JPH01153782A - Flame retardant bonding agent - Google Patents

Abstract

PURPOSE:To obtain the title bonding agent useful for vehicles, having excellent flame resistance, improved feeling and good storage stability contriving to reduce the price of bonding agent, by mixing a powdery flame retarder with a specific copolymer emulsion having a structure of a different layers in a specific ratio. CONSTITUTION:(A) 100pts.wt. copolymer emulsion having a structure of different layers obtained by using a halogenated vinyl copolymer emulsion as a seed and subjecting (ii) one or more vinyl monomers copolymerizable with the component (i) to emulsion polymerization is mixed with (B) 3-50pts.wt. calculated as a solid content powdery flame retarder containing halogen atom to give the aimed bonding agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a multi-mulsion type adhesive for preparing composite materials for vehicles having excellent flame retardancy.

More specifically, composite materials that have recently been used as seat cushioning materials for automobiles, trains, etc. include urethane foam, cotton cloth, nonwoven fabrics, Kanreishi V (chilling gauze),
There is an increasing demand for flame retardant lamination with chemical fibers and adhesive products. The present invention relates to a flame-retardant emulsion adhesive for vehicle composite material II that meets this requirement.

[Conventional technology]

In the United States, materials for automobiles are MVSS (Hot
r Vehicle 5afety 5standard
) Strict regulations have been established that the product must pass the flammability safety standards set forth in

Therefore, vehicles exported to the United States (passenger cars, trucks, buses, etc.) must pass this standard. It is expected that similar standards will be established in Japan sooner or later. In order to meet these demands, the general methods currently in use include using urethane foam, cotton cloth, non-woven fabric, canrayon, and chemical fiber base materials that have undergone a flame retardant treatment in advance, as well as bonding them. Also used are flame retardant agents.

Conventionally, adhesives containing halogen atoms, that is, solvent-type chloroprene-based adhesives, have been mainly used as flame-retardant adhesives for composite materials. When using this chloroprene adhesive, there is no problem with regard to flame retardancy, but it is necessary to remove the solvent from the viewpoint of resource conservation, including occupational safety and health problems caused by the scattering of organic solvents during work, fire and poisoning problems. Demand for mold adhesive development is increasing.

In order to address these problems, we have developed copolymer emulsions such as: ■ Chloroprene latex ■ Vinyl chloride emulsion ■ Vinylidene chloride emulsion ■ Vinyl chloride-acrylic acid ester copolymer emulsion ■ Vinyl chloride-ethylene-vinyl acetate copolymer emulsion. It has been proposed to use aqueous liquids.

In addition to the fatal problem that when such polymer emulsions are used alone, the biggest problem of imparting flame retardance cannot be achieved, except for chloroprene latex (2), -
It has not been put into practical use due to problems in the suitability and drying properties for laminating composite materials inside the shell.

As a flame-retardant adhesive that solves these problems, an adhesive containing a polymer emulsion and a powdered flame retardant containing a halogen atom has already been published by the present applicant in JP-A-57-187372. It is used.

[Problems to be solved by the present invention]

Since the bromine-based flame retardant and antimony trioxide used as an adjuvant or synergist for the flame retardant described in the above publication are expensive, ordinary fibers, paper, metal foil, film, etc. are used as adhesives for laminating. There is a problem in that it is more expensive than those used for laminate adhesive processing.

At the same time, due to the use of a powdered combustion agent and auxiliary or synergist, there is a problem that the feel required for a composite material for vehicles is impaired.

Due to these problems, it has excellent flame retardancy and a good texture.
There has been an increasing demand for emulsion type adhesives that reduce adhesive costs.

In order to meet this demand, Mizude A'1 has developed a copolymer emulsion containing synthetic rubber latex as the main component, a powdered flame retardant, and a halogenated vinyl compound to reduce the cost of the adhesive and reduce the cost of the adhesive. We have developed an adhesive with improved adhesive properties. However, depending on the type of coating machine used for actually laminating composite materials, i.e., the type of roll coater, a low viscosity adhesive may be required. Since the reconstituted copolymer emulsion has a high polymer specific gravity, when it is blended with other emulsions such as synthetic rubber latex, two-layer separation tends to occur during storage, which has been a practical problem.

The purpose of the present invention is to create a composite material for vehicles that has excellent adhesion and flame retardancy, has a good texture, reduces the price of an adhesive, has great storage stability, and does not have the problem of organic solvents. Our objective is to provide emulsion type adhesives.

[Means for solving problems]

The present inventors have worked diligently to solve the above problems. conducted research.

As a result, a copolymer emulsion having a different layer structure obtained by emulsion polymerization of one or more vinyl monomers copolymerizable with the halogenated vinyl compound using a halogenated vinyl copolymer emulsion as a seed is used. In addition to the adhesion, flame retardance, texture, and cost reduction, they found that it is particularly effective in improving storage stability. The present invention was completed by discovering that it is effective to incorporate a flame retardant into the copolymer emulsion.

That is, the present invention provides a copolymer having a different layer structure obtained by emulsion polymerization of one or more vinyl monomers copolymerizable with the halogenated vinyl compound using a halogenated vinyl copolymer emulsion as a seed. This flame-retardant adhesive is made by blending 3 to 50 parts by weight of a powdered flame retardant containing a halogen atom as a solid content with respect to 100 parts by weight of an emulsion.

The above copolymer emulsion having a different layer structure means an emulsion in which two or more types of polymer molecules having different compositions coexist in one emulsion particle, as seen in the example of a core-shell type emulsion.

Using the halogenated vinyl copolymer emulsion used in the present invention as a seed, 1Fli or two or more types of vinyl monomers copolymerizable with the halogenated vinyl compound are emulsion polymerized, resulting in a different layer structure. Specifically, the polymer emulsion is a halogenated vinyl copolymer emulsion with a solid content of 20 to 60% by weight and a mucus content of 10 to 100%.
Qcps.

p1] Use of vinyl chloride emulsion, vinylidene chloride emulsion, vinyl chloride-acrylic acid copolymer emulsion, vinyl chloride-ethylene-vinyl acetate copolymer emulsion, ■ dylene-vinyl chloride copolymer emulsion, chloroprene latex, etc. of p1] 2 to 12 can be mentioned. In addition, vinyl monomers copolymerizable with the halogenated vinyl compound include ethylene, propylene, butadiene,
Polymerizable hydrocarbons such as isobutylene, isoprene, styrene, and styrene derivatives, methyl acrylate, ethyl acrylate, ethyl acrylate, methyl methacrylate, edyl methacrylate, 2-edylhexyl acrylate-1, and hydroxyethyl acrylate. 1-, acrylic esters such as hydroxyethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid,
unsaturated acids such as maleic anhydride, acrylonitrile,
Examples include one or more unsaturated monomers selected from nitrogen vinyl compounds such as acrylamide and mediloacrylamide.

Among these, particularly preferred combinations from the viewpoints of adhesion, flame retardance, and texture of the composite material as well as reduction of adhesive costs are as follows:
A vinyl chloride emulsion is used as a vinyl halide copolymer emulsion, styrene and butadiene are copolymerized as vinyl monomers that can be copolymerized with the vinyl halide compound, and acrylic acid and medirollamide are copolymerized as functional group monomers, or Similarly, a vinyl chloride emulsion is used as a halogenated vinyl copolymer emulsion, with ethyl acrylate and methyl acrylate as main components as vinyl monomers copolymerizable with the halogenated vinyl compound, and acrylic acid and acrylamide as functional group monomers. It is a combination enzyme that polymerizes.

A preferable ratio of each layer of the copolymer emulsion having a different layer structure is such that the vinyl halide copolymer ratio is in the range of 10.-90% by weight based on the solid content of the polymer.

Particularly preferably, said proportion is in the range 30-70% by weight. If it is less than 10ffii%, it lacks the flame retardancy which is the main objective, and it is not practical in terms of cost as it requires powdered flame retardants to be added in multiple ways to satisfy this objective.
).

If it is more than 90% by weight, the adhesion and texture will be impaired, causing a practical problem.

This copolymer emulsion can be obtained by a conventional emulsion polymerization method for synthetic rubber latex or acrylic emulsion. For example, put a predetermined amount of vinyl chloride polymer emulsion, a polymerization initiator, and an emulsifier into a crepe, seal it, replace it with nitrogen, heat it to 60-70℃, and prepare butadiene, styrene, and a chain transfer agent. , a general synthetic rubber latex polymerization method in which mixed monomers such as functional group monomers are continuously administered for a certain period of time, and residual monomer treatment polymerization is performed, or a vinyl chloride polymer emulsion with a predetermined n, a polymerization initiator, and an emulsifier. The mixture was charged into a polymerization tank, sealed, purged with nitrogen, heated to 60-80°C, and a monomer mixture of ethyl acrylate, methyl methacrylate, and functional group monomers prepared in advance was continuously administered for a certain period of time to treat the remaining monomers. It is obtained by a method of polymerizing acrylic emulsions. After polymerization, these were subjected to steam deodorization treatment to remove coarse particles, and the p l-1 was 6 to 12.
An emulsion having a different layer structure used in the present invention can be obtained.

The powdered flame retardant with a chemical structure containing a halogen atom used in the present invention refers to a compound (hereinafter referred to as a flame retardant) that can make a combustible substance with a chemical structure containing a halogen atom flame retardant when mixed with the substance. ) and can form a powdery solid at room temperature.

Specifically, hexabrombenpine, decabrombiphenyl, decabrom diphenylconythyl, tetrabrom bisphenol A, 4,4'-bis(2,3-dibrom bromo bisphenol)-de1-labrom bisphenol. A,
Representative compounds include aromatic brominated compounds such as 2.3-dibromopropoxytribromophenol, aromatic chlorinated compounds, and perchlorocyclodecane, hexabromocyclodecane, and dodecachloropentacyclodecane, among which decabromobiphenyl, decabrom diphenyl ether,
Tetrabromobisphenol A and perchlorocyclodecane are preferred because they have excellent dispersibility in polymer emulsions.

Generally, it is advantageous to incorporate a liquid flame retardant from the viewpoint of workability, but it may have an adverse effect on the emulsion particles and cause the adhesive formulation to thicken, separate, gel, etc. during storage. At the same time, the problem arises that adhesive performance is also inhibited.

The flame retardant is added in an amount of 3 to 1001 ffi parts of the solid content of the copolymer emulsion seeded with the vinyl chloride emulsion.
It is used in a range of 50 parts by weight, particularly preferably,
A range of 10 to 35 parts by weight is preferred.

If the amount of flame retardant is less than 3 parts by weight, the desired flame retardant effect cannot be obtained, and if it is more than 50 parts by weight, the viscosity of the resulting adhesive will be too high and the applicability with a roll coater will be extremely poor. It also has a negative effect on adhesive performance and texture.

The flame retardant may be added directly to the copolymer emulsion, but in order to disperse the flame retardant more uniformly, it is preferable to use a flame retardant dispersed in water in advance. When dispersing flame retardants in water, surfactants such as argyl sulfate Nisder salts, naphthalene sulfonic acid polymerine condensates, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, and alkyl amine salts may be used. desirable.

In the present invention, ammonium phosphate, ammonium polyphosphate, 1-riphenylbosphate, 1-riphenylphosphite 1-, tricresyl are used as adjuvants or synergists for the purpose of enhancing the effect of flame retardants. It is desirable to use a phosphoric acid compound such as phosphate [·, tris(halogenated alkyl) phosphate, etc.], an antimony compound such as an antimonate, an organic antimony compound, or antimony trioxide. Among these compounds, a particularly effective and preferred compound is antimony trioxide.

The amount of antimony trioxide added is in the range of 10 to 200% by weight, preferably 20 to 5% by weight, based on the above flame retardant.
The range is 0%.

If it is less than 10% by weight, the desired flame retardant effect cannot be obtained, and if it is more than 200% by weight, the viscosity of the flame retardant obtained will become high and the applicability with a roll coater will be extremely poor, resulting in poor adhesive performance. and the texture deteriorates significantly.

A preferred method of addition is to mix a predetermined amount with the above-mentioned flame retardant and disperse it in water, which is convenient for work.

The adhesive of the present invention is usually used in order to adjust the viscosity to suit the type of coating machine, that is, the roll coater.
In addition to using water-soluble polymers such as gel, methylcellulose, carboxymethylcellulose, and hydroxymethylcellulose, polyacrylic acid, polyacrylates, and nonionic surfactants as thickeners, as necessary, antifoaming agent,
Coloring agents, anti-aging agents, film forming aids, plasticizers, dixoating agents,
Antifreeze agents, fillers, etc. may be used within the range that does not impede the purpose of the present invention.

The adhesive of the present invention is prepared by charging the main component, a synthetic rubber or acrylic copolymer emulsion polymerized with vinyl chloride emulsion as a seed, into a container equipped with a stirrer, and then adding a flame retardant pre-dispersed in water and an auxiliary agent. The agent or synergist is gradually added and mixed with stirring, and if necessary, the above-mentioned thickener is further used.

When the adhesive of the present invention is put to practical use, that is, when applied to a base material, it is usually applied using a roll coater, and the applied surface is
It does not matter which side of the two materials it is applied to.

Also, when curing or drying the adhesive, it may be done at room temperature or under heating, but in actual production factories it is
Forced drying in a hot air dryer at ℃.

[For production]

Since the adhesive of the present invention is an aqueous emulsion that does not use organic solvents, there is no problem with organic solvents, and since it has a different layer structure with the vinyl halide copolymer emulsion as the core, the vinyl halide copolymer can be used in a sufficient amount. Even if the amount is increased, the shell component contains vinyl polymers and functional group polymers that are effective for adhesion, so it maintains sufficient adhesion and can be used as a low-viscosity liquid, which is required depending on the type of roll coater. Since the vinyl copolymer, vinyl polymer, and functional group polymer are bonded together, there is no risk of separation during storage. In addition, since a sufficiently large amount of vinyl halide copolymer can be blended, flame retardancy can be maintained at a high level even if the blend of flame retardants, flame retardant auxiliaries, or synergists is reduced, which not only reduces adhesive costs. As a result, TR of viscosity can be further avoided, so that the feel when applied to a composite material can be improved.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way.

In addition, unless otherwise specified, parts and percentages are based on weight below.

Production Example 1 150 parts of distilled water, 1 part of sodium dodecylbenzenesulfonate, 0.2 parts of potassium persulfate, and 100 parts of vinyl chloride were subjected to emulsion polymerization in an autoclave at 60°C by a normal seeding polymerization method to obtain a solid content of 40%. , a vinyl chloride emulsion with a viscosity of 15 cps was obtained.

Next, 175 parts of the vinyl chloride emulsion, 47 parts of distilled water, and 1.0 parts of sodium dodecylbenzenesulfonate were placed in a polymerization tank.
2 parts of potassium persulfate and 0.15 parts of potassium persulfate were charged, sealed, and replaced with nitrogen in the same manner as in the emulsion polymerization of ordinary acrylic emulsions.The temperature was raised to 60°C. 6.1 parts of acrylate, 0.6 parts of methacrylic acid, 0.6 parts of acrylamide, t
A mixed solution consisting of 0.03 parts of ert-dodecyl mercaptan was administered continuously over 4 hours, and after polymerization was carried out on a crosspiece for 3 hours at the same temperature, steam deodorization treatment was performed, and the coarse particles were separated using a 300-mesh wire mesh. filtered at 20%
l) l-1 was adjusted to 7.0 with caustic soda to obtain a copolymer emulsion having a heterolayer structure with a concentration of 40 parts for the present invention. (hereinafter referred to as copolymer emulsion) Production Example 2 125 parts of the vinyl chloride emulsion obtained in Production Example 1, 78 parts of distilled water, 2 parts of sodium dodecylbenzenesulfonate,
0.25 parts of potassium persulfate was charged in the same manner as in Production Example 1, and then 3 parts of ethyl acrylate, 9 parts of ethyl acrylate, 10.1 parts of methyl acrylate, and 1 part of methacrylic acid were added in the same manner as in Production Example 1.
0 part of acrylamide and 1.0 part of acrylamide were continuously added, and the treatment according to Production Example 1 was carried out to obtain a copolymer emulsion with a concentration of 40 parts for use in the present invention.

Production Example 3 75 parts of vinyl chloride emulsion obtained in Production Example 1, 100 parts of distilled water, 2.5 parts of sodium dodecylbenzenesulfonate
1 part, and 0.35 parts of potassium persulfate were added in the same manner as in Production Example 1, and then in the same manner as in Production Example 1, ■ Delacrylate 53
．． 1 part of methyl acrylate, 14.1 parts of methacrylic acid, and 1.4 parts of acrylamide were successively administered and treated according to Production Example 1 to produce a copolymer with a concentration of 40 parts for the present invention. A combined emulsion was obtained.

Production Example 4 5 parts of the vinyl chloride emulsif obtained in Production Example 1 was charged into an autoclave, and then 47 parts of distilled water, 0.6 parts of sodium dodecylbenzenesulfonate, and 0.2 parts of potassium persulfate were charged and the autoclave was sealed. After replacing with nitrogen and heating to 65°C in the same manner as the emulsion polymerization of ordinary synthetic rubber latex, 17.6 parts of styrene, 0.6 parts of acrylic acid, 1.0 parts of methylolacrylamide, and tert-dodecyl prepared in advance were added. A mixed monomer consisting of 0.1 mercaptan and 10.9 parts of butadiene were continuously administered over 8 hours, and the remaining monomer treatment was further polymerized for 10 hours at the same temperature, and the same treatment as in Production Example 1 was carried out. A 40 parts copolymer emulsion for use in the present invention was obtained.

Production Example 5 125 parts of vinyl chloride emulsion obtained in Production Example 1, 78 parts of distilled water, 1.0 parts of sodium dodecylbenzenesulfonate
29.5 parts of styrene and 0.3 parts of potassium persulfate were charged into an autoclave, and 29.5 parts of styrene was prepared in the same manner as in Production Example 4.
part, 1.0 part of acrylic acid, 1 part of methylol acrylamide
．． 5 parts and 18.0 parts of butadiene were continuously administered, and the same treatment as in Production Example 4 was carried out to obtain a copolymer emulsion with a concentration of 40 parts for use in the present invention.

Production Example 6 75 parts of vinyl chloride emulsion obtained in Production Example 1, 100 parts of distilled water, 1.5 parts of sodium dodecylbenzenesulfonate
41.2 parts of styrene, 1.4 parts of acrylic acid, and 2.0 parts of methylolacrylamide were charged in an autoclave in the same manner as in Production Example 4.
0 parts and 25.3 parts of butadiene were continuously administered, and the same treatment as in Production Example 4 was carried out to obtain a copolymer emulsion with a concentration of 40 parts for use in the present invention.

Example 1 110 parts of tetrabromobisphenol A as a flame retardant, 240 parts of Andemo trioxide as an auxiliary agent or synergist, and 0.1 part of Thymol N as a dispersing surfactant were mixed into 100 parts of water, and thoroughly kneaded. A paste with a solids content of 60% was obtained. (hereinafter referred to as flame retardant paste) To 100 parts of the copolymer emulsion obtained in Production Example 1, 25 parts of the flame retardant paste was blended as a flame retardant and thoroughly stirred and mixed to prepare the flame retardant adhesive of the present invention. I got it. A composite material was prepared using the method shown below, and its physical properties were similarly evaluated using the test method below, and the results are shown in Table 1.

1) Composite monthly interest sample creation (sheet cushion material) thickness 5
The flame-retardant adhesive described above was applied at 50 sheets/m2 to a flame-retardant urethane foam with a specific gravity of 0.022, and immediately covered with a flame-retardant polyester nonwoven fabric having a thickness of 0.15 m. Crimp with a rubber roll of m 2 Kt;
Dry for 1 minute in a hot air dryer at 80°C to create a vehicle seal 1.
- Created a composite material to be used as a cushion material.

2) Test method 2-1) From the sheet cushion material obtained on the adhesive performance, a width of 25 mm and a length of 10
A sample of 0111#I was cut and heated at 25°C, 50% R,
A 180° peeling test was carried out at a load speed of 200 mm/min using a Tensilon type tensile tester under the conditions of H. This was carried out at 5 points and the average value was determined.

2-2) Width 100m, length 32 from sheet cushion material obtained on flame retardant
Cut a 0m sample and cut it according to MVSS302.
A flame retardancy test was conducted for each point, and the average value was determined. This was ranked and evaluated as shown below.

Evaluation method: Items that self-extinguish in front of the marked line after ignition...5 points.
Items that are 5 cm or less beyond the marked line after ignition and extinguish within 60 seconds: 3 points. Items that burn more than the above 3 points: 1 point or less. The same evaluation method as above was used.

2-3) Cut a 1100m x 100mm sample of the sheet cushion obtained above, observe the degree of hardness and softness by touching it with your fingers, and place a 500g weight on the non-woven fabric side of the sheet cushion material for 1 minute. The subsequent sinking length was measured on a scale and displayed as shown below.

○...Soft to the touch and sinking length of 2m or more △・
・・Hard to the touch) and sinking length of 1~2M×・・・
Hard to the touch and with a sinking length of 1 mm or less2-4)
Price The market price of commercially available solvent-type chloroprene is used as the standard and is displayed as follows.

○... Direction of price reduction △... Same price ×... Direction of higher price 2-5) Storage stability: Stored in a furan oven at 40°C for 3 months, the viscosity of the adhesive changed, The presence or absence of layer separation was checked and displayed as shown below.

○...No abnormality ×...Viscosity change or two-layer separation large The mixture was thoroughly stirred and mixed to obtain a flame retardant adhesive of the present invention. A composite material was prepared using the same method as in Example 1, and its physical properties were evaluated using the same test method as in Example 1. The results are shown in Table 1.

Example 3 25 parts of the flame retardant paste obtained in Example 1 was blended with 32,100 parts of the copolymer l malta obtained in Production Example 3 and thoroughly stirred and mixed to obtain the flame retardant adhesive of the present invention. Ta. A composite material was prepared using the same method as in Example 1, and its physical properties were evaluated using the same test method as in Example 1. The results are shown in Table 1.

Example 4 25 parts of the flame retardant paste obtained in Example 1 was blended with 100 parts of the copolymer emulsion obtained in Production Example 4 and thoroughly stirred and mixed to obtain a flame retardant adhesive of the present invention. . A composite material was prepared using the same method as in Example 1, and its physical properties were evaluated using the same test method as in Example 1. The results are shown in Table 1.

Example 5 25 parts of the flame retardant paste obtained in Example 1 was blended with 100 parts of the copolymer emulsion obtained in Production Example 5 and thoroughly stirred and mixed to obtain a flame retardant adhesive of the present invention. . A composite material was prepared using the same method as in Example 1, and its physical properties were evaluated using the same test method as in Example 1. The results are shown in Table 1.

Example 6 25 parts of the flame retardant paste obtained in Example 1 was blended with 100 parts of the copolymer emulsion obtained in Production Example 6 and thoroughly stirred and mixed to obtain a flame retardant adhesive of the present invention. . A composite material was prepared using the same method as in Example 1, and its physical properties were evaluated using the same test method as in Example 1. The results are shown in Table 1.

Example 7 2.8 parts of the flame retardant paste obtained in Example 1 was added to 100 parts of the copolymer emulsion obtained in Production Example 5, and the mixture was thoroughly stirred and mixed to prepare the flame retardant adhesive of the present invention. Obtained. Example 1
A composite material F31 was prepared in the same manner as in Example 1, and its physical properties were evaluated using the same test method as in Example 1. The results are shown in Table 1.

Example 8 45 parts of the flame retardant paste obtained in Example 1 was blended with 100 parts of the copolymer emulsion obtained in Production Example 5 and thoroughly stirred and mixed to obtain a flame retardant adhesive of the present invention. . A composite material was prepared using the same method as in Example 1, and its physical properties were evaluated using the same test method as in Example 1. The results are shown in Table 1.

Comparative Example 1 Example 1 using the copolymer emulsion obtained in Production Example 5
A composite material was prepared in the same manner as in Example 1, and its physical properties were evaluated using the same test method as in Example 1. The results are shown in Table 1.

Comparative Example 2 Synthetic rubber latex (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name Polylac 750, modified with methylol groups and carboxyl groups, thretin-butadiene latex, solid content 48%, viscosity 100 cps, pH 6,
5) 30 parts of the flame retardant paste obtained in Example 1 was added to 100 parts and thoroughly stirred and mixed to obtain the flame retardant adhesive of the present invention. A composite material was prepared using the same method as in Example 1, and its physical properties were evaluated using the same test method as in Example 1. The results are shown in Table 1.

Comparative Example 3 750,100 parts of polylac used in Comparative Example 2 and vinyl chloride emulsion [manufactured by Nippon Zeon, Zeon PVC]
Latex 576 (product containing dioquidyl phthalate), solid content 55%, viscosity 35CpS.

1 to 30 parts of the flame retardant paste obtained in Example 1 were added to 45 parts (pH 9.5) and sufficiently stirred and mixed to obtain a flame retardant adhesive of the present invention. A composite material was prepared using the same method as in Example 1, and its physical properties were evaluated using the same test method as in Example 1. The results are shown in Table 1.

〔Effect of the invention〕

As is clear from Table 1, the flame retardant adhesive of the present invention has no concerns about environmental issues or occupational safety and health issues, and also has flame retardancy and adhesive properties that have not been achieved with conventional emulsion type adhesives. It improves the texture of the material 1, reduces adhesive costs, and at the same time significantly improves storage stability, so it has extremely high practical value as an adhesive for vehicles with high flame retardant requirements. It's large.

Claims (1)

[Claims] Vinyl monomer 1 copolymerizable with the halogenated vinyl compound using a halogenated vinyl copolymer emulsion as a seed
3 to 5 parts by weight of a powdered flame retardant containing a halogen atom as a solid content per 100 parts by weight of a copolymer emulsion having a different layer structure obtained by emulsion polymerization of one species or two or more species.
A flame-retardant adhesive containing 0 parts by weight.