JPS62174114A - Formation of foam from synthetic resin emulsion - Google Patents

Abstract

PURPOSE:To give a foam excellent physical properties as foam and foam moldability by a method wherein synthetic resin emulsion is used in the presence of specified substances. CONSTITUTION:Synthetic resin emulsions consisting of a single salt or at least two salts out of metaphosphate I, polyphosphate II and ultraphosphate III as represented by structural formulae or preferably a single emulsion or mixed emulsions of polyurethane emulsion and conjugated diene and/or vinyl polymer emulsions are mechanically expanded. After that, the resultant expanded liquid is applied onto a base material or poured into a mold and finally heat-treated in order to obtain a foam, which has large surface smoothness and is uniform and porous and excellent in mechanical strength and durability even with high expansion ratio, high speed processing (high speed delivery, coating and drying with a continuous mechanical foaming machine), large coating thickness and the like.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for obtaining a foam from a synthetic resin emulsion, and more specifically, a method for obtaining a foam from a synthetic resin emulsion, and more specifically, a method for obtaining a foam from a synthetic resin emulsion, and more specifically, a method for obtaining a foam from a synthetic resin emulsion. The present invention relates to a method for stably forming a modified high-strength foam from a synthetic resin emulsion containing a specific phosphate.

(Prior art) Conventionally, natural and synthetic resin emulsions include foaming agents, coagulants,
Add crosslinking agent and other additives, mechanically foam,
Coat this on the base material or inject it into a mold, dry, solidify,
Methods of kearing to form foams are known.

Such natural and synthetic resin emulsions include natural demlatex styrene-butadiene copolymer emulsion, acrylonitrile-butatsuene copolymer emulsion, and acrylic acid ester copolymer emulsion. The formed foams are used in a variety of applications due to their structural advantages such as lightness, wall thickness, texture, and tactility.

However, many of these foams are inferior in performance such as mechanical strength and durability, and in order to be used in a wider range of applications, improvements such as higher strength and sieve durability are required. For example, natural rubber and butadiene copolymers improve durability such as light resistance and heat resistance, and mechanical strength, while acrylic ester copolymers improve mechanical strength, solvent resistance, and cold resistance. It is necessary to improve properties such as properties or elasticity.

On the other hand, various methods have been proposed for forming foams from polyurethane emulsions, and these foams are attracting attention as having high performance that has improved the above-mentioned drawbacks.

However, polyurethane emulsion is not satisfactory in terms of foam moldability using the conventionally proposed mechanical foaming method, and it has not been possible to utilize the inherent properties of stool oil for a wide range of applications, and improvements are needed. For example, it is unsatisfactory in terms of stable and wide foaming moldability, which allows for freely forming foams with a high madder expansion ratio and coating thickness, and improvements are needed.

In this way, when forming a foam from a synthetic resin emulsion, it is possible to combine the physical properties of a foam with high strength and high durability with foam moldability that allows it to be freely formed into a stable and industrially useful form. Although it is strongly demanded, it has not been realized.

(Problems to be Solved by the Invention) An important and difficult technical issue in such prior art is foam moldability. That is, when foaming an emulsion, it is necessary to generate and maintain fine and uniform air bubbles, and to cause air bubbles to coalesce or disappear from an aqueous dispersion of an emulsion that essentially has no strength to form partition walls containing air bubbles. The objective is to form a resin film strong enough to withstand permanent bubble retention without causing any damage. That is, contradictory properties are required, firstly, the ability to stabilize the dispersion of the emulsion, and secondly, the ability to destabilize the dispersion to quickly fuse the dispersed resin particles. Therefore, it is difficult to improve physical properties by combining different emulsions used in non-foaming systems because the dispersion stabilizing ability and destabilizing ability of each emulsion are different in foaming systems. Met. In fact, mixed emulsions of polyurethane emulsions and styrene-butatsuene conjugate emulsions according to the prior art either thicken significantly during mechanical foaming and solidify into a tofu-like shape, or only a large number of coarse bubbles are mixed in, resulting in foaming. The same is true for mixed emulsions of polyurethane emulsions and acrylic acid ester copolymer emulsions, which had no commercial value as a body.Especially when molding at high expansion ratios and high coating thicknesses, air bubbles Because of the coarsening and disappearance of the foam, the commercial value of the foam was lost.

Of course, if one emulsion is kept in a very small amount, or two emulsions are of the same type, or if the foaming ratio is low or the coating thickness is low (for example, about 1 mm), then the product may have some commercial value. Although it is not impossible to obtain such a product, it has not been possible to significantly improve both the physical properties and foam moldability of the foam, and the above-mentioned requirements have not been met.

The present invention seeks to solve the above problem.

(Means for Solving the Problems) The present inventors have discovered a foam that has both significantly improved physical properties such as strength and durability, and foam moldability that allows it to be freely molded into a stable and industrially useful form. As a result of intensive research into the moldability of foams made from synthetic resin emulsions, the present inventors discovered that when synthetic resin emulsions are used in the presence of specific substances, excellent physical properties and foam moldability can be imparted to foams, resulting in the present invention. .

That is, the present invention provides metaphosphate (I) represented by the following structural formula.
), polyphosphate (II), and ultraphosphate (II), a synthetic resin emulsion comprising one or more of them;
Preferably, a polyurethane emulsion, a conjugated polymer emulsion and/or a vinyl polymer emulsion alone or a mixed emulsion thereof is foamed mechanically, the foamed liquid is applied onto a substrate or poured into a mold, and then heat-treated. A method of forming characterized high strength foams is provided.

An object of the present invention is to provide a foam having excellent mechanical strength, heat resistance, cold resistance, light resistance, solvent resistance, and elasticity. Another object is to provide an emulsion with advantageous foam formability that allows the formation of such high-performance foams in stable and wide forms. Yet another object is to provide a method for forming a cutting body from a mixed emulsion of a polyurethane emulsion and another emulsion obtained by a completely different manufacturing method.

CI) (MPO3)nM: Na, K,
Ca(■) Mn+2Pn03n+1
n; positive differential number (I~10) (I11) Na2P4
According to the present invention, metaphosphate (
I), polyphosphate (II), ultraphosphate (II)
Foaming aids, viscosity modifiers, foam stabilizers, crosslinking agents, etc. are added as necessary to a synthetic resin emulsion containing one or more of l), and gas (mainly air) is mechanically blown in and stirred. By applying the foaming liquid onto a base material or injecting it into a mold, and then heat-treating it, a high foaming ratio, high-speed processing (high-speed discharge using a continuous mechanical foaming machine, coating, and drying), high Even under certain conditions such as coating thickness, a foam with uniform porous surface smoothness and excellent mechanical strength and durability can be obtained.

The synthetic resin emulsion of the present invention includes polyolefin-based (polynoloprene, polyethylene), fluororesin-based, polyacetal thread, phenolic resin-based, epoxy resin-based,
Single or mixed emulsions of alkyd resins, polyester resins, polyurethanes, conjugated dienes and/or vinyl polymers, preferably single or mixed emulsions of polyurethane emulsions, conjugated dienes and/or vinyl polymers. It is.

The polyurethane emulsion used in the present invention is already known and can be produced by various methods. For example, emulsified polyurethane solvent solutions,
As basically described in Publication No. 3-1141,
A polyhydroxy compound having a hydroxyl group at the end is reacted with an organic polyisocyanate in excess of the stoichiometric amount, and then the obtained prepolymer is emulsified in an aqueous dispersion medium using a surfactant, and a chain extender is added to the prepolymer. It is also possible to use a polyurethane emulsion obtained by adding a prepolymer to chain extension of the prepolymer.

Such polyhydroxy compounds usually have a molecular weight of 300
-4000 preferably 600-3000,
Typical examples include polyether polyols, polyester polyols, and polycarnate polyols.

Polyether polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1-2-
Propylene glycol, trimethylene glycol, 1Φ
3-butylene glycol, tetramethylene glycol,
hexamethylene glycol, decamethylene glycol,
Glycerin, sorbitol, sucrose, aconitic acid, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, propylene diamine, diethylenetriamine, triinzolonozonolamine, pyrogallol, sohydrobenzoic acid, hydroxyphthalic acid, 1, 2, 3-pro-hydrochloric acid One or more monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc. using one or more compounds having at least two active hydrogen atoms such as trithiol as an initiator It is produced by addition polymerization of more than that by a conventional method.

On the other hand, polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol,
At least two such as 1,2-zolopylene glycol, trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, glycerin, trimethylolpro/4', pentaerythritol, sorbitol, etc. one or two compounds having hydroxyl groups
species and above, malonic acid, maleic acid, conolic acid, adipic acid, tartaric acid, pimelic acid, heptad/sinic acid, oxalic acid,
At least two cals, such as phthalic acid, terephthalic acid, hexahydrophthalic acid, aconitic acid, trimellitic acid, hemimellitic acid, etc. It is produced by combining one or more xyl group-containing compounds by a conventional method.

Polyhydroxy compounds such as polyether polyols and polyester polyols can be used alone or in combination of two or more, and can also be used in combinations of ethylene glycol, diethylene glycol, diethylene glycol, Recall, 1,2-propylene glycol, trimethylene glycol, l,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, chrycerin, trimethylolpro-9, pentaerythyl, sorbitol, etc. It can be used in combination with low molecular weight polyols such as polyols.

1-4a polyisocyanates include aliphatic, cycloaliphatic or aromatic polyisocyanates, such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
m-phenylene diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, ■
・4-cyclohexylene diisocyanate, 4,4'-
Dicyclohexyl diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3
-dimethoxy-4,41-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 4-1.3, dichloro-4,4'-biphenylene diisocyanate, l,5-naphthalene diisocyanate, Examples include 1,5-tetrahydronaphthalene diisocyanate and diphenyl-2,4,4-triisocyanate.

Chain extenders are compounds having at least two active aqueous atoms capable of reacting with isocyanate groups, such as ethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, monoethanolamine, ethylenediamine, triethylenediamine,
1,2-propylenediamine, hexamethylenediamine, N-ethanolethylenediamine, N-N'-jethanolethylenediamine, m-phenylenediamine, 2
- Typical examples include glycols, alkanolamines, and diamines such as 4-tolylene diamine, bis-4-aminophenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, piperazine, and 2-methylbiperacin. As an example, the reaction product of 1 mole of alkylene diamine and 2 moles of acrylamide, 1 mole of alkylene diamine
A reaction product of 2 moles of acrylonitrile can also be used.

In the case of the present invention, the solid content concentration of the polyurethane emulsion is not particularly limited, but considering the economical efficiency during drying and the homogeneity of the foam material, the solid content concentration of the polyurethane emulsion is preferably 30 to 60% by weight.
A weight ratio of 0 to 50 is appropriate.

The conjugated diene and/or vinyl polymer emulsion used in the present invention is a radical emulsion polymerization emulsion synthesized from one or more monomers selected from ethylenically unsaturated monomers and/or conjugated cyphene monomers. It is. The art also includes all-C conjugated tzene and/or vinyl polymer emulsions for mechanical photonic foams. For example, acrylic ester polymers, styrene-butadiene polymers,
Examples include emulsions of acrylonitrile-butadiene polymers, methyl methacrylate-butanoene polymers, vinyl acetate polymers, ethylene-vinyl acetate polymers, vinyl chloride polymers, and the like. The solid content concentration of these is 30
~60% by weight, preferably 40-60% by weight.

Among these, particularly preferred are acrylonitrile-butadiene copolymers, styrene-butadiene copolymers, and acrylic acid ester copolymers containing carmexyl groups.

Conjugated dienes used in the method of the present invention include:
Butadiene-1,3,2-methyl-butadiene f-/-1
, 3,2-chlorobutadiene-1,a'4, but in consideration of copolymerizability with other monomers and economic efficiency, it is preferable to use butadiene-1,3.

Particularly preferred are ethylenically unsaturated monomers in the process of the invention. The concentration process is usually at a temperature of 50-70℃ and a pressure of 500-70℃.
Although it is carried out at 600 mmHg, there is no particular limitation.

The effects of the presence of phosphates (I) to (2) that characterize the present invention will be described below. This phosphate (I) ~(
2) has the effect of improving the mixing stability when a polyurethane emulsion is mixed with a conjugated diene and/or vinyl polymer emulsion which is different in terms of resin properties and water dispersion form properties.

Therefore, the synthetic resin emulsion of the present invention improves the stability of the synthetic resin emulsion mainly due to the presence of the phosphate salt, enables stable blending with various additives, and fully utilizes the functions of the additives. It can give rise to excitement. For example, uniform coloring and quantitative color matching are possible when mixing coloring agents, which increases the commercial value. In addition, the stability of the foamed emulsion is improved, and there are almost no problems such as bubble breakage during application or injection of the foamed emulsion, and the homogeneity of the bubbles is maintained when forming the υ foam by heat treatment. It also has the effect of increasing film thickness retention.

At the same time, it enables stable production of high-magnification foams containing a large amount of gas. Furthermore, by using phosphate (I) in the concentration process after the production of synthetic resin emulsions, it is possible to stabilize high solids concentration synthetic resin emulsions that are advantageous for foam molding, and to help in AA molding. It is.

In this way, it is possible to mix and use a polyurethane emulsion and a conjugated diene and/or vinyl polymer emulsion as a base, and the foam obtained by the present invention has fundamental strength, heat resistance, cold resistance, light resistance, and bath resistance. It can exhibit superior physical properties such as physical properties and elasticity that cannot be obtained by conventional methods.

Foaming aids added to the synthetic resin emulsion containing phosphates (I) to (g) of the present invention include sodium laurate, coconut oil soap, sodium myristate, ammonium stearate, sodium tucrumitate,
Sodium oleate, sodium higher alcohol sulfate, sodium homologue fatty acid amide alkyl sulfonate, saponin, gelatin, or casein are used. A fluorosurfactant having a perfluoroalkyl group or a fluoroalkyl group having 1 to 20 carbon atoms is also used.

Viscosity modifiers include casein, alginate, gum arabic, bentonite, clay, and Cal? Oxylated methylcellulose, polyvinyl alcohol, polyvinylpyrrolidone copolymer, polyethylene oxide polymer, polyacrylic acid emulsion, etc. are used. The amount of these added is usually 0.1 to 5 parts, preferably 0.5 to 3 parts.

The viscosity of synthetic resin emulsion is 1000-15000e
p is appropriate.

As the crosslinking agent, water-soluble melamine-formaldehyde resin, water-soluble urea-formaldehyde resin, water-soluble or water-dispersible epoxy resin, azolysine compound, polyisocyanate resin, etc. are used.

Addition of silicone oil is effective in sufficiently reflecting the elastic properties of a polyurethane resin in the properties of the resulting foam. Examples include dimethyl silicone oil, methylphenyl silicone oil, amine-modified silicone oil, and polyether-modified silicone oil. The amount added is 0.1 to 3 parts by weight per 100 parts by weight of the emulsion. Pre-emulsified silicone oil is also used.

In addition, colorants, fillers, anti-aging agents, anti-mold agents, etc. may be used within the range that does not impair the purpose of the present invention.

In this way, the synthetic resin emulsion containing phosphate (I) and adjusted to an appropriate viscosity is then foamed in a known method using CO9M latex, resulting in a synthetic resin emulsion containing uniform and fine bubbles. It can be changed to Yon. In this case, mechanical foaming is most common, but the type of foaming machine is not particularly limited, and those generally used for foaming rubber latex can be used. -An example is as follows. A synthetic resin emulsion containing a random copolymer, adjusted to an appropriate viscosity, and further containing a foaming aid, a viscosity modifier, a foam stabilizer, a crosslinking agent, etc. as necessary, is particularly preferred for gear 4 pumps. The concentration process is usually performed at a temperature of 50-70℃ and a pressure of 500-600℃.
Although it is performed at mmHg, there is no particular restriction.

The effects of the presence of phosphates (I) to (2) that characterize the present invention will be described below. This phosphate (I) ~(
2) has the effect of improving the mixing stability when a polyurethane emulsion is mixed with a conjugated diene and/or vinyl polymer emulsion which is different in terms of resin properties and water dispersion form properties.

Therefore, the synthetic resin emulsion of the present invention improves the stability of the synthetic resin emulsion mainly due to the presence of phosphorus salt, and allows stable blending with various additives.
The function of the additive can be fully developed. For example, when colorants are mixed, uniform 78 colors and constant mN colors can be produced, which has the effect of increasing commercial value. In addition, the stability of the foamed emulsion is improved, and there are almost no problems such as bubble breakage during application or injection of the foamed emulsion, and the homogeneity of air curvature is maintained when forming the foamed body through heat treatment. This has the effect of increasing the retention of the formed film thickness.

