JPH0689083B2 - Ethylene / vinyl chloride / styrene emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to an emulsion composition having a special particle form obtained by seed-polymerizing an ethylene / vinyl chloride copolymer emulsion with a styrene monomer. It is about.

The emulsion obtained according to the present invention has a film-forming property, a rigidity, and a flame retardance, and therefore, a carpet backing agent,
It can be used in a wide range of application fields of emulsions such as hard type fiber processing agents typified by non-woven fabric binders, paper processing agents, adhesives, paints and the like.

<Prior Art> Ethylene / vinyl chloride copolymer emulsions have excellent adhesion to various paper / fiber base materials and have flame retardancy due to vinyl chloride, which makes them suitable for paper / fiber processing. It is widely used in the above-mentioned various applications centering on agents.

For example, Japanese Patent Publication Nos. 48-22855, 48-8316, and 4
No. 9-47675 proposes to use an ethylene / vinyl chloride copolymer as a binder for a bonded non-woven fibrous product.

In addition, JP-A-58-41972, JP-A-58-104935, JP-A-5-
8-125738, JP-A-58-17602, JP-A-58-154631 and the like disclose flame-retardant rug packing materials using an ethylene / vinyl chloride copolymer emulsion.

By the way, in recent years, there has been a demand for the development of an emulsion having higher rigidity and good film-forming property for various purposes and further having flame retardancy. As a means of increasing the rigidity, there is a method of increasing the copolymerization amount of vinyl chloride, styrene, methyl methacrylate, etc. in the polymer composition, in which case the film-forming temperature rises as the copolymerization amount increases. Since an excessive heat source is required at the time of machining, the workability is remarkably poor. In the above-mentioned known ethylene / vinyl chloride copolymer emulsion, the rigidity and flame retardancy are improved by increasing the vinyl chloride copolymerization amount, but the minimum film forming temperature, which is an important function of the emulsion, is significantly increased. Processing workability deteriorates, and it becomes unusable.

In addition, the method of simultaneously terpolymerizing ethylene / vinyl chloride and styrene is inferior in the copolymerizability of ethylene, so that an ethylene / vinyl chloride / styrene terpolymer emulsion cannot be easily obtained. Ethylene / vinyl chloride /
Although a methyl methacrylate terpolymer emulsion can be easily obtained, as the copolymerization amount of methyl methacrylate increases, the rigidity improves but the flame retardancy and film-forming property deteriorate, so the physical property balance is improved. Can't take

Therefore, it is conceivable to seed polymerize the ethylene / vinyl chloride copolymer emulsion with methyl methacrylate. In this case, the film-forming temperature becomes higher than that of the ethylene / vinyl chloride / methyl methacrylate terpolymer emulsion. It does not lead to improvement of film forming property.

<Problems to be Solved by the Present Invention> It is an object of the present invention to provide an emulsion having improved film forming properties, high rigidity and high flame retardancy, which are improved from the drawbacks of the conventional techniques. .

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

<Means for Solving Problems> In view of the present situation as described above, the present inventors have earnestly studied to develop an emulsion composition having physical properties such as film-forming property, flame retardancy and rigidity. As a result, in the presence of the ethylene / vinyl chloride copolymer emulsion, 10 to 150 parts by weight of styrene-based monomer was added to 100 parts by weight of the solid content of the copolymer emulsion to start the water-soluble radical initiation. It was found that an emulsion meeting the above-mentioned purpose can be obtained by polymerizing with an agent, and the present invention was started.

That is, the present invention relates to a vinyl chloride copolymer emulsion having a composition of ethylene: 10 to 40% by weight, vinyl chloride: 50 to 90% by weight, and optionally a copolymerizable modifying monomer: 0 to 10% by weight. 10 to 1 per 100 parts by weight of solids in polymer emulsion
An emulsion obtained by adding 50 parts by weight of a styrene-based monomer and polymerizing with an aqueous radical initiator,
The present invention relates to an ethylene / vinyl chloride / styrene emulsion composition, which has a film forming temperature of ℃ or less and a vinyl chloride content in the resin solid matter of 20 to 80% by weight. The ethylene / vinyl chloride copolymer emulsion (composition of ethylene: 10 to 40% by weight, vinyl chloride: 50 to 90% by weight, and optionally a copolymerizable modified monomer: 0 to 10% by weight) used in the present invention ( In the following, referred to as a seed emulsion), when the ethylene content is less than 10% by weight or the vinyl chloride content is more than 90% by weight, flame retardancy and rigidity can be increased, but the film forming temperature becomes high, which is not preferable. When the ethylene content exceeds 40% by weight, or when the vinyl chloride content is less than 50%, the film-forming temperature can be lowered, but the flame retardancy is poor, and the rigidity of the post-polymerized styrene monomer is low. Is also inferior, which is not preferable.

In addition, the seed emulsion contains not only the above-mentioned main monomer but also a copolymerizable modified monomer for the purpose of improving various other physical properties such as water resistance, solvent resistance, weather resistance, and heat resistance within a range not impairing the features of the present invention. ~ 10 wt% can be used. Examples of the copolymerizable modified monomer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, acid vinyl esters such as tertiary higher fatty acid vinyl ester, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid. Such as unsaturated carboxylic acid, and ester anhydrides of the unsaturated carboxylic acid, N-methylol acrylamide, N-methylol methacrylamide, N-methylol derivative monomer such as N-butoxymethylol acrylamide, allyl alcohol, 2-hydroxyethyl acrylate , 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, hydroxyl group-containing monomers such as monoallyl ethers such as polyhydric alcohols dimethylaminoethyl methacrylate, Nylperidine, amino group-containing monomers such as tert-butylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, epoxy group-containing monomers such as allyl glycidyl ether, amide group-containing monomers such as acrylamide, methacrylamide, maleamide, diallyl phthalate, triacrylate , Tetraacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and other compounds having a polymerizable vinyl bond.
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 there is no particular limitation on the emulsion concentration and the like.

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 a vinyl chloride content close to the upper limit of the claimed range is used, the polymer itself of the seed emulsion has relatively high rigidity and excellent flame retardancy, but the film forming temperature becomes relatively high. Therefore, it is preferable to use a relatively small amount of styrene-based monomer for seed polymerization.
When the amount is less than 10% by weight per 100 parts by weight, the film-forming temperature hardly increases, but the effect of improving the rigidity is not sufficiently exhibited, 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.

Conversely, when an ethylene / vinyl chloride copolymer emulsion having a vinyl chloride content close to the lower limit of the claimed range is used as a seed emulsion, the film-forming temperature of the seed emulsion is sufficiently low, but the hardness of the polymer is low. Since it is inferior, it is necessary to use a large amount of styrene-based monomer for seed polymerization. However, if the amount of the styrene-based monomer used exceeds 150 parts by weight per 100 parts by weight of the solid content in the seed emulsion, flame retardant characteristics are not exhibited, and coarse particles may be generated in the produced emulsion, which is preferable. Absent.
Therefore, in such a case, the optimum amount is 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 initiation used when polymerizing the styrene-based monomer in the present invention, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate and the like are optimal, but coarse particles during the polymerization. An oily radical initiator such as an organic peroxide or an azo compound may be used in combination as long as it does not occur.

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 initiator. As the reducing agent used at that time, Rongalit (formaldehyde sulfoxylate), sodium thiosulfate, sodium sulfite, sodium hyposulfite,
L-ascorbic acid and salts thereof, succinic acid and salts thereof, ferrous salts and the like can be used as long as they can be generally used in emulsion polymerization.

The amount of polymerization initiator used is 100
It is 0.01 to 5 parts by weight with respect to parts by weight, and the addition method may be such that the entire amount is added at the beginning of the polymerization, or a part thereof may be added and the rest may be added in timely with the progress of the polymerization.

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

If a good emulsion is obtained when the styrene-based monomer is polymerized, it is not necessary to add an emulsifier and a protective colloid, but if the viscosity of the produced emulsion is abnormally increased or coarse particles are generated. It is necessary to add an emulsifier 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.

