JP2003165914A - Aqueous resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an aqueous resin composition capable of giving excellent flame retardance essentially containing no halogen compound, in more details, its content of the halogen compound is not more than 1,000 ppm, and it must contains a polymer compound having hydroxy group and a phosphorus flame retardant. <P>SOLUTION: This aqueous resin composition is the one having a halogen content of not greater than 1,000 ppm and hydroxy group, and it has a solid content of 10-65 wt.%, and it contains 70-97 wt.% polymer compound having hydroxy group and 3-30 wt.% phosphorus flame retardant based on the solid content. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous resin composition. More specifically, it relates to an aqueous resin composition containing an acrylic polymer.

[0002]

2. Description of the Related Art A water-based resin composition containing a flame retardant is in the form of, for example, an aqueous resin dispersion containing a flame retardant, and is difficult to apply to these fiber products as a fiber treatment agent for carpets, curtains and the like. Used to impart flammability. Such water-based resin compositions have attracted attention in various fields due to their functionality and safety due to being water-based, but at present, halogen compounds that are highly effective in suppressing oxidation reactions during combustion are flame retardants. The one used as is widely used.

As described above, an aqueous resin composition using a halogen compound as a flame retardant is disclosed in JP-A-2-2659.
No. 73 discloses a resin aqueous emulsion obtained by adding 0.3 to 100 parts by weight of an organic halide of a flame retardant to 100 parts by weight of an unsaturated monomer and carrying out emulsion polymerization. Further, JP-A-5-25447 also discloses a resin aqueous emulsion containing a halogen atom as a flame retardant component. Furthermore, JP-A-8-34893
Japanese Patent Laid-Open Publication No. 2003-242242 discloses a flame-retardant resin aqueous emulsion composition obtained by adding a flame retardant to a resin aqueous emulsion mixed liquid having a specific composition in a ratio of 1 to 20 parts by weight based on 100 parts by weight of the total resin solid content of the mixed liquid. Regarding the products, examples using a halogen compound, antimony trioxide, or antimony pentoxide as a flame retardant are disclosed.

However, although an aqueous resin composition containing these halogen compounds can impart flame retardancy, it may pollute the environment.
With the recent increasing awareness of environmental issues, there is a demand for substances that do not substantially contain halogen compounds. On the other hand, when a non-halogen compound is used as the flame retardant, it is usually impossible to impart the same flame retardancy as when the halogen compound is contained. Therefore, there was room for research on a water-based resin composition that does not substantially contain a halogen compound and that can impart flame retardancy equivalent to that when a halogen compound is contained.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides an aqueous resin composition capable of imparting excellent flame retardancy without substantially containing a halogen compound. The purpose is to do.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted various studies on water-based resin compositions capable of imparting flame retardancy, and have generally found that the effect of imparting flame retardancy to halogen compounds is inferior. By using the phosphorus-based flame retardant that becomes a water-based resin composition having a hydroxyl group, paying attention to the fact that excellent flame retardancy can be imparted by the synergistic effect of the presence of the phosphorus-based flame retardant and the hydroxyl group. It has been conceived that the above-mentioned problems can be successfully solved by appropriately adjusting the existing amounts of the flame retardant and the hydroxyl group.
Further, a high molecular compound having a hydroxyl group, for example, by adding an acrylic polymer having a hydroxyl group or a compound having a hydroxyl group, the aqueous resin composition will have a hydroxyl group. It is preferable to use, and when this acrylic polymer is polymerized in the presence of a phosphorus-based flame retardant, the phosphorus-based flame retardant easily disperses uniformly and eliminates stickiness and flame retardancy caused by the flame retardant. They have also found that they can be achieved and have reached the present invention.

That is, the present invention is an aqueous resin composition having a halogen compound content of 1000 ppm or less and having a hydroxyl group, wherein the aqueous resin composition has a solid content of 1
0 to 65% by weight, with the solid content being 100% by weight, the polymer compound having a hydroxyl group is 70 to 97% by weight,
It is an aqueous resin composition containing 3 to 30% by weight of a phosphorus-based flame retardant. The present invention is described in detail below.

The water-based resin composition of the present invention is specifically an emulsion type resin composition. The aqueous system in the present invention means that water is a main component, but may contain an organic solvent as long as the action and effect of the present invention are not impaired. As the organic solvent, for example, methanol, ethanol, isopropyl alcohol, acetone,
Acetonitrile etc. are mentioned. The amount of such organic solvent used is, for example, 100% by weight of the aqueous resin composition.
It is preferably 0 to 20% by weight. More preferably, it is 0 to 10% by weight.

The water-based resin composition of the present invention has a halogen compound content of 1000 ppm or less. 1000 pp
If it exceeds m, the environment may be polluted. Thus, in order to set the content of the halogen compound in the water-based resin composition to 1000 ppm or less, it is preferable not to include the halogen compound as the flame retardant. That is, it is preferable that the halogen compound is intentionally not contained, and the halogen compound is not substantially contained. The water-based resin composition having such a form has a halogen compound content of 800 ppm.
The following is preferable. More preferably, 600p
pm or less, more preferably 400 ppm or less, and most preferably 200 ppm or less.

The water-based resin composition of the present invention also has a hydroxyl group. Thus, in order for the water-based resin composition to have a hydroxyl group, it may contain a polymer having a hydroxyl group or a compound having a hydroxyl group, but in the present invention, by containing a polymer compound having a hydroxyl group, the water-based resin composition Will have a hydroxyl group.

In the present invention, the above water-based resin composition is
The solid content is 10 to 65% by weight. That is, when the water-based resin composition is 100% by weight, the solid content is 10 to 65% by weight.
Is. If it is less than 10% by weight, the flame retardant effect is insufficient. If it exceeds 65% by weight, the polymerization stability is poor. It is preferably 30 to 60% by weight, more preferably 40 to 55% by weight.

The above water-based resin composition has a solid content of 10%.
The polymer compound having a hydroxyl group is 70 to 70% by weight.
97% by weight and 3 to 30% by weight of phosphorus flame retardant. The water-based resin composition of the present invention contains a polymer compound having a hydroxyl group and a phosphorus-based flame retardant as essential components. These may be used alone or in combination of two or more. When the amount of the polymer compound having a hydroxyl group is less than 70% by weight or the amount of the phosphorus-based flame retardant is less than 3% by weight, the synergistic effect between the two is not sufficiently exerted, and flame retardancy is imparted by the water-based resin composition. The effect will not be sufficient, or the effect of imparting flame retardancy will vary,
Further, if the amount of the polymer compound having a hydroxyl group exceeds 97% by weight, the flame retardancy will be reduced. Further, when the phosphorus-based flame retardant exceeds 30% by weight, it becomes difficult to uniformly disperse in the water-based resin composition, and the stickiness of the coating surface formed from the water-based resin composition becomes large.
The polymer compound having a hydroxyl group is preferably 80 to 96% by weight, and the phosphorus-based flame retardant is preferably 4 to 20% by weight. More preferably, the polymer compound having a hydroxyl group is 8
5 to 96% by weight, and 4 to 15% by weight of phosphorus flame retardant
Is.

As the phosphorus-based flame retardant in the present invention, non-halogen phosphorus-based flame retardants such as phosphoric acid esters and organic phosphines are suitable, and examples thereof include triaryl phosphate (triphenyl phosphate) and triclenzel phosphate. Fate, trixylenyl phosphate,
Non-halogen phosphate ester monomers such as triethyl phosphate, xylenyl diphenyl phosphate, krenzel bis (di-2,6-xylenyl) phosphate, 2-ethylhexyl diphenyl phosphate, dimethyl methyl phosphate; resorcinol bis ( Diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate, resorcinol bis (di-)
Non-halogen phosphate ester condensates such as 2,6-xylenyl) phosphate; phosphonates such as diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphate; triphenylphosphine, tributylphosphine, etc. And organic phosphines of
Among these, it is preferable to use triaryl phosphate.

As the polymer compound having a hydroxyl group in the present invention, for example, the hydroxyl group equivalent (moles of hydroxyl group) is preferably 0.3 to 4.0 mol / g. 0.
If the amount is less than 3 mol / g or more than 4.0 mol / g, the effects of the present invention may not be sufficiently exhibited. More preferably 0.5 to
It is 3.2 mol / g, and more preferably 0.7 to
It is 2.3 mol / g. Examples of such a polymer compound include an acrylic polymer having a hydroxyl group, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like. Among these, it is preferable to use an acrylic polymer having a hydroxyl group or polyvinyl alcohol. It is more preferable to use an acrylic polymer which is essentially formed of a (meth) acrylate having a hydroxyl group. Therefore, the polymer compound having a hydroxyl group contains an acrylic polymer which is essentially formed of a (meth) acrylate having a hydroxyl group and has a hydroxyl group equivalent of 0.3 to
It is one of the preferable forms of this invention that it is 4.0 mol% / g.

In the acrylic polymer formed essentially by the (meth) acrylate having a hydroxyl group,
The amount of the (meth) acrylate having a hydroxyl group is
It is preferably 10 to 50% by weight based on 100% by weight of the total of the monomer component forming the acrylic polymer and the phosphorus flame retardant, and such an acrylic polymer is used as the polymer compound having a hydroxyl group. Use is one of the most preferred forms of the invention. Have a hydroxyl group (meta)
In the acrylic polymer formed by essentially including acrylate, the (meth) acrylate having a hydroxyl group is 10
If it is less than 50% by weight, the effect of imparting flame retardancy by the water-based resin composition may be insufficient, or the effect of imparting flame retardancy may vary. When producing a coalesced product, there is a possibility that aggregates may be generated during the polymerization to lower the polymerization stability. More preferably, it is 15 to 25% by weight.

The acrylic polymer which is essentially formed of the (meth) acrylate having a hydroxyl group requires the (meth) acrylate (a) having a hydroxyl group and, if necessary, a monomer containing another monomer. It is formed by polymerizing the body component, and examples of the other monomer include a polymerizable monomer (b) having a carboxyl group and / or a (meth) acrylic acid ester, an aromatic The polymerizable monomer (c) is preferably at least one kind selected from the group consisting of unsaturated monomers, polyfunctional unsaturated monomers and unsaturated monomers having a glycidyl group. These may be used alone or in combination of two or more.

The (meth) acrylate (a) having a hydroxyl group is not particularly limited as long as it is a (meth) acrylate having one or more hydroxyl groups in the molecule, and examples thereof include hydroxyethyl (meth) acrylate and hydroxypropyl ( Examples thereof include (meth) acrylate.

The polymerizable monomer (b) is not particularly limited as long as it is a polymerizable monomer having a carboxyl group in the molecule, and examples thereof include (meth) acrylic acid, crotonic acid,
Examples thereof include unsaturated carboxylic acids such as itaconic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, monomethyl myate and monoethyl myate, or derivatives thereof. When the polymerizable monomer (b) having a carboxyl group is used, the amount is 0.1% by weight based on 100% by weight of the total of the monomer component forming the acrylic polymer and the phosphorus flame retardant. It is preferably set to 10% by weight.

Examples of the polymerizable monomer (c) include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth).
Acrylate, cyclohexyl (meth) acrylate, etc .; Aromatic unsaturated monomer, styrene, etc .; Polyfunctional unsaturated monomers, divinylbenzene, ethylene glycol di (meth) acrylate, etc .; Unsaturation having a glycidyl group Examples of the monomers include glycidyl (meth) acrylate and acryl glycidyl ether.

The polymerization method for producing the above acrylic polymer is not particularly limited, and, for example, emulsion polymerization, suspension polymerization, solution polymerization and the like can be applied. Among them, emulsion polymerization is preferable. It is preferably applied. In this case, first, prepare a pre-emulsion (monomer emulsion) containing water, a surfactant and a monomer component,
Next, a method is preferred in which the pre-emulsion is dropped into a polymerization tank to form micelles, and a polymerization initiator is allowed to act to carry out emulsion polymerization. In this method, it is preferable that water is charged in the polymerization tank for dropping the pre-emulsion, but if necessary, a surfactant, a monomer component and the like may be charged in addition to water. The polymerization conditions may be appropriately set and are not particularly limited, but for example, the polymerization temperature is preferably 40 to 100 ° C. More preferably, it is 50 to 80 ° C.

Examples of the surfactant used in the emulsion polymerization include anionic surfactants such as sodium lauryl sulfate; nonionic surfactants such as polyoxyethylene alkyl ether; and reactions of ethylenically unsaturated surfactants. Examples of the surface active agent include one type or two or more types. Further, as the polymerization initiator, for example,
Known water-soluble or oil-soluble initiators such as ammonium persulfate, potassium persulfate, hydrogen peroxide, and butyl hydroperoxide can be used, and one or more can be used. Further, in order to promote emulsion polymerization, sodium bisulfite, L-ascorbic acid or the like can be used as a reducing agent and used in combination as a redox type initiator.

In the water-based resin composition of the present invention, the phosphorus-based flame retardant may be added together with, for example, a polymer compound having a hydroxyl group. For example, the polymer compound having a hydroxyl group may be an acrylic resin. In the case of using a polymer, when the monomer component is polymerized, it is polymerized in the presence of a phosphorus-based flame retardant to produce an acrylic polymer containing phosphorus-based flame retardant. It is preferable to add a phosphorus-based flame retardant by blending the acrylic polymer with the water-based resin composition. That is, the acrylic polymer is preferably polymerized in the presence of a phosphorus flame retardant. In this case, it is one of the more preferable embodiments of the present invention to include a phosphorus-based flame retardant in the pre-emulsion when producing the acrylic polymer. According to these preferable forms, the phosphorus-based flame retardant is uniformly contained in the acrylic polymer, so that the phosphorus-based flame retardant is uniformly dispersed in the water-based resin composition, and the flame retardant It is possible to eliminate the stickiness on the surface of the coating film and the unevenness of the flame retardancy caused by the above. In addition, in order to include the phosphorus-based flame retardant in the pre-emulsion or the like, it is preferable to add it in the form of an aqueous solution.

The water-based resin composition of the present invention may contain various additives as required. Such additives include, for example, plasticizers, defoamers, antisettling agents, thickeners, antifreezing agents, lower alcohols, pigments, dyes, fillers, wetting agents, texture modifiers, crosslinking agents, Antistatic agents, water repellents, pH adjusters and the like can be mentioned.

Since the 4-based resin composition of the present invention can impart excellent flame retardancy without substantially containing a halogen compound, various flame retardant properties are required without polluting the environment. It can be used in various fields. The application and usage of such an aqueous resin composition are not particularly limited, and for example, it can be suitably used as a fiber treatment agent for carpets, curtains and the like by coating these fiber products.

[0025]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, "part" indicates "part by weight", and "%"
Indicates "% by weight".

Example 1 40 parts of deionized water was placed in a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
Prepared 4.5 parts. Then, the internal temperature was raised to 67 ° C. while stirring under a nitrogen gas stream. On the other hand, 440 parts of butyl acrylate, 340 parts of methyl methacrylate, 10 parts of glycidyl methacrylate, 200 parts of hydroxymethyl methacrylate, 1 part of acrylic acid were added to the dropping funnel.
0 parts, high tenol 18E adjusted to a 20% aqueous solution in advance
(Brand name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyethylene ammonium sulfate) 150 parts and 40 parts of Naloacti 200 (trade name, manufactured by Sanyo Kasei Co., Ltd., higher alcohol-based alkylene oxide adduct) adjusted to a 20% aqueous solution, A monomer emulsion consisting of 200 parts of deionized water was charged. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 67 ° C. At this time, 50 parts of a 5% aqueous solution of potassium persulfate and 40 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 3 hours. After dripping, aging at 67 ° C for 1 hour and cooling to 2
3.8 parts of 5% aqueous ammonia was added. Then, 50 parts of triaryl phosphate was added and stirring was added.
After cooling these emulsions, they were filtered through a 100-mesh stainless wire mesh and taken out. Thereby, a flame-retardant aqueous resin composition was obtained. The obtained flame-retardant aqueous resin composition has a nonvolatile content of 55%, a pH of 7.0, and a viscosity of 1000 mPas.
・ It was s. The compositions of the monomer components and the like in the flame-retardant aqueous resin composition are summarized in Table 1.

Example 2 A separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with deionized water 40.
9.5 copies were prepared. Then, the internal temperature was raised to 67 ° C. while stirring under a nitrogen gas stream. On the other hand, 320 parts of butyl acrylate, 410 parts of methyl methacrylate, 10 parts of glycidyl methacrylate, 200 parts of hydroxymethyl methacrylate, 1 part of acrylic acid were added to the dropping funnel.
0 part, triaryl phosphate 50 parts, 20% in advance
NALOACTY 20 with 150 parts of Hitenol 18E (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyethylene ammonium sulfate) adjusted to an aqueous solution and a 20% aqueous solution
0 (trade name, manufactured by Sanyo Kasei Co., Ltd., a higher alcohol-based alkylene oxide adduct) was added to 40 parts of a monomer emulsion consisting of 200 parts of deionized water. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 67 ° C. At this time, 50 parts of a 5% aqueous solution of potassium persulfate and 40 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 3 hours. After completion of dropping, the mixture was aged at 67 ° C. for 1 hour, cooled, and 3.8 parts of 25% ammonia water was added. Then, after cooling the emulsion, 10
It was filtered through a 0-mesh stainless wire mesh and taken out. Thereby, a flame-retardant aqueous resin composition was obtained. The nonvolatile content of the obtained flame-retardant aqueous resin composition is 55%, and the pH is 7.
The viscosity was 0 and the viscosity was 800 mPa · s. The compositions of the monomer components and the like in the flame-retardant aqueous resin composition are summarized in Table 1.

Example 3 A separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with deionized water 40.
I prepared 3.1 copies. Then, the internal temperature was raised to 67 ° C. while stirring under a nitrogen gas stream. On the other hand, 410 parts of butyl acrylate, 570 parts of methyl methacrylate, 10 parts of glycidyl methacrylate and 10 parts of acrylic acid were added to the dropping funnel and Hitenol 18E (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxy) Naroacty 200 (trade name, manufactured by Sanyo Chemical Industry Co., Ltd., a higher alcohol-based alkylene oxide adduct) prepared by adjusting 150 parts of ethylene ethylene sulfate) and a 20% aqueous solution to 5
A monomer emulsion consisting of 0 part and 200 parts of deionized water was charged. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 67 ° C. At the same time, 50 parts of a 5% potassium persulfate aqueous solution,
40 parts of a 2% aqueous sodium hydrogen sulfite solution was uniformly added dropwise over 3 hours. After dripping, after aging at 67 ° C for 1 hour,
After cooling, 3.8 parts of 25% aqueous ammonia was added. After that, Kuraray Poval PVA-1 adjusted to a 10% aqueous solution
17 (trade name, manufactured by Kuraray Co., Ltd., polyvinyl alcohol: polymerization degree 1700, saponification degree 98 to 99 mol%) is 948.4.
Parts and 50 parts triaryl phosphate were added and stirring was added. After cooling these emulsions, they were filtered through a 100-mesh stainless wire mesh and taken out. Thereby, a flame-retardant aqueous resin composition was obtained. The obtained flame-retardant aqueous resin composition has a nonvolatile content of 41.9%, a pH of 7.0, and a viscosity of 1
It was 50 mPa · s. The compositions of the monomer components and the like in the flame-retardant aqueous resin composition are summarized in Table 1.

Comparative Example 1 Deionized water 40 was added to a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
9.5 g was charged. Then, the internal temperature was raised to 67 ° C. while stirring under a nitrogen gas stream. On the other hand, 500 parts of butyl acrylate, 480 parts of methyl methacrylate, 10 parts of glycidyl methacrylate, 10 parts of acrylic acid, and Hitenol 18E (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) previously adjusted to a 20% aqueous solution were added to the dropping funnel. Naroacty 200 (trade name, manufactured by Sanyo Kasei Co., Ltd., higher alcohol alkylene oxide adduct) prepared by adjusting 150 parts of ethylene ethylene sulfate) and a 20% aqueous solution to 4
A monomer emulsion consisting of 0 part and 200 parts of deionized water was charged. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 67 ° C. At this time, 55 parts of 5% potassium persulfate aqueous solution at the same time,
44 parts of a 2% aqueous sodium hydrogen sulfite solution was uniformly added dropwise over 3 hours. After dripping, after aging at 67 ° C for 1 hour,
After cooling, 3.8 parts of 25% aqueous ammonia was added. After that, the emulsion was cooled, filtered through a 100-mesh stainless wire mesh, and taken out. Thereby, a flame-retardant aqueous resin composition was obtained. The obtained flame-retardant aqueous resin composition has a nonvolatile content of 55%, a pH of 7.8 and a viscosity of 200 mPa · s.
Met. The compositions of the monomer components and the like in the flame-retardant aqueous resin composition are summarized in Table 1.

Comparative Example 2 Deionized water 40 was placed in a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
9.5 copies were prepared. Then, the internal temperature was raised to 67 ° C. while stirring under a nitrogen gas stream. On the other hand, 490 parts of butyl acrylate, 470 parts of methyl methacrylate, 10 parts of glycidyl methacrylate, 20 parts of hydroxymethyl methacrylate, 10 parts of acrylic acid were added to the dropping funnel.
Part, Hitenol 18E adjusted to 20% aqueous solution in advance
(Brand name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyethylene ammonium sulfate) 150 parts and 40 parts of Naloacti 200 (trade name, manufactured by Sanyo Kasei Co., Ltd., higher alcohol-based alkylene oxide adduct) adjusted to a 20% aqueous solution, A monomer emulsion consisting of 200 parts of deionized water was charged. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 67 ° C. At this time, 50 parts of a 5% aqueous solution of potassium persulfate and 40 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 3 hours. After dripping, aging at 67 ° C for 1 hour and cooling to 2
3.8 parts of 5% aqueous ammonia was added. After that, the emulsion was cooled, filtered through a 100-mesh stainless wire mesh, and taken out. Thereby, a flame-retardant aqueous resin composition was obtained. The nonvolatile content of the obtained flame-retardant aqueous resin composition is 55.
%, PH was 7.7, and viscosity was 300 mPa · s.
The compositions of the monomer components and the like in the flame-retardant aqueous resin composition are summarized in Table 1.

Comparative Example 3 Deionized water 40 was placed in a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
9.5 copies were prepared. Then, the internal temperature was raised to 67 ° C. while stirring under a nitrogen gas stream. On the other hand, 480 parts of butyl acrylate, 450 parts of methyl methacrylate, 10 parts of glycidyl methacrylate, 10 parts of acrylic acid, 50 parts of triaryl phosphate were added to the above dropping funnel, and high tenol 18E (trade name, first product) previously adjusted to a 20% aqueous solution. 40 parts of NaroActi 200 (trade name, Sanyo Kasei Kogyo Co., Ltd., higher alcohol alkylene oxide adduct) in which 150 parts of polyoxyethylene ammonium sulfate manufactured by Kogyo Seiyaku Co., Ltd. and a 20% aqueous solution are prepared, and 200 parts of deionized water Was charged. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 67 ° C. At the same time, 55 parts of a 5% aqueous solution of potassium persulfate and 44 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 3 hours.
After completion of dropping, the mixture was aged at 67 ° C. for 1 hour, cooled, and 3.8 parts of 25% ammonia water was added. After that, the emulsion was cooled, filtered through a 100-mesh stainless wire mesh, and taken out. Thereby, a flame-retardant aqueous resin composition was obtained.
The nonvolatile content of the obtained flame-retardant aqueous resin composition is 55%, p
H was 7.6 and viscosity was 500 mPa · s. The compositions of the monomer components and the like in the flame-retardant aqueous resin composition are summarized in Table 1.

Comparative Example 4 Deionized water 40 was added to a separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel.
9.5 copies were prepared. Then, the internal temperature was raised to 67 ° C. while stirring under a nitrogen gas stream. On the other hand, 340 parts of butyl acrylate, 440 parts of methyl methacrylate, 10 parts of glycidyl methacrylate, 200 parts of hydroxymethyl methacrylate, 1 part of acrylic acid were added to the dropping funnel.
0 parts, high tenol 18E adjusted to a 20% aqueous solution in advance
(Trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyethylene ammonium sulfate) 150 parts and 40 parts of Naloacty 200 (trade name, manufactured by Sanyo Chemical Industry Co., Ltd., higher alcohol-based alkylene oxide adduct) adjusted to a 20% aqueous solution, A monomer emulsion consisting of 200 parts of deionized water was charged. Next, the monomer emulsion was uniformly added dropwise over 3 hours while maintaining the internal temperature of the separable flask at 67 ° C. At this time, 50 parts of a 5% aqueous solution of potassium persulfate and 40 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 3 hours. After dripping, aging at 67 ° C for 1 hour and cooling to 2
3.8 parts of 5% aqueous ammonia was added. After that, the emulsion was cooled, filtered through a 100-mesh stainless wire mesh, and taken out. Thereby, a flame-retardant aqueous resin composition was obtained. The nonvolatile content of the obtained flame-retardant aqueous resin composition is 55.
%, PH was 7.3, and viscosity was 700 mPa · s.
The compositions of the monomer components and the like in the flame-retardant aqueous resin composition are summarized in Table 1.

In Examples 1 to 3 and Comparative Examples 1 to 4
To the emulsion (flame retardant aqueous resin composition) obtained by
Then, the following flame retardancy test was conducted. The results are shown in Table 1.
Each was as shown.Flame retardance test Specimen preparation: Aqueous resin emulsion, 3mm on release paper
A film with the thickness of
A test piece was dried in a semi-solid state for 7 days or more. Test method: JIS A1322 Flame retardancy of thin building materials
Sex test method (1) Shape of test piece: 30 × 20 cm (2) Test burner: Meckel burner (height 160m
m, inner diameter 20 mm) (3) Heating test: Overheating time (10 seconds) (4) Evaluation items: afterflame, dust, carbonization length (5) Evaluation results: flameproof grade 1, grade 2, grade 3 (6) Flame retardant types are shown in Table 2.

[0034]

[Table 1]

Table 1 will be described below. PVA-
117 is (trade name "Kuraray Poval PVA-11
7 ", manufactured by Kuraray Co., Ltd., polyvinyl alcohol polymerization degree 170
0, saponification degree 98 to 99 mol%).

[0036]

[Table 2]

[0037]

EFFECTS OF THE INVENTION The water-based resin composition of the present invention, which has the above-mentioned constitution, can impart excellent flame retardancy without substantially containing a halogen compound. As an agent or the like, it can be used in various fields where flame retardancy is required.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme coat (reference) D06M 15/263 D06M 15/263 F term (reference) 4J002 AA051 AB031 BE021 BG071 CH021 EW046 EW136 FD136 GK02 HA07 4J011 PA46 PB29 PC02 PC06 4L033 AB04 AB09 AC05 BA36 BA39 CA05 CA18 CA29 CA60

Claims (3)

[Claims] 1. The content of a halogen compound is 1000 pp.
A water-based resin composition having a hydroxyl group of not more than m and having a hydroxyl group, wherein the water-based resin composition has a solid content of 10 to 65% by weight, and the solid content is 100% by weight to obtain a polymer compound having a hydroxyl group. 70 to 97% by weight, 3 phosphorus-based flame retardant
The water-based resin composition is characterized by containing 30 to 30% by weight. 2. The polymer compound having a hydroxyl group contains an acrylic polymer that is essentially formed of a (meth) acrylate having a hydroxyl group and has a hydroxyl group equivalent of 0.3 to
It is 4.0 mol% / g, The water-based resin composition of Claim 1 characterized by the above-mentioned. 3. The water-based resin composition according to claim 2, wherein the acrylic polymer is polymerized in the presence of a phosphorus flame retardant.