At the same time, it is possible to stably produce a high-magnification foam containing a large amount of gas Z. Furthermore, by using phosphates (I) to (lit) in the concentration step after producing the synthetic resin emulsion, it is possible to stably produce a high solids concentration hM dendrite emulsion, which is advantageous for foam molding. It is useful for

In this way, it is possible to mix and use a polyurethane emulsion and a conjugated diene and/or vinyl polymer emulsion as a paste.The foam obtained by the present invention has fundamental strength, heat resistance, cold resistance, light resistance, and It can exhibit superior physical properties such as solvent properties and elasticity that cannot be obtained with conventional methods.

Foaming aids added to the synthetic resin emulsion containing phosphates (I) to (2) of the present invention include sodium laurate, coconut oil soap, sodium myristate, ammonium stearate, and sodium curmitate. ,
Sodium oleate, higher a/l/near ap-myl ester sodium grade &7 aliphatic e7midoalkyl sulfonate, saponin, gelatin, casein, etc. are used. A fluorine-based surfactant having a 4-fluoroalkyl group or a fluoroalkyl group having 1 to 20 carbon atoms is also used.

As the viscosity modifier, casein, alginate, gum arabic, bentonite, clay, cal-oxylated methylcellulose, polyvinyl alcohol, polyvinylpyrrolidone copolymer, polyethylene oxide polymer, polyacrylic acid emulsion, etc. are used. The amount of these added is usually 0.1 to 5 parts, preferably 0.5 to 3 parts.

The viscosity of synthetic resin emulsion is 1000-15000e
p is appropriate.

As the crosslinking agent, water-soluble melamine-formaldehyde resin, water-soluble urea-formaldehyde resin, water-soluble or water-dispersible epoxy resin, azirinone compound, polyisocyanate resin, etc. are used.

Addition of silicone oil is effective in sufficiently reflecting the elastic properties of a polyurethane resin in the properties of the resulting foam. Examples include dimethyl silicone oil, methylphenylcligo/oil, amine-modified silicone oil, and polyether-modified silicone oil. The amount added is 100i of emulsion! It is used in an amount of 0.1 to 3 parts by weight. Pre-emulsified silicone oil may also be used.

In addition, colorants, fillers, anti-aging agents, anti-mold agents, etc. may be used within the range that does not impair the purpose of the present invention.

In this way, the synthetic resin emulsion containing phosphate (I) and adjusted to an appropriate viscosity is then foamed in a known method using CO9M latex, resulting in a synthetic resin emulsion containing uniform and fine bubbles. Can be changed to vI-in. In this case, mechanical foaming is most common, but the type of foaming machine is not particularly limited, and those generally used for foaming rubber latex can be used. -An example is as follows. A synthetic resin emulsion containing a random copolymer, adjusted to an appropriate viscosity, and further blended with a foaming aid, viscosity modifier, foam stabilizer, crosslinking agent, etc. as necessary, is transferred to a foaming machine using a gear 4, etc. sent. Meanwhile, gas (usually air) is pumped into the foaming machine by a compressor or the like. Each flow rate is controlled by a dart. The emulsion and gas that have been sent to the foaming machine are mixed there, and the gas that has been sent is fragmented and dispersed in the synthetic city fat emulsion by a rotating cylinder, and the foamed synthetic resin emulsion is then exited from the foaming machine. It's coming. The amount of gas mixed in (the ratio of gas to the synthetic resin emulsion), which is related to the density of the synthetic resin emulsion foam obtained by drying, is controlled by controlling the gas injection i1, and the size of the bubbles is determined by the synthetic resin emulsion. It is controlled by the viscosity of the resin emulsion and the rotation speed of the cylinder. (Note that a hand mixer is experimentally sufficient for foaming the synthetic resin emulsion.) In this case, the foaming ratio is generally 1.5 to 6.

The synthetic resin emulsion thus foamed is poured into a mold or cast onto a substrate and dried. In this case, a doctor knife is generally used to coat the substrate to a uniform thickness. The base materials include fiber fabrics, fiber knitted fabrics, textile products such as raised fabrics, flocked fabrics, non-woven fabrics, paper, polyvinyl chloride sheets, leather sheets), release papers, films with release properties such as polyzolopyrene, polyester, etc. Examples include a glass plate, a metal plate, and the like.

The applied synthetic resin emulsion containing air bubbles is dried to remove the dispersion medium (water) and obtain a foamy substance having uniform and fine air bubbles. Drying temperature is 60~
The temperature is preferably 160°C, preferably 100 to 140°C. When the emulsion is cured by heat treatment, the drying is followed by heat treatment.