An anionic surfactant is used as the emulsifier,
This can also be used 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 the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.

As the protective colloid, completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, cation-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, hydrophobic group-modified polyvinyl alcohol, silicon-containing polyvinyl alcohol and other polyvinyl alcohols, hydroxyethyl cellulose, hydroxypropyl, etc. Examples thereof include water-soluble cellulose derivatives such as cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, styrene-maleic acid-based copolymers, and water-soluble starch.

For the purpose of lowering the film forming temperature when using the multi-component synthetic resin emulsion of the present invention, a film forming auxiliary such as 2,2,4-trimethylpentadiol-1,3-monobutyrate or butyl carbitol acetate, dibutyl phthalate , Tricresyl phosphate, butylbenzyl phosphate, 2
Plasticity such as ethylhexyldiphenyl phosphate may be added and used, but in that case, the amount used must be kept to the minimum necessary amount in order to prevent the decrease 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): Film thickness of emulsion on a metal plate (manufactured by Riken Seiki Co., Ltd.) with continuous temperature gradient
It was applied at 50μ (wet state) and dried to determine the minimum temperature at which a uniform film without cracks was formed. From the viewpoint of workability during drying, the MFT is preferably 60 ° C or lower.

2. Flame retardance: Using a 0.5 mm thick film made by drying an emulsion, the oxygen index type combustion 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. Stiffness: Emulsion is applied to 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.
Take a 25 × 150 mm sample from a work cloth and use the cantilever method (JIS
L-1005) Place the test piece in line with the scale base line, then push the test piece in the direction of the 45 ° angled slope, and measure the extruded distance when one end of the test piece touches the slope. 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 A separable flask (reactor) was charged with 425 g of an ethylene / vinyl chloride copolymer emulsion (solid content 47.0%) having a composition of 25% by weight of ethylene, 72% by weight of vinyl chloride and 3% by weight of acrylamide. After charging, the inside of the reactor is replaced with nitrogen (all the following operations are performed under a nitrogen atmosphere). After adding 150 g of styrene, stirring is continued for 30 minutes to allow the added styrene to sufficiently penetrate into the seed emulsion particles.

After that, the temperature was raised to 50 ° C, and a 3% ammonium persulfate aqueous solution 5
2.5 ml and 17.5% of Rongalit solution 97.5 ml each 2
It was supplied from one supply port for 3 hours at a constant rate. After the completion of the addition of the polymerization initiator and the reducing agent aqueous solution, the internal temperature was further kept at 50 ° C. and the aging reaction was carried out for 1 hour. The resulting emulsion was a stable emulsion having a solid content of 48.3% by weight, 25 ppm of coarse particles that could not be filtered through a 100-mesh wire net, and no sedimentation during storage.

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 exhibits a low temperature film-forming property of 26 ° C. and at the same time exhibits a sufficient rigidity, and the flame retardancy level is also good corresponding to the vinyl chloride content level. there were.

Comparative Example-1 The above-mentioned properties were evaluated as they were without modifying the ethylene / vinyl chloride copolymer emulsion used in Example-1. The results are shown in Table 1. In the case of Comparative Example-1, although the film-forming property and the flame retardancy are good, the rigidity, which is the main object of the present invention, is extremely poor.

Comparative Example-2 638 g of the ethylene / vinyl chloride copolymer emulsion used in Example-1 was charged into a one-separable flask and replaced with nitrogen. After adding 15 g of styrene, stirring is continued for 30 minutes to allow the added styrene to sufficiently penetrate into the seed emulsion particles. After that, the temperature was raised to 50 ° C., and 19 ml of 1.0% ammonium persulfate aqueous solution and 10 ml of 1.0% rongalite aqueous solution were added to 2 ml.
Feed at constant rate over time. After that, aging reaction was performed for 1 hour to obtain a produced emulsion. The emulsion contained 19 ppm of coarse particles that could not be filtered through a solid mesh of 46.2 wt% 100 mesh wire mesh.

