-based monomer per 100 parts by weight of the solid content in the seed emulsion.

On the contrary, an ethylene / vinyl chloride / vinyl ester copolymer emulsion having an ethylene content close to the upper limit of the claims or a vinyl chloride content close to the lower limit of the claims is used as the seed emulsion. In this case, the film-forming temperature of the seed emulsion is sufficiently low, but the rigidity of the polymer is poor, so it is necessary to use a large amount of the styrene-based monomer to be seed-polymerized. , Solid content in seed emulsion
If the amount exceeds 150 parts by weight per 100 parts by weight, flame retardant characteristics are not exhibited, and coarse particles may be generated in the produced emulsion, which is not preferable. Therefore, in such a case, it is optimum to use 50 to 150 parts by weight of the styrene-based monomer per 100 parts by weight of the solid content in the seed emulsion.

When the styrene-based monomer is polymerized, the styrene-based monomer may be added all at once to the seed emulsion for polymerization, or a part or all of the styrene-based monomer may be sequentially added and polymerized.

Next, as the water-soluble radical initiator used when polymerizing the styrenic monomer in the present invention, hydrogen peroxide,
Although ammonium persulfate, sodium persulfate, potassium persulfate and the like are optimal, oily radical initiators such as organic peroxides and azo compounds can be used together as long as coarse particles are not generated during polymerization.

In the polymerization, it is more preferable to use a so-called redox catalyst system in which a reducing agent is used in combination with the water-soluble radical dye initiator. As the reducing agent used at that time, Rongalit (formaldehyde sulfoxylate), sodium thionitrate, sodium sulfite, sodium hyposulfite, L
-Ascorbic acid and its salts, succinic acid and its salts, ferrous salts, etc. can be used as long as they are generally used in emulsion polymerization.

The amount of the polymerization initiator used is 0.01 to 5 parts by weight with respect to 100 parts by weight of the styrene-based monomer, and the addition method is to add the entire amount at the beginning of the polymerization, or to add a part of the polymerization initiator and the rest to proceed the polymerization in a timely manner. It may be added together with.

When carrying out the polymerization with a redox catalyst system, the amount of the reducing agent used is appropriate such that the molar ratio of the polymerization initiator / reducing agent is 0.5 to 5.0. , Or a part thereof may be added, and the rest may be added appropriately with the progress of polymerization.

When a good emulsion is obtained when the styrene monomer is polymerized, it is not necessary to add an emulsifier and a protective colloid, but when the viscosity of the produced emulsion is abnormally increased or coarse particles are generated. It is necessary to add an emulsifier and / or a protective colloid. Even in this case, the addition amount is set to the minimum necessary amount in order to prevent deterioration of water resistance and the like.

The emulsifier and protective colloid to be added can be arbitrarily selected as long as they are emulsifiers and protective colloids usually used in emulsion polymerization.

As the emulsifier, an anionic surfactant and a nonionic surfactant are used, but these can also be used in combination in any combination.

Examples of the anionic surfactant include alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, polyoxyethylene alkali sulfates, polyoxyethylene alkyl phosphates, and the like.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene fatty acid esters.

Examples of protective colloids include polyvinyl alcohols such as completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, cation-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, hydrophobic group-modified polyvinyl alcohol, and silicon-containing polyvinyl alcohol, hydroxyethyl cellulose, hydroxy. Examples thereof include water-soluble cellulose derivatives such as propyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, styrene-maleic acid-based copolymers, water-soluble starch and the like.

In addition, 2,2,4-trimethylpentanediol-1,3-monobutyrate for the purpose of lowering the film forming temperature when using the multi-component synthetic resin emulsion of the present invention, a film forming aid such as butyl carbitol acetate, dibutyl Plasticity such as styrate, tricresyl phosphate, butylbenzyl phosphate, and 2-ethylhexyldiphenyl phosphate can be added, but in that case, the amount used must be kept to the minimum necessary amount in order to prevent reduction in rigidity.

In addition, if necessary, various additives such as antifoaming agents, dispersants, preservatives, thickeners, coloring pigments, inorganic fillers, flame retardants, antiaging agents, melamine resins, polyamide resins, epoxy resins, urethanes. Thermosetting resin such as resin, styrene / butadiene rubber, natural rubber, chloroprene rubber, polyisoprene rubber, acrylonitrile / butadiene copolymer rubber, methyl methacrylate / butadiene copolymer rubber, etc. , Vinyl acetate, vinyl chloride, vinylidene chloride, styrene / acrylic copolymer, vinyl acetate / acrylic copolymer, vinyl acetate / ethylene copolymer, etc. Can also be used for.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to this.

In addition, each physical-property value displayed in the Example is based on the following measuring method.

(1) MFT (minimum film forming temperature): A metal plate (manufactured by Riken Seiki Co., Ltd.) with a continuous temperature gradient is coated with the emulsion at a coating thickness of 50 μ (wet state) and dried to prevent cracking. The minimum temperature for forming a uniform film was determined.

From the viewpoint of workability during drying, the MFT is preferably 60 ° C or lower.

(2) Flame retardance: A film with a thickness of 0.5 mm made by drying an emulsion is used, and the oxygen index burning tester (Suga Test Instruments Co., Ltd.) burns the film to the limit oxygen index (LO).
I) was asked.

The higher this value, the more flame retardant.

(3) Rigidity: Emulsion is applied to a polyester non-woven fabric having a basis weight of 150 g / m ² so as to be 75 g / m ² in a dry state, and then dried and then a test piece of 25 × 150 mm is cut from the work cloth. Using the cantilever method (JIS L-1021), place the test piece in line with the base line of the scale, then push the test piece in the direction of the 45 ° angled slope, and when one end of the test piece touches the slope, the distance extruded Measure The longer the distance, the harder it is, and the shorter the distance, the more supple it is.

In the present invention, the level at which the rigidity is satisfied is 20
It should be 0 mm or more.

Example-1 10 wt% ethylene, 60 wt% vinyl chloride, 28 vinyl acetate
%, N-methylol acrylamide 2% by weight
Ethylene / vinyl chloride copolymer emulsion (solid
(51.3% min) 390g was charged into a separable flask and
Margen 911 (Polyoxyethylene nonylphenyl ether
Ether: HLB 13.7 Kao Soap Co., Ltd. 1.0g dissolved in water 10g
After adding and stirring, the inside of the reactor is replaced with nitrogen (see the following procedure).
All work is done under nitrogen atmosphere) 100g of styrene added
And continue stirring for 30 minutes to seed the added styrene.
Sufficiently penetrate into the emulsion particles.

After that, the temperature rises to 50 ° C and 3.0% ammonium persulfate aqueous solution 3
5 ml and 65 ml of 1% Rongalit aqueous solution were fed from each of the two feeding ports for 3 hours at a constant rate. After the completion of the addition of the aqueous catalyst solution, the internal temperature was kept at 50 ° C. and the reaction was aged for 1 hour. The resulting emulsion has a solids content of 50.3% by weight.
Coarse particles that cannot be filtered through a 100-mesh wire mesh were 20 ppm, and the emulsion was a stable emulsion with no sedimentation during standing.

The results of evaluating the properties of the produced emulsion by the above-mentioned method are as shown in Table 1. That is, the emulsion obtained in Example 1 exhibited a low temperature film-forming property of 37 ° C. and at the same time showed sufficient rigidity, and the flame retardancy level was also good corresponding to the vinyl chloride content. It was

Comparative Example-1 The above-mentioned properties were evaluated as they were without modifying the ethylene / vinyl chloride / vinyl acetate copolymer emulsion used as the seed emulsion in Example-1.
The results are shown in Table 1.

Although the film-forming property and flame retardancy are good, the rigidity, which is the main object of the present invention, is extremely poor.

Comparative Example-2 Ethylene used as a seed emulsion in Example-1
・ Vinyl chloride / vinyl acetate copolymer emulsion 580g
Charge 1 separable flask, Emulgen 911
(Kao Soap Co., Ltd.) 0.09g, Rongalit 0.059g
Is dissolved in 10 g of water, added and stirred, and the inside of the reactor is replaced with nitrogen.
It (The following operations are all performed under a nitrogen atmosphere). Su
After adding 9 g of ethylene, continue stirring for 30 minutes and add the added starch.
Len is thoroughly penetrated into the seed emulsion particles. So
After that, the temperature is raised to 50 ° C. and a 0.5% ammonium persulfate aqueous solution 19 m is added.
l was fed at a constant rate for 2 hours. Catalyst aqueous solution addition
After the addition, keep the internal temperature at 50 ° C and let it mature for 1 hour.
It was The resulting emulsion had a solids content of 49.6% by weight and had 18 ppm of coarse particles that could not be filtered through a 100 mesh wire mesh.
It was

Table 1 shows the results of evaluation of the properties of the produced emulsion by the method described above.

In the case of Comparative Example-2, the amount of styrene polymerized is too small, and the effect of improving the rigidity is poor, which is not preferable.

Comparative Example-3 Ethylene used as a seed emulsion in Example-1
・ Vinyl chloride / vinyl acetate copolymer emulsion 390g
Emulgen 911 charged into a separable flask (flower
1.0 g of Wang Soap Co., Ltd.) was dissolved in 110 g of water, and after adding and stirring,
Replace the inside of the reactor with nitrogen. (The following operations are all in a nitrogen atmosphere
Conduct below). Then, after raising the temperature to 70 ° C, add 100 g of styrene.
Mixture of 0.755 g of α, α'-azobisisobutyronitrile
Is fed at a constant rate for 3 hours to carry out polymerization. Predetermined
After adding the monomer catalyst mixture, keep the internal temperature at 70 ° C.
The aging reaction was continued for 1 hour. The resulting emulsion is a solid
Coarse particles that cannot be filtered with 100 mesh wire mesh at 50.0%
 It is not preferable because a large amount of 9000ppm is generated.

The results of evaluating the properties of the produced emulsion by the above-mentioned method are shown in Table 1.

There is an example in which the aqueous radical initiator ammonium persulfate used in Example 1 was replaced with azobisisobutyronitrile, which is an oily radical initiator, and post-polymerization of styrene was performed. It is generated in a large amount and cannot withstand industrial use.

Comparative Example-4 An emulsion was produced in the same manner as in Example 1 except that the same amount of methyl methacrylate (MMA) was used in place of styrene in Example 1.

The produced emulsion had a solid content of 50.3% by weight, and the amount of coarse particles that could not be filtered through a 100 mesh wire mesh was 25 ppm.

Table 1 shows the results of evaluation of the properties of the produced emulsion by the method described above.

We examined whether MMA could achieve the same effect as styrene.However, when MMA was used, no improvement in rigidity was observed, but the film-forming temperature became extremely high, making it unusable. It was

Example-2 18% by weight of ethylene, 40% by weight of vinyl acetate 40% by weight of vinyl acetate
%, N methylol acrylamide 2% by weight
Ethylene / vinyl chloride / vinyl acetate copolymer
300g of Rojon (solid content 50.0%) in 1 separable frass
Emulsion 911 charged in Ko (Kao Soap Co., Ltd.) 1.56
g, Nimar 2F needle (Soda lauric acid, Kao stone
0.39 g of Sapon Co., Ltd. was dissolved in 1.5 g of water, and after adding and stirring,
Replace the inside of the reactor with nitrogen. (The following operations are all in a nitrogen atmosphere.
Conduct below). After adding 195 g of styrene, stir for 30 minutes.
Continue stirring and add the styrene monomer added to the seed emulsion.
To penetrate into the particles.

After that, the temperature is raised to 50 ° C. and a 3% ammonium persulfate aqueous solution is added.
68 ml and 126 ml of 1% Rongalit aqueous solution were fed from each of the two feeding ports for 3 hours at a constant rate. After the completion of the addition of the aqueous catalyst solution, the internal temperature was kept at 50 ° C. and the reaction was aged for 1 hour.

The produced emulsion had a solid content of 49.6% by weight and contained 25 ppm of coarse particles that could not be filtered through a 100-mesh wire net, and was a stable emulsion in which no sedimentation occurred during standing.

Table 1 shows the results of evaluation of the properties of the produced emulsion by the above-mentioned method.

This is an example of using ethylene / vinyl chloride / vinyl acetate copolymer with a relatively low vinyl chloride content as a body seed emulsion. In this case, the resin of the seed emulsion becomes soft, so in order to obtain sufficient rigidity. However, it is necessary to post-polymerize a relatively large amount of styrenic monomer.

Therefore, in Example 2, the solid content of the seed emulsion was 10
It was shown that by post-polymerizing 130 parts with respect to 0 parts by weight, an emulsion having an extremely low film forming temperature, sufficient rigidity and flame retardancy can be obtained.

Comparative Example-5 The above-mentioned characteristics were evaluated as they were without modifying the ethylene / vinyl chloride / vinyl acetate copolymer emulsion used in Example-2. The results are shown in Table 1.

The film-forming property is extremely excellent and the flame retardancy is also satisfactory, but the rigidity is remarkably poor, which is not preferable.

Example-3 5% by weight of ethylene, 63% by weight of vinyl chloride, 30% of vinyl acetate
% Separation of 600 g of ethylene / vinyl chloride / vinyl acetate copolymer emulsion (solid content: 50.0%) consisting of 2% by weight of N-methylol acrylamide and 5% of solid content in one separable frus and replacing the inside of the reactor with nitrogen (all operations below are in a nitrogen atmosphere. Conduct below). After adding 60 g of styrene, stirring is continued for 30 minutes to allow the added styrene to sufficiently penetrate into the seed emulsion particles. Then, the internal temperature was raised to 50 ° C., and 21 ml of a 3.0% ammonium persulfate aqueous solution and 39 ml of a 1% rongalite aqueous solution were respectively fed from two feeding ports at a constant rate for 2 hours. After the completion of the addition of the aqueous catalyst solution, the internal temperature was kept at 50 ° C. and the reaction was aged for 1 hour.

The produced emulsion had a solid content of 50.1% by weight and contained 35 ppm of coarse particles that could not be filtered through a 100-mesh wire net. The results of evaluating the properties of the produced emulsion by the above-mentioned method are shown in Table 1. Contrary to the case of Example-2, an example of using a hard ethylene / vinyl chloride / vinyl acetate copolymer having a relatively low ethylene content as a seed emulsion was shown. By polymerizing, a good emulsion was obtained, and all the required physical properties such as film-forming property, rigidity and flame retardancy were satisfied.

Comparative Example-6 The above-mentioned properties were evaluated as they were without modifying the ethylene / vinyl chloride / vinyl acetate copolymer emulsion used in Example-3. The results are shown in Table 1.

In Comparative Example 6, although the film-forming property and flame retardancy were good, the rigidity, which is the main object of the present invention, was insufficient.

Example-4 Instead of the ethylene / vinyl chloride / vinyl acetate copolymer emulsion used in Example-3, 5% by weight of ethylene,
Other conditions except that an ethylene / vinyl chloride / vinyl acetate copolymer emulsion (solid content 50.0%) having a composition of 63% by weight of vinyl chloride, 29% by weight of vinyl acetate and 3% by weight of 2-hydroxyethyl acrylate was used. An emulsion was prepared in the same manner as in -3.

This emulsion had a solid content of 50.1% by weight and contained 38 ppm of coarse particles that could not be filtered through a 100-mesh wire net.

Table 1 shows the results of evaluation of the properties of the produced emulsion by the method described above.

Even when an ethylene / vinyl chloride / vinyl acetate-based copolymer emulsion in which 3% by weight of 2 hydroxyethyl acrylate was copolymerized was used as the copolymerizable modified monomer, film-forming property, rigidity equivalent to that of Example-3, It shows flame retardancy and gives good results.

Comparative Example-7 The ethylene / vinyl chloride / vinyl acetate copolymer emulsion used in Example-4 was evaluated as it was without modification. The results are shown in Table 1.

Although the film-forming property, the rigidity, and the flame retardancy were good as in Comparative Example 6, the rigidity, which is the main object of the present invention, was insufficient.

Example-5 Instead of the ethylene / vinyl chloride / vinyl acetate copolymer emulsion used in Example-2, ethylene / chlorine having a composition of 20% by weight of ethylene, 40% by weight of vinyl chloride and 40% by weight of vinyl acetate was used. An emulsion was produced in the same manner as in Example-2 except that a vinyl / vinyl acetate copolymer emulsion (solid content 50.0%) was used.

The emulsion produced has 49.6% by weight solids, 28 ppm of coarse particles that cannot be filtered through a 100 mesh wire mesh, and no sedimentation occurs during storage.

Table 1 shows the results of evaluation of the properties of the produced emulsion by the above-mentioned method.

Even when the ethylene / vinyl chloride / vinyl acetate copolymer emulsion without using the copolymerizable modified monomer was used, the same film-forming property, rigidity and flame retardance as those of Example-2 were obtained, and the results were good. .

Comparative Example-8 The above-mentioned properties were evaluated as they were without modifying the ethylene / vinyl chloride / vinyl acetate copolymer emulsion used in Example-5. The results are shown in Table 1.

Similar to Comparative Example-5, the film-forming property was extremely good and the flame retardancy was satisfactory, but the rigidity was remarkably inferior.

<Effect of the Invention> In order to obtain a composition satisfying all the required physical properties such as film-forming property, rigidity, and flame retardancy, which are the objects of the present invention, from the performance evaluation results of the above Examples and Comparative Examples, ethylene: 5-40% by weight Vinyl chloride: 30-80% by weight Vinyl ester: 65% by weight and optionally a copolymerizable modifying monomer: 0-10% by weight Ethylene / vinyl chloride / The vinyl acetate copolymer emulsion was used as a seed emulsion, and the solid content of the copolymer emulsion was 10
By polymerizing 10 to 150 parts by weight of styrene-based monomer per 0 parts by weight with an aqueous radical initiator, a good emulsion can be obtained, and the film-forming temperature is 60 ° C or less, and the vinyl chloride content in the polymer is The composition of 15 to 73% by weight satisfied all of the film forming property, flame retardancy and rigidity.

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Claims (1)

[Claims] 1. Ethylene: 5-40% by weight Vinyl chloride: 30-80% by weight Vinyl ester 65% by weight or less and, if necessary, a copolymerizable modifying monomer: 0-10% by weight ethylene chloride An emulsion prepared by adding 10 to 150 parts by weight of a styrene-based monomer to 100 parts by weight of the solid content in the vinyl-vinyl ester copolymer emulsion and polymerizing the resulting emulsion with an aqueous radical initiator. An emulsion composition having a film forming temperature of 60 ° C. or less, a rigidity of 200 mm or more by a cantilever method, and a vinyl chloride content in a polymer of 12 to 73% by weight.