(Effects) In the method of the present invention, since the foam of the synthetic resin emulsion is stable, it can be easily formed on various substrates, and the resulting foam can be used for various purposes. For example, bags, clothing, shoes,
Synthetic leather for bags, artificial leather, other fake leather coated fabrics, carpets (backings), kotatsu mats,
Entrance/bath mats, sponge sheets or other molded products, how to use it not only to form a foam, but also to act as an adhesive layer while forming a foam, to apply embossing after forming a foam, etc. may also be included. For example, a foam layer is formed between the base material (I) and the base material ω), and the base materials are fixed together at the same time, or a foam is formed on the top of one base material, and at the same time, the foam layer is formed between the base material and the other base material. These include those in which a dense base material is fixed, and foam flocking in which the foam also serves as a binder for the pile. In addition, the formed foam is subjected to post-emboss processing to give a secondarily uneven pattern. This is an example of another feature of the foam of the present invention, which is the good adhesion of the cell walls under constant heat/pressure, and the high elasticity of the remaining foam with a high expansion ratio.

The above examples of applications and uses are not intended to be limiting, but are merely examples that take advantage of the wide range of industrially advantageous foam-forming features of the present invention.

Next, the present invention will be specifically explained with reference to Examples. still,
The parts and parts indicated in the text are 9 parts and weight % unless otherwise specified.

Reference example 1 Polyoxyzolopyrene glycol (average molecular weight 1000
) and 175 parts of tolylene diisocyanate were mixed and reacted at 80° C. for 2 hours to produce a prepolymer of NCO f712, and 270 parts of toluene was added thereto to form a homogeneous solution. 140 parts of this prepolymer solution at 120 parts per minute
00 rpm, add 70 parts of an aqueous solution containing 6 parts of polyoxyethylene nonylphenol ether with 25 moles of ethylene oxide addition, and stir for 3 minutes. While slowly stirring the resulting emulsion, To,
An aqueous chain extender solution prepared by dissolving 8.2 parts of 1,6-hexamethylene diamine in 30 parts of water was added dropwise over a period of 2 minutes. After the dropwise addition, stirring was continued for 2 hours to obtain a stable polyurethane emulsion (A-1). The solid content concentration was 46 centipoise, and the viscosity was 850 centipoise.

Next, 1.0 part of sodium hexametaphosphate was added to this polyurethane emulsion (A-1), and the resulting urethane emulsion (A-2) had a solid content concentration of 55% and a viscosity of 900 cps. Ta.

Reference example 2 1 ion exchanged water in a nitrogen-substituted autoclave with a stirrer
10 parts, 1.0 part of Luxstar DS-801 (manufactured by Dainippon Ink Chemical) as a solid content, diphenyl ether sulfonic acid sol/(=ny:=y-le 271A).

Nippon Nyukazai d) 1.0 parts, 0.5 parts of tertiary dodecyl mercaptan, and 0.1 parts of ammonium ethylenediaminetetraacetate were charged, and 100 parts of the monomer composition (60 parts of butadiene, 35 parts of methyl methacrylate, 5 parts of itaconic acid) was added. ) was added with 0.5 part of potassium persulfate and stirred at 60°C until the loading rate was 99. Emulsion polymerization was carried out up to Oq6. Next, 1.0 part of sodium hexametaphosphate and 0.5 part of tribori sodium phosphate dissolved in a 10% potassium hydroxide solution were added to the polymer water after the polymerization was completed, and unreacted by steam distillation. After monomer removal and concentration, the solid content was reduced to 55゜0.
Methyl methacrylate-ptazoene copolymer emulsion (n-
1) was obtained.

The solid content was 55. Same as above except that sodium hexametaphosphate and sodium tripolyphosphate were not used. .

As a result, an aqueous polymer dispersion having a viscosity of 4500 cps and a pH of 8.7 was obtained (B-2).

Example 1 Methyl methacrylate-butadiene copolymer emulsion (B) containing 50 parts of polyurethane emulsion (A-1), sodium hexametaphosphate, and sodium tripolyphosphate
-1) Add an aqueous solution of carboxymethyl cellulose to the mixed emulsion with 50 parts to adjust the viscosity to 500 centipoise, and then add 1 part of silicone oil, 3 parts of glycerol triglycidyl ether, and 4 parts of ammonium stearate to make it uniform. mixed with.

This mixture was foamed using a continuous mechanical foaming machine (manufactured by Suga Kitan Co., Ltd.), applied onto a cotton cloth, and heat-treated at 120° C. for 8 minutes to obtain a foamed sheet with uniform fine bubbles and a smooth surface. This foamed sheet was found to be excellent in abrasion resistance, light resistance, etc.

Table 1 shows the physical properties.

Comparative Example 1 In Example 1, instead of the methyl methacrylate-butadiene copolymer emulsion (B-1) containing sodium hexametaphosphate and sodium tripolyphosphate, a methyl methacrylate-butadiene copolymer emulsion containing no sodium hexametaphosphate and sodium tripolyphosphate was used. Polymer emulsion (
B-2) was blended in the same manner as in Example 1 except that B-2) was used. Table 1 shows the physical properties.

Example 2 Polyurethane emulsion (A-1) in Example 1
The mixture was prepared in the same manner as in Example 1, except that a polyurethane emulsion (A-2) containing hexametaphosphoric acid sorta was used instead. Table 1 shows the physical properties.

Example 3 In Example 2, the methyl methacrylate-butadiene copolymer emulsion (B-1) containing sodium hexametaphosphate and sodium tripolyphosphate was replaced with a methyl methacrylate-butadiene copolymer containing no sodium hexametaphosphate and sodium tripolyphosphate. Emulsion (B-2)
The formulation was carried out in the same manner as in Example 2 except that . Table 1 shows the physical properties.

Reference Example 3 In a stainless steel reaction vessel, 120 parts of ion-exchanged water, sodium alkylbenzene sulfonate (Neoperex F-2)
5, manufactured by Kao) 0.3 parts, then ammonium persulfate 0,
4 parts of sodium bicarbonate and 0.2 parts of sodium bicarbonate were charged and dissolved, and the temperature was raised to 75 to 80°C in a nitrogen stream. Two parts of N-methylolmethacrylamide was mixed with three parts of water using 0.3 parts of alkylbenzenesulfonic acid sorter (Neoperex F-25, Kao m).
0 parts of a monomer emulsion was charged to start polymerization. After 30 minutes, add the remaining monomer emulsion at the same temperature.
The mixture was added dropwise over a period of 80 minutes, and after copolymerization, the mixture was maintained for 30 minutes to complete the copolymerization.

The solid content at the end of emulsion polymerization was 44.5%. Next, 1.0 part of sodium pyrophosphate dissolved in water was added to the synthetic resin emulsion after emulsion polymerization and concentrated to give a solid content of 55.0%, a viscosity of 250 cps, and a pH of 7.
A synthetic resin emulsion (C-1) of No. 0 was obtained.

Example 4 The procedure of Example 1 was repeated except that 100 parts of methyl methacrylate-butadiene copolymer emulsion (B-1) containing sodium hexametaphosphate and sodium tripolyphosphate was used alone. Table 1 shows the physical properties.

Example 5 The same procedure as in Example 1 was carried out except that 100 parts of the urethane resin emulsion (A-2) containing sodium hexametaphosphate was used alone. Table 1 shows the physical properties.

Example 6 In JM Example 1, the acrylic copolymer emulsion (C-1) containing sodium pyrophosphate was substituted for the methyl methacrylate-butadiene copolymer emulsion (B-1) containing sodium hexametaphosphate and sodium tripolyphosphate. The procedure was the same as in Example 1 except that the sample was used in Example 1. Table 1 shows the physical properties.

Claims (1)

[Scope of Claims] Metaphosphate (I), polyphosphate (II), and ultraphosphate (III) represented by the following structural formula alone or in combination
Mechanically foaming a synthetic resin emulsion containing at least one species, applying the foaming liquid onto a base material or injecting it into a mold,
A method of forming a foam, the method comprising: subsequent heat treatment. (I) (MPO_3)_n M
;Na, K, Ca (II) M_n_+_2P_nO_3_
n_+_1 n; Positive integer (III) Na_2P_4O_
1_1 2. The method for forming a foam according to claim 1, wherein the synthetic resin emulsion is a polyurethane emulsion, a conjugated diene, and/or a vinyl polymer emulsion alone or a mixed emulsion thereof.