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 A 1-separable flask was charged with 425 g of the ethylene / vinyl chloride copolymer emulsion used in Example-1 and 150 g of water, the inside of the reactor was replaced with nitrogen, and the temperature was raised to 70 ° C. Then 150 g of styrene and α, α′-azobisisobutyronitrile 1.
Polymerization is carried out by feeding 13 g of the mixture at a constant rate for 3 hours. After the addition of the predetermined monomer initiator mixed solution was completed, the internal temperature was kept at 70 ° C. and the aging reaction was continued for 1 hour. The resulting emulsion is unfavorable because it has a large amount of coarse particles of 9000 ppm which cannot be filtered through a 100 mesh wire net at a solid content of 48.2% by weight.

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

In Comparative Example-3, an example in which post-polymerization of styrene was performed by replacing the aqueous radical initiator ammonium persulfate used in the examples with the oily radical initiator α, α′-azobisisobutyronitrile However, in this case, an extremely large amount of coarse particles are generated, which is not suitable for industrial use.

Example-2 An ethylene-vinyl chloride copolymer emulsion having a composition of 30% by weight of ethylene, 67% by weight of vinyl chloride and 3% by weight of acrylamide in a separable flask (solid content: 47.0%).
%) 319 g was replaced with charged nitrogen. Next, after adding 195 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 68 ml of a 3% ammonium persulfate aqueous solution and 126 ml of a 1% rongalite aqueous solution were respectively fed from two feeding ports at a constant rate for 3 hours.

After adding the polymerization initiator and reducing agent aqueous solution, further increase the internal temperature.
The temperature was kept at 50 ° C. and the aging reaction was performed for 1 hour. The resulting emulsion was a stable emulsion having a solid content of 48.1% by weight, 15 ppm of coarse particles that could not be filtered through a 100-mesh wire net, and no sedimentation during storage.

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

In Example-2, an example in which an ethylene vinyl chloride-based copolymer having a relatively high styrene content was used as a seed emulsion was shown. In this case, since the resin of the seed emulsion becomes soft, in order to obtain sufficient rigidity. Therefore, it is necessary to post-polymerize a relatively large amount of styrene.

Therefore, in Example-2, by post-polymerizing 130 parts of styrene with respect to 100 parts by weight of the solid content of the seed emulsion, all requirements of film-forming property, rigidity and flame retardancy are satisfied. I showed that.

Comparative Example-4 The ethylene / vinyl chloride copolymer emulsion used in Example-2 was directly evaluated for the above properties without modification. The results are shown in Table 1.

In Comparative Example-4, the film-forming property was extremely good and the flame retardancy was satisfactory, but the rigidity was remarkably inferior.

Example-3 An ethylene / vinyl chloride copolymer emulsion having a composition of 10% by weight of ethylene, 87% by weight of vinyl chloride, and 3% by weight of acrylamide in a separable flask (solid content 47.1%).
%) 638 g was replaced with charged nitrogen.

Next, after adding styrene 60, stirring is continued for 30 minutes to allow the added styrene to sufficiently penetrate into the seed emulsion particles.

After that, the internal temperature was raised to 50 ° C., and 21 ml of 3% ammonium persulfate aqueous solution and 39 ml of 1% rongalite aqueous solution were respectively fed from two feed ports at a constant rate for 2 hours.

After that, aging reaction was performed for 1 hour to obtain a produced emulsion.
This emulsion had a solid content of 47.6% and contained 58 ppm of coarse particles that could not be filtered through a 100 mesh wire mesh. Table 1 shows the results of evaluation of the properties of the produced emulsion by the method described above. In Example-3, Example-2
Contrary to the above case, an example of using a hard ethylene-vinyl chloride copolymer having a relatively low styrene content as a seed emulsion was shown.In this case, a good emulsion was obtained with a relatively small amount of styrene after weight. can get.

That is, in Example-3, the solid content of the seed emulsion was 10
By post-polymerizing 20 parts by weight of styrene per 0 parts by weight, it was shown that all required physical properties such as film-forming property, rigidity and flame retardancy were satisfied.

Comparative Example-5 The above-mentioned properties were evaluated as they were without modifying the ethylene / vinyl chloride copolymer emulsion used in Example-3. The results are shown in Table 1.

In Comparative Example-5, although the film-forming property and flame retardancy were good, the rigidity, which is the main object of the present invention, was insufficient.

Comparative Example-6 In Example-3, the same amount of methyl methacrylate (MMA) was used instead of styrene, and all other conditions were used in Example-3.
An emulsion was prepared in the same manner as in. The resulting emulsion had a solid content of 47.5% by weight and contained 32 ppm of coarse particles that could not be filtered through a 100 mesh wire mesh.

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

Comparative Example-6 is an examination as to whether or not the same effect as styrene can be obtained by using MMA. When MMA is used, the rigidity is improved but the film-forming property is remarkably increased. , It will not be usable.

Example-4 Instead of the ethylene / vinyl chloride copolymer emulsion used in Example-3, 11% by weight of ethylene and vinyl chloride were used.
Other conditions were the same as in Example-3 except that an ethylene / vinyl chloride copolymer emulsion (solid content: 47.1%) having a composition of 87% by weight and 2% by weight of N-methylolacrylamide was used.
An emulsion was prepared in the same manner as in. This emulsion had a solid content of 47.6% by weight and contained 52 ppm of coarse particles that could not be filtered through a 100 mesh wire mesh. Table 1 shows the results of evaluation of the properties of the produced emulsion by the method described above. In Example 4, 2% by weight of N-methylolacrylamide was used as the copolymerizable modifying monomer.
Even when the copolymerized ethylene / vinyl chloride-based copolymer emulsion was used, the same film-forming property, rigidity and flame retardancy as in Example-3 were exhibited, and the results were good.

Comparative Example-7 The above-mentioned characteristics were evaluated as they were without modifying the ethylene / vinyl chloride copolymer emulsion used in Example-4. The results are shown in Table 1. Similar to Comparative Example-5, the film-forming property and flame retardancy were good, but the rigidity, which is the main object of the present invention, was insufficient.

Example-5 Instead of the ethylene / vinyl chloride copolymer emulsion used in Example-2, 28% by weight of ethylene and 72% of vinyl chloride were used.
An emulsion was prepared in the same manner as in Example 2, except that an ethylene / vinyl chloride copolymer emulsion (solid content: 47.0 wt%) having a composition of wt% was used.

This emulsion had a solid content of 48.1% by weight and contained 20 ppm of coarse particles that could not be filtered through a 100-mesh wire mesh, and was a stable emulsion in which no sedimentation occurred during storage. Table 1 shows the results of evaluation of the properties of the produced emulsion by the method described above. In Example-5,
Even when the ethylene / vinyl chloride copolymer emulsion not using the copolymerizable modified monomer was used, the same film-forming property, rigidity and flame retardancy as those of Example-2 were obtained, which was a good result.

Comparative Example-8 The above-mentioned properties were evaluated as they were without modifying the ethylene / vinyl chloride copolymer emulsion used in Example-5. The results are shown in Table 1. Similar to Comparative Example-4, the film-forming property and flame retardancy were extremely good, but the rigidity, which is the main object of the present invention, was extremely poor.

<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: 10-40% by weight Vinyl chloride: 50-90% by weight and optionally a copolymerizable modified monomer: 0-10% by weight A seed emulsion having a specific polymer composition is used, and a styrene-based monomer is used. It was clarified that this can be achieved for the first time by adding a specific amount of the body and polymerizing with an aqueous radical initiator.

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Claims (1)

[Claims] 1. A vinyl chloride copolymer emulsion comprising ethylene: 10 to 40% by weight, vinyl chloride: 50 to 90% by weight, and optionally a copolymerizable modifying monomer: 0 to 10% by weight. 10 to 1 per 100 parts by weight of solids in polymer emulsion
An emulsion obtained by adding 50 parts by weight of a styrene-based monomer and polymerizing with an aqueous radical initiator,
An ethylene / vinyl chloride / styrene emulsion composition, which has a film-forming temperature of ℃ or less and has a vinyl chloride content of 20 to 80% by weight in a resin solid matter.