JPH10237764A - Aqueous composition of slow burning resin for backing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous composition of a slow burning resin for backing of an automobile interior material excellent in water blocking property and strength by blending an epoxy resin with an aqueous emulsion of an ethylenic polymer. SOLUTION: This aqueous composition of a slow burning resin for backing is prepared by blending 1-50 pt.wt., preferably 3-30 pt.wt. solid portion of an epoxy resin having glycidyl group at the terminal of a bisphenol type epoxy resin with 100 pts.wt. solid portion of an aqueous emulsion of an ethylenic polymer obtained by performing an emulsion polymerization of an ethylenic monomer such as ethylacrylate, methylmethacrylate, etc. An automobile interior material is obtained by backing the composition by 50-500g/m<2> based on solid portion thereof to a needle-punched carpet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automobile interior material,
The present invention relates to an aqueous backing flame retardant resin composition for backing a carpet or the like on the floor of a house, office, etc., which imparts water-blocking and strength to the backing by giving a backing treatment to the carpet, etc. The present invention relates to an aqueous slow-flammable resin composition for backing, which does not sometimes generate toxic gases such as halogen-containing gases, and does not fog window glasses or the like due to the adhesion of volatile components in normal times.

[0002]

2. Description of the Related Art With the recent increase in the number of automobiles and densely populated houses, it is extremely important to take measures against such fires. In particular, there is a great demand for flame retardancy for various vehicles and interior materials of houses, and various flame retardant technologies have been proposed. Regarding the flame retardancy of textile products used in automotive interiors, use halogen-containing flame-retardant copolymer emulsions such as vinyl chloride and vinylidene chloride as backing agents used as reinforcing agents for textile products, Alternatively, a flame retardant is blended with an ordinary synthetic rubber-based, acrylic-based, acrylic-styrene-based, ethylene-vinyl acetate-based copolymer emulsion, or a blend thereof, and then flame-retarded by applying it to textiles. A method has been proposed. Such flame retardants include liquid or powdered phosphate esters,
Organic flame retardants such as halogenated phosphate esters and halogen compounds, and inorganic flame retardants such as antimony, aluminum and boron are used alone or in combination as appropriate.

[0003]

However, the above-mentioned halogen-containing flame-retardant copolymer emulsions and halogen-based flame retardants generate toxic gases such as halogen gas at the time of fire or combustion such as heat recycling to the human body. It has serious drawbacks, such as causing serious harm and causing air pollution and deterioration of the incinerator. It is also known that these flame retardants increase the amount of carbon monoxide generated due to incomplete combustion of textiles and backing agents at the time of fire due to their strong flame retardancy. Furthermore, when these flame retardants are used for interior materials of automobiles even in normal times, hydrogen halide generated by decomposition of halogen compounds contained therein and amines in urethane foam which is a buffer material for car seats are used. There is also a problem that the reaction product of (1) foggs the window glass. Further, a phosphorus-based flame retardant, which is a general flame retardant other than a halogen-based flame retardant, also has a problem in that it evaporates to fog the window glass.

[0004]

Means for Solving the Problems The present inventors have found that when a car is injured in the event of a fire, the fire is quickly turned around, the opportunity to escape is lost, and human beings are poisoned by harmful gases and carbon monoxide generated. In view of the fact that many cases have occurred, as a result of extensive research with the primary objective of obtaining a backing material that has sufficient slow-flammability and does not generate harmful gases in the event of a fire, it was found that epoxy-based It has been found that an aqueous resin composition obtained by blending a system resin solves this problem altogether, and further studies have been made to complete the present invention. That is, the present invention relates to (1) an aqueous backing flame retardant resin composition comprising 1 to 50 parts by weight of an epoxy resin as a solid content based on 100 parts by weight of a solid content of an aqueous emulsion of an ethylene polymer, 2) The composition according to the above (1), which contains 3 to 30 parts by weight of an epoxy resin as a solid content, (3) the composition according to the above (1), which is used for backing automotive interior materials, (4) 50 to 500 g / m as a solid content of the composition according to (1).
⁽² ) The retarded sheet-like fiber product according to the above (4), wherein the backed sheet-like textile product is backed, and (5) the retarded sheet-like fiber product is an automobile interior material. The term "slow flammability" as used herein means "slow flammability" used as a flammability category in "Method for testing the flammability of organic materials for automobile interiors" in JIS D _1201-1977 .
That is, a property in which a material once ignited in a windless atmosphere continues to burn slowly at a burning speed of 100 mm / min or less even after the ignition source is removed. This JIS D 1201 _-1977 flammability test method is based on the US Federal Motor Vehicle Safety Standard.
d) It complies with the combustion test specified in FMVSS-302.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous ethylene polymer emulsion referred to in the present invention refers to one or more ethylene monomers.
Homopolymer obtained by emulsion polymerization of at least one species in an aqueous medium in the presence or absence of a surfactant and / or protective colloid, or post-emulsification of a polymer polymerized by a method other than emulsion polymerization Or a homopolymer of a copolymer aqueous emulsion or a blend of a plurality of polymer emulsions. For reasons of easiness of production, economy, etc., homopolymers or homopolymers usually obtained by emulsion polymerization of ethylene monomers. It is preferably a single polymer emulsion or a blend of a plurality of polymer emulsions. Examples of the ethylene monomer include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, and stearyl acrylate. Monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-
Ethylhexyl methacrylate, alkyl methacrylate monomers such as stearyl methacrylate, for example, styrene, α-methylstyrene, vinyltoluene,
Aromatic vinyl monomers such as ethylvinylbenzene, for example, saturated fatty acid vinyl monomers such as vinyl acetate, vinyl propionate and vinyl versatate, and vinyl cyanide monomers such as acronitrile and methacrylonitrile Monomer, for example, ethylene, propylene, olefinic monomers such as butadiene, for example, acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, ethylene carboxylic acid such as fumaric acid, for example, anhydrous Ethylene carboxylic anhydrides such as maleic acid, for example, monoalkyl esters of ethylene dicarboxylic acids such as monobutyl maleic acid, and ethylene carboxylic acid salts such as ammonium salts or alkali metal salts thereof, for example, acrylamide, methacrylamide , Diacetone acrylamide, etc. Acid amides of ethylene-based carboxylic acids, for example, N-methylolacrylamide, N-methylolmethacrylamide, methylolated diacetoneacrylamide, and etherified products of these monomers with alcohols having 1 to 8 carbon atoms (for example, , N-isobutoxymethylacrylamide) and the like, and methylolates of ethylene-based carboxylic acid amides and derivatives thereof, for example, esters of an ethylene-based carboxylic acid such as glycidyl acrylate and glycidyl methacrylate with an alcohol having an epoxy group, for example, 2 Hydroxyalkyl esters of ethylene-based carboxylic acids such as -hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxy methacrylate, for example, dimethylaminoethyl methacrylate, diethylamido; Esters of an ethylenic carboxylic acid such as ethyl methacrylate and an alcohol having an amino group, for example, divinylbenzene, diallyl phthalate, triallyl cyanurate, diethylene glycol dimethacrylate and other monomers having two or more non-conjugated unsaturated groups The body can be mentioned.

The type and amount of the above-mentioned ethylene monomer are not particularly limited, and can be appropriately selected depending on various required physical properties of a sheet-like fiber product to be subjected to the slow burning process. For example, in a field requiring a relatively hard texture such as a floor or a deck of an automobile, it is preferable to use an ethylene monomer having a glass transition point (Tg) of 10 ° C. or more of the cