JPS6241237A - Formation of flame-retarding form from synthetic resin emulsion - Google Patents

Abstract

PURPOSE:To form a flame-retarding foam improved in strength, durability, etc., by foaming a liquid mixture of a specified synthetic resin emulsion containing a specified substance and a flame retardant and heating it after applying to a base or pouring into a mold. CONSTITUTION:A liquid mixture of a synthetic resin emulsion comprising a polyurethane emulsion (A) and a conjugated diene and/or a vinyl polymer emulsion (B) and containing an ethylene oxide/propylene oxide/propylene oxide random copolymer (D) and a flame retardant (C) is mechanically foamed. By heating the foamed liquid after applying to a base or pouring into a mold, a flame-retarding foam is formed. This foam can be used to form a foam layer closely bonded to a base such as a fabric or to be poured into a mold to obtain a foamed molding which can retain its shape. Because of its flame retardance and high performances such as improved strength or durability, it is useful in a variety of industrial fields and is particularly suitable as a flame-retarding formed coating for a car seat.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for forming a flame-retardant foam from a specific synthetic resin emulsion containing a specific substance and a flame retardant. Oxidorundum; relates to a method for stably forming a high-strength flame-retardant foam modified from a urethane emulsion containing a polymer, a conjugated diene and/or vinyl polymer emulsion, and a flame retardant.

The flame-retardant foam of the present invention can form a foam layer that adheres to a base material such as a textile or a foam molded product that can maintain its shape by being injected into a mold, and has flame retardancy and property modification. Due to its high physical properties, it is useful in a wide range of industrial fields. It is particularly suitable for use as a flame-retardant foam coating for car seats.

[Conventional technology]

Conventionally, blowing agents, coagulants, crosslinking agents, and other additives are added to natural and synthetic resin emulsions, the foam is mechanically foamed, and this is applied onto a substrate or poured into a mold, and then dried, solidified, and cured. A method is known in which foams are formed by Such natural and synthetic resin emulsions include natural rubber latex, styrene-butadiene copolymer emulsion, acrylonitrile-butadiene 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 light weight, wall thickness, texture, and feel.

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 higher durability are required. For example, natural comb and butadiene copolymers improve durability such as light resistance and heat resistance, and mechanical strength, while acrylic ester copolymers improve mechanical strength and solvent resistance. ,
It is necessary to improve cold resistance, elasticity, etc.

In addition, many proposals have been made for forming foams from I-urethane emulsions, and these foams are attracting attention as having high performance that has improved the above-mentioned drawbacks. However, the previously proposed mechanical foaming method for polyurethane emulsion is not satisfactory in terms of foam moldability, and it has not been possible to utilize the resin's original properties for a wide range of applications, and improvements are needed. It is. For example, it is unsatisfactory in terms of stable and wide foaming moldability, which allows it to freely form foams with high expansion ratios and high coating thicknesses, and improvements are needed.

On the other hand, it is known that a flame retardant is added to a synthetic resin emulsion and applied to a base material (non-foamed) to impart flame retardancy, but the combined use of a flame retardant tends to reduce the strength of the synthetic resin film. It is in. This is because flame retardants are generally in liquid or insoluble powder form.

It has also been proposed to add a flame retardant to a synthetic resin emulsion, mechanically foam it, and apply the foamed liquid to a substrate to impart flame retardancy. For example, in 1977, special public interest was created based on a vinylidene chloride synthetic resin emulsion based on a special manufacturing method.
There is No.-24272. There is also a proposal suggesting the possibility of incorporating flame retardants into general polyurethane emulsion foams (Japanese Patent Publication No. 36112/1982). However, the former requires a large amount of chlorine content and has the disadvantage of being inferior in flexibility and rebound. Addition only makes things worse.

In this way, foaming from an acid-containing resin emulsion.

In addition to these properties, the foam has excellent physical properties such as high strength and high durability, and foam moldability that allows it to freely grow into a stable and industrially useful form. Although there has been a strong demand for flame retardancy, it has not been possible to achieve this.

[Problem that the invention seeks to solve]

An important and difficult technical issue in such prior art is foam moldability. That is, when the emulsion is foamed, the air bubbles are finely and uniformly removed and maintained, and the air bubbles are caused to coalesce or disappear from the water content of the emulsion, which essentially has no strength, and forms the partition wall containing the air bubbles. It is possible to form a resin film strong enough to withstand permanent bubble retention without causing any damage. That is, 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.'! The point is that it requires certain characteristics. Therefore, the method of improving physical properties by combining different types of emulsions, which is used in non-foaming systems, is difficult in foaming systems because the dispersion stabilizing ability and destabilizing ability of each emulsion are different. . Furthermore, it has become increasingly difficult to create a metal band 1 in which a flame retardant is added to these systems, since the stability of compatibility, film formation (fusion), blocking resistance, etc. are inhibited. In fact, in the case of a mixed emulsion of a polyurethane emulsion and a styrene-butadiene copolymer emulsion and a flame retardant according to the prior art, the viscosity increased significantly during mechanical foaming and solidified into a tofu-like shape, or a large number of coarse bubbles were mixed in. It is one of those products that can only be obtained as a foam and has no commercial value. The same is true for mixed emulsions of polyurethane emulsions and acrylic acid ester copolymer emulsions and flame retardants.Especially when molding at high expansion ratios and high coating thicknesses, the bubbles become coarse. The product value of the foam was lost due to the disappearance of the foam. Of course, it is not impossible to obtain something that has some commercial value with a low expansion ratio and low coating thickness (for example, about 1fi thickness), but it is possible to significantly improve both the physical properties and foam moldability of the foam. It was not possible to do so, and the above requirements could not be met.

[Means for resolving the gap]

The present inventors have developed a foam made from a synthetic resin emulsion that has significantly improved foam physical properties such as strength and durability, flame retardancy, and foam moldability that allows it to be freely molded into stable and industrially useful forms. As a result of extensive research into the moldability of foams, it was discovered that by using a mixture of a specific synthetic resin, Emulzolone, containing a specific substance, and a flame retardant, excellent physical properties and flame retardance as well as excellent foam moldability can be imparted to the foam.The present invention has been made. reached.

Namely, the present invention is directed to a synthetic resin emulsion containing ethylene oxide/glopylene oxide random copolymer (D), namely (A) polyurethane emulsion) (B)
Mechanically foaming a mixed liquid of emulzolone mixed with a conjugated diene and/or vinyl polymer emulsion and a flame retardant (C), applying the foamed liquid onto a substrate or injecting it into a mold, and then heat-treating. A method of forming a flame retardant high strength foam is provided.

An object of the present invention is to provide a foam having excellent mechanical strength, flame retardance, heat resistance, cold resistance, light resistance, solvent resistance, and elasticity. Another object is to provide Emulzolone, which has industrially useful foam moldability that allows the formation of such high-performance foams in stable and wide forms. Yet another purpose is to develop a method for forming a flame-retardant foam with excellent physical properties and moldability from an emulsion that is a mixture of I-urethane emulsion and other emulsions obtained by completely different manufacturing methods. It is about providing.

[Effect]

According to the present invention, a flame retardant, a foaming aid, a viscosity modifier, a foam stabilizer, a crosslinking agent, etc. are added to a synthetic resin emulsion containing an ethylene oxide/glopylene oxide random copolymer, and a gas (mainly, Blow air), stir to foam, apply the foaming liquid onto a base material or pour it into a mold,
Then, by heat treatment, high expansion ratio and high speed processing (
Flame-retardant foam with uniform porous surface smoothness and excellent mechanical strength and durability even under conditions such as high-speed discharge, application, and drying using a continuous mechanical foaming machine, and high I fabric thickness. is obtained.

〔composition〕

The polyurethane resin used in the present invention is already known and can be produced by various methods. For example, an emulsified IJ urethane solvent solution or a polyhydroxy compound having a hydroxyl group at the end and an excess of organic polyisocyanate than the stoichiometric amount as basically described in Japanese Patent Publication No. 33-1141. react,
Then, a polyurethane emulsion obtained by emulsifying the obtained bre polymer in an aqueous dispersion medium using a surfactant and adding a chain extender to this to extend the chain of the bre polymer can also be used. can.

Such polyhydroxy compounds usually have a molecular weight of 300
-4000 preferably 600-3000,
Typical examples include polyether 7 reols and polyester polyols.

d? I7 ether polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1
．． 2-7'ropylene glycol, trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, glycerin, sorbitol, sucrose, aconitic acid, trimellitic acid, hemimellitic acid, phosphoric acid, One or more compounds having at least two active hydrogen atoms, such as ethylene diamine, propylene diamine, diethylene triamine, triynegulonolamine, pyrogallol, dihydrobenzoic acid, hydroxyphthalic acid, 1,2,3-pronocuntrichiol, etc. It is produced by addition polymerization of one or more monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc. by a conventional method using as an initiator.

On the other hand, polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol,
At least 1.2-f robylene glycol, trimethylene glycol, 1.3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, glycerin, trimethylolglobin, pentaerythritol, sorbitol, etc. One or more compounds having two hydroxyl groups and malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, pimelic acid, sepacic acid, oxalic acid, phthalic acid, terephthalic acid, hexahydrophthalic acid. It is produced by condensation polymerization of one or more compounds having at least two calxyl groups, such as acid, aconitic acid, trimellitic acid, hemimellitic acid, etc., by a conventional method.

Polyhydrocarbon compounds such as polyether polyols and polyester polyols can be used alone or in combination of two or more, and further include ethylene glycol, diethylene glycol, triethylene glycol, 1.2- Propylene glycol, trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol.

It can be used in admixture with low molecular weight polyols such as glycerin, trimethylol chloride, intererythritol, sorbitol and the like.

Examples of the organic I diisocyanate include aliphatic, cyclic, or aromatic polyisocyanates, such as 2.4-)lylene diisocyanate, 2.6-)lylene diisocyanate, 4,4'-diphenylmethane diisocyanate, m-phenylene diisocyanate, and xylylene diisocyanate. , tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate,
1.4-cyclohexylene diisocyanate, 4.4'
-dicyclohexyl diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3
．． 3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-piphenyl diisocyanate) -3,3'-3,3-dichloro-4,4'-pipheny diisocyane), 1.5-
Naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, diphenyl-2,4,4-
) diisocyanates, etc.

Chain extenders are compounds having at least two active hydrogen atoms capable of reacting with incyanate groups, such as ethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, monoethanol alumine, ethylenediamine, triethylenecyamine. , 1.2-propylenezamine, hexamethylenediamine, N-ethanolethylenediamine, N,N'-jetanolethylenediamine, m-7 enylenediamine,
2.4-) Glycols, alkanolamines, diamines such as lylenediamine, bis-4-aminophenylmethane, 3,3'-dichloro-4,4'-cyaminodiphenylmethane, piperazine, 2-methylpipedecine, etc. As a representative example, a reaction product of 1 mole of alkylene diamine and 2 moles of acrylamide, or a reaction product of 1 mole of alkylenezamine and 2 moles of acrylonitrile can also be used.

In the case of the present invention, the concentration of the I-urethane emulsion is not particularly limited, but considering the economic efficiency during drying and the homogeneity of the foam material, the concentration is preferably 30 to 60% by weight, preferably 40 to 50%.
The weight section is appropriate.

The conjugated diene and/or vinyl polymer emulsion used in the present invention is synthesized by radical emulsion polymerization from one or more monomers selected from ethylenically unsaturated monomers and/or conjugated diene monomers. It is an emulsion. It includes all mechanically foamable conjugated diene and/or vinyl polymer emulsions in the art. For example, acrylic ester polymers, styrene-butadiene polymers, acrylonitrile-butadiene polymers, methyl methacrylate-butadiene polymers, vinyl acetate polymers, ethylene-vinyl acetate polymers, and vinyl chloride polymers. Examples include emulsions such as The solid content concentration of these is 30-6
03ii-t, preferably 40-60% by weight.

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

Conjugated dienes used in the method of the present invention include:
butadiene-1,3,2-methyl-butadiene-1,3
, 2-chlorptazoene-1,3, etc., but it is preferable to use butadiene-1,3 in consideration of copolymerizability with other monomers and economical efficiency.

Examples of ethylenically unsaturated monomers used in the method of the present invention include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, and acrylic acid. Alkyl acrylates and alkyl methacrylates exemplified by pentyl, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, octyl acrylate, octyl methacrylate, octadecyl acrylate, octadecyl methacrylate, etc. Ester; Ethylenically unsaturated aromatic monomer exemplified by styrene, α-methylstyrene, vinyltoluene, chlorstyrene, 2,4-dipromustyrene, etc.; Unsaturated nitrile such as acrylonitrile, methacrylonitrile; Acrylic acid , methacrylic acid, crotonic acid, maleic acid and its anhydride, fumaric acid, itaconic acid, and unsaturated radicals? Ethylenically unsaturated carboxylic acid monoalkyl esters, monomethyl maleate, monoethyl fumarate, mono-n-butyl itaconate, etc. vinyl esters such as vinyl acetate and vinyl gropionate; vinylidene halides such as vinylidene chloride and vinylidene bromide; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, etc. hydroxyalkyl esters of ethylenically unsaturated carboxyl acids such as; glycidyl esters of ethylenically unsaturated carboxyl acids such as glycidyl acrylate, glycidyl methacrylate, and acrylamide, methacrylamide;
Examples include radically polymerizable skin polymers such as N-methylol acrylamide, N-methylol methacrylamide, N-butoxymethyl acrylamide, and diacetone acrylamide.

When mixing the polyurethane emulsion and the conjugated diene and/or vinyl polymer emulsion (B), the mixing ratio is CA)/(B) = 80/20 to 10/9.
It is preferable that it is 0 (solid content weight ratio). If the polyurethane emulsion has a weight ratio of less than 10, a foam with high strength and high durability, which is one of the objectives of the present invention, cannot be obtained.
Furthermore, if the weight of the polyurethane emulsion exceeds 80% by weight, the wide foaming moldability, which is one of the objects of the present invention, is impaired, and the object of the invention cannot be accomplished. However, this does not preclude deviating from the above range in order to achieve other objectives at the expense of part of the present invention. The resin concentration in the mixed emulsion should be 4, considering economic efficiency and high foam moldability.
0 to 60% by weight, particularly 45 to 55% by weight, is preferred.

It should be noted that this does not hinder pH adjustment or particle size adjustment prior to mixing the emulsion, and may be preferable in some cases.

The ethylene oxide/propylene oxide copolymer (D) used in the present invention is made from ethylene oxide using monoalcohols such as methyl alcohol, ethyl alcohol, furoyl alcohol, butyl alcohol, polyalcohols such as ethylene glycol and glycerin, and polyamines as starting materials. and propylene oxyr '95~5
It can be produced by adding randomly at a molar ratio of 0:5 to 50. Although not particularly limited to this, ethylene oxide has a mole content of 50 to 95, preferably 70 to 95.
90 mol, propylene oxide 5 to 50 mol, preferably 10 to 30 mol, and preferably has a viscosity of 3,000 to 50,000 ape at 38°C. A typical example is Tergitol XD (manufactured by TYCC). Amount of ethylene oxide/propylene oxide random copolymer: 0.01 to 10 parts by weight, preferably 0.05 parts by weight, based on 100 parts by weight of the synthetic resin emulsion
~5 parts by weight.

There is no particular restriction on the timing of adding the ethylene oxide/propylene oxide random copolymer, but it is preferable to add it to the synthetic resin emulsion in advance and to homogenize it before adding the additives.

It is particularly preferable to use it as part or all of an emulsifier during emulsion polymerization of both or one of a polyurethane emulsion and a conjugated diene and/or vinyl polymer emulsion.

The effects of the presence of ethylene oxide/propylene oxide random copolymer (abbreviated as random copolymer) that characterize the present invention will be described below. This random copolymer is a conjugated diene and/or vinyl polymer emulsion that is different from polyurethane emulsions in terms of resin properties and moisture morphology properties! Improves miscibility stability when used in combination with In addition, as an additional effect, by using it as part of an emulsifier during polymerization, it is useful for stably producing a high concentration emulsion that is advantageous for foam molding.

In addition, random copolymers increase the retention of blown air, making it possible to achieve a high expansion ratio (for example, around 6 times).
Since it also has the effect of improving mechanical stability, it also improves suitability for high-speed processing using a continuous mechanical foaming machine.

Moreover, the random copolymer has a
To help solidify quickly at 80℃),
It suppresses the decrease in bulk due to heat treatment and enables high coating thickness (for example, around 5 layers). It should be noted that the behavior is completely different from that of ethylene oxide/propylene oxide block copolymers, which are obtained from similar components and are also commonly used as emulsifiers.

Conventionally used ethylene oxide/propylene oxide block copolymers, such as Zolronic F-
88 (manufactured by Jishu Kakogyo ■, ethylene oxide/propylene oxide = 80,720 weight ratio, molecular weight approximately 12,000
In the case of solids, the ability to retain air in the foaming liquid during foaming and the mechanical stability of the foaming liquid are poor, and the volume tends to decrease and the bubbles become coarser during heat treatment and burial. It is not possible to stably convert a good foam into cedar bark.

The foam obtained by the present invention has excellent mechanical strength, heat resistance, cold resistance, light resistance, solvent resistance, and repulsion. It can exhibit excellent physical properties such as elasticity and flame retardancy that cannot be obtained with conventional methods.

The flame retardant (C) used in the present invention is not particularly limited, but it is preferably one that does not reduce the performance of the synthetic resin emulsion or base material, and one that does not reduce the foamability of the bottom shape during the foaming process. and those that do not reduce the heat resistance and light resistance of processed products, and those that are less toxic and corrosive, such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tris (halozolovir) phosphate, tris (haloethyl) phosphate. Phosphorus esters such as chlorinated) L? Roughin, chlorinated polyethylene/9-chloro-pentane clodecane, hexabromobenzene, decabromodiphenyl oxide, tetrabromobisphenol A, hexabromocyclododecane and other halone-containing organic compounds, ammonium bromide, antimono dioxide, aluminum hydroxide , antimonate, barium metaborate, and other inorganic compounds alone or in a mixture of two or more thereof.

The mixing ratio of the flame retardant and the synthetic resin emulsion is not particularly limited, but preferably the solid content weight ratio of the flame retardant/synthetic resin emulsion is 10/90 to 70/30.

Foaming aids added to the synthetic resin Emulson, including random copolymers, include sodium laurate, coconut soap, sodium myristate, ammonium stearate, palmitic acid, sodium oleate, and higher alcohols. sodium sulfate ester,
Sodium higher fatty acid amidoalkyl sulfonate, saponin, gelatin, casein, etc. are used. A fluorosurfactant having a perfluoroalkyl group or a fluoroalkyl group having 1 to 20 carbon atoms is also used.

As the viscosity modifier, casein, alginate, gum arabic, bentonite, clay, carboxylated methylcellulose, folivinyl alcohol, I-rivinylpyrrolidone copolymer, polyethylene oxide nolimer, polyacrylic acid emulsicon, etc. are used. The amount of these added is usually 0.1 to 5 parts, preferably 0.5 to 3 parts.

A suitable viscosity is 1,000 to 15,000 cpS.

As the crosslinking agent, a water-bathable melamine-formaldehyde resin, a water-bathable urea-formaldehyde resin, a water-soluble or water-dispersible epoxy resin, an asolinone compound, etc. are used.

Addition of silicone oil is effective in order to fully reflect the elastic properties of the foam, which are similar to those of polyurethane resins. 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 100M parts of the emulsion. Pre-emulsion silicone oil is also used.

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

In this way, the synthetic resin emulsion containing the ethylene oxide/propylene oxide random copolymer and adjusted to an appropriate viscosity is then foamed in rubber latex by a known method to convert it into a synthetic resin emulsion having uniform, fine cells. 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 and a flame retardant, adjusted to an appropriate viscosity, and further blended with a foaming aid, viscosity modifier, foam stabilizer, crosslinking agent, etc., is processed by a foaming machine using a gear pump, etc. will be sent to. Meanwhile, gas (usually air) is pumped into the foaming machine by a compressor or the like. Each flow rate is r-
controlled by seo. The emulsion and gas fed into the foaming machine are mixed there, and the gas fed is finely divided and fractionated into a synthetic resin emulsion by a rotating cylinder, and the foamed synthetic resin emulsion is then released from the foaming machine. come. 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 amount of gas injected, and the size of the bubbles is controlled 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 woven fabrics, fiber knitted fabrics, textile products such as raised fabrics, flocked fabrics, and nonwoven fabrics, paper, polyvinyl chloride sheets, leather sheets, release paper, films with release properties such as polypropylene and polyester, and glass plates. , a metal plate, etc., respectively.

By drying the applied synthetic resin emulsion containing air bubbles, the dispersion medium (water) is removed, and a foamy material having uniform and fine air bubbles is obtained.

Drying temperature is 60-160℃, preferably 100-140℃
It is. When the emulsion is cured by heat treatment, the drying is followed by heat treatment.

〔Effect of the invention〕

Foams according to the present invention can be formed on various substrates and used in various applications. For example, synthetic leather for bags, clothing, shoes, bags, etc., artificial leather, and other fake leather coated fabrics,
Car seat backings, car kits (° backings), kotatsu mats, entrance/bath mats, sponge sheets or other molded products, how to use them not only to form foam but also to serve as an adhesive layer while forming foam. It may also include methods of use in which a foam is formed and then engosed, for example, a foam layer is formed between the base material (1) and the base material (II), and the base materials are fixed together at the same time. These include those in which a foam is formed on the upper part of one base material and the same base material and another dense base material are fixed at the same time, and foam flocking in which the foam also serves as a binder for the pile. Also, what about the formed foam? It is a material that has been subjected to a process to give it a secondary 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 limiting, but 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. same,
Unless otherwise specified, all portions and weights indicated in the text are weight percentages.

Reference Example 1 I-lioxyglopylene glycol (average molecular weight 1000
) and 175 parts of tolylene diisocyanate were mixed and reacted at 80° C. for 2 hours to produce a prerimer having an NGO equivalent of 712. To this was added 270 parts of toluene 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 gently stirring the resulting emulsion, to this,
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 slowly for 2 hours to obtain a stable polyurethane emulsion (A-1). The solid content concentration was 46 centipoise, and the viscosity was 850 centipoise.

Reference Example 2 Ethylene oxide-propylene oxide block co-I lima was added to 210 parts of a prepolymer solution obtained from 525 parts of polyester diol (average molecular weight 1050) obtained from diethylene glycol and adipic acid, 222 parts of inphorone diincyanate, and 300 parts of toluene. - (Zoluronic F-88: manufactured by Kadenka Kogyo) 106 parts of an aqueous solution containing 6 parts was added to form an emulsion, and 36 parts of an aqueous solution containing 6 parts of piperazine was added thereto and reacted in the same manner as in Reference Example 1. A stable polyurethane emulsion (A-2) was obtained. The solid content concentration was 46% and the viscosity was 900 centipoise.

Reference Example 3 A hexamer consisting of 60 parts of butadiene, 30 parts of acrylonitrile, and 10 parts of methacrylic acid was mixed with ethylene oxide.
0.5 parts of propylene oxide random copolymer (Targitol D trademark), 2 parts of sodium alkylbenzenesulfonate, 0.5 parts of sodium pyrophosphate, 0.1 il of ammonium ethylenediaminetetraacetate, 0.3 parts of tertiary dodecyl mercaptan, 0 potassium persulfate. Polymerization was carried out in an autoclave equipped with a stirrer in the presence of 120 parts of ion-exchanged water and 6Q'C for 12 hours. Then, after adding potassium hydroxide and adjusting the pi to 48.5,
Unreacted monomers were removed and concentrated to obtain a stable acrylonitrile-butadiene copolymer emulsion (B-1) containing an ethylene oxide-propylene oxide random copolymer. Solid concentration 55%, viscosity 1
It was 00 cm 2 size.

For values without using Tergitol Ω, a stable emulsion (B-2) was obtained in the same manner as above. The solid content concentration was 55 cm, and the viscosity was 2000 centipoise.

Reference example 4 70 parts of ethyl acrylate, 25 parts of methyl methacrylate,
A hexamer consisting of 5 parts of acrylic acid was polymerized in the presence of 3 parts of sodium alkylbenzenesulfonate, 0.3 parts of potassium persulfate, and 150 parts of ion-exchanged water at 60 DEG C. over a period of 4 hours. Next, stripping was performed to obtain a stable emulsion (B-3). Solid concentration 60chi, viscosity 15
00 centipoise.

Reference Example 5 Hexabromocyclododecane (hereinafter referred to as HBCD) 4
78. ! i+,! Mix 20J of J geninsulfonate, 2g of Calxyl methylcellulose, and 500 parts of water, and use an emulsifier to make a stable flame retardant aqueous dispersion (C-1) with a concentration of 50%.
) was obtained.

Reference Example 6 A flame retardant (C
-2) was obtained.

Reference Example 7 23 parts of polyoxyethylene nonylphenol ether with 12 moles of ethylene oxide added was dissolved in 450 parts of tris÷2-chloropropyl) phosphate, and water was added in the usual manner to emulsify the phase inversion emulsification to obtain a milky white product with a concentration of 50%. An emulsion (C-3) was obtained.

Reference Example 8 350 parts of 5000 polyphosphonate compound and Tris+
Add 100 parts of 2-chloroethyl) phosphate, dissolve 20 parts of polyoxyethylene nonylphenol ether with 20 moles of ethylene oxide, and add water in a conventional manner to emulsify by phase inversion to obtain a milky white emulsion (C- 4) was obtained.

Example 1 50 parts of polyurethane emulsion (A-1), acrylonitrile-butadiene copolymer emulsion (B-2)
) 50 parts, 40 parts of flame retardant (C-1) and Tergitol °C
An aqueous solution of carboxylmethyl cellulose was added to a mixed emulsion with 5 parts of a 10% aqueous solution of 10% of the above mixture to give a viscosity of 8,000 centimeters. Then, 1 part of silicone oil and 4 parts of glycerol triglycidyl ether were added and mixed uniformly. This mixture is processed using a continuous mechanical foaming machine (manufactured by Suga Kikai).
The foamed sheet was foamed in a vacuum cleaner, applied on cotton broadcloth and polyester napkin, 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.

Examples 2 to 4 40 parts of flame retardant (C-2) in place of 40 parts of flame retardant (C-1)
A foam sheet was obtained in the same manner as in Example 1 except that
Example 2), and a foamed sheet was obtained in the same manner as in Example 1 except that 40 parts of the flame retardant (C-3) was used instead of 40 parts of the flame retardant (C-1) (Example 3); A foamed sheet was obtained in the same manner as in Example 1 except that 40 parts of the flame retardant (C-4) was used in place of the flame retardant (C-1) (Example 4). The physical properties are shown in Table-1.

Comparative Example 1 A foamed sheet was obtained in the same manner as in Example 1 except that the flame retardant (C-1) was omitted. The physical properties are shown in Table-1.

Comparative Example 2.3 Polyurethane emulsion (A-1) and Tergitol °C
A foam sheet was obtained in the same manner as in Example 2 except for (
Comparative Example 2). Further, a foamed sheet was obtained in the same manner as in Example 3 except that the polyurethane emulsion (A-1) and Tergitol °C were omitted (Comparative Example 3). The physical properties are shown in Table-1.

Comparative Example 4 A foamed sheet was obtained in the same manner as Comparative Example 2 except that the flame retardant (C-2) was removed. The physical properties are shown in Table-1.

Example 5 50 parts of polyurethane emulsion (A-1), acrylonitrile-butadiene copolymer emulsion (B-1)
A foamed sheet was obtained in the same manner as in Example 1 using 50 parts of the flame retardant (C-2) and 40 parts of the flame retardant (C-2).

The physical properties are shown in Table-1.

Example 6 A foam sheet was made in the same manner as in Example 1 using 50 parts of polyurethane emulsion (A-2), 50 parts of acrylic acid ester emulsion (B-3), and flame retardant (C-2). Obtained. The physical properties are shown in Table-1.

Comparative Example 5 A foamed sheet was obtained in the same manner as in Example 5 except that the flame retardant (C-2) was omitted. The physical properties are shown in Table-1.

Comparative Example 6 A foamed sheet was obtained in the same manner as in Example 6 except that the flame retardant (C-2,) was omitted. The physical properties are shown in Table-1.

Comparative Example 7 Except for vinyl copolymer emulsion (B-t),
A foamed sheet was obtained in the same manner as in Example 5.

The physical properties are shown in Table-1.

Comparative Example 8 A foamed sheet was obtained in the same manner as in Example 5, except that the vinyl copolymer emulsion (B-1) and the random copolymer (D) were removed. The physical properties are shown in Table-1.

Regarding Table-1 ■A is A-1 and A-2 of the polyurethane aqueous dispersion obtained in Reference Example 1, and B is B of the conjugated diene and/or vinyl polymer emulsion obtained in Reference Example 2゜3. −
1, B-2, B-3, pc is the flame retardant C-1 to C-11 shown above and in Table-1, D represents ethylene oxide-propylene oxide random copolymer,
A/B/C is their solid content weight ratio.

0 In the table, (a) is the case when 1 inch of the 2x foaming liquid is applied on the cotton broadcloth, and (b) is the case when the 5x foaming liquid is applied 511cm on the cotton broadcloth.
m is applied, and p is when 5 mx of the 5x foaming solution is applied to the back side of the polyester napkin.

■ "State of the foaming liquid" refers to the state of bubbles when the mechanically foaming liquid is received in a 500 cc beaker, and the upper layer after leaving it for 5 minutes.
The state of the bubbles was observed and compared with that when c+++ was scraped off.

◎: Bubbles are fine and uniform with no change. 0: The bubbles are fine and uniform, but become slightly coarser. Δ: Bubbles were slightly non-uniform and quite coarse. ×: Contains many coarse bubbles and is significantly non-uniform.

(2) "State of foam" was observed by observing the state of cells and the smoothness of the surface of the cross section of the foam after coating and drying.

◎: The bubbles are fine and uniform, and the surface is smooth. ○: There are coarse bubbles and the surface smoothness is slightly inferior. △: Bubble is rough and there are some cracks. ×: There are cracks.

■ "Abrasion strength" was measured using a Gakushin type friction tester (flat method, load 5ooy, number of times until breakage).

◎: 500 times or more Good 0: 499-2001 times Δ: 1
99-50 times: 49 times or less.

(2) Light resistance was determined by examining the degree of discoloration and abrasion strength after 20 hours of irradiation using a fade meter.

Degree of discoloration ◎: No discoloration Δ: Slight yellowing ×: Significant discoloration (yellow-browning).

■ "Flame retardancy" was determined by measuring the burning rate in accordance with the MVSS-302 standard. Unit: CrrL/ml n.

N: Fire extinguished by the start line n2 burning rate 5cIrL
/min, and extinguished within 1 minute.■ "Hand" was examined by hand touch.

Claims (1)

[Claims] A mixed solution of (A) a polyurethane emulsion, (B) a conjugated diene and/or vinyl polymer emulsion, and (D) a synthetic resin emulsion containing an ethylene oxide/propylene oxide random copolymer, and (C) a flame retardant is machined. 1. A method for forming a flame-retardant foam, which comprises foaming the foam, coating the foaming liquid on a substrate or injecting it into a mold, and then heat-treating the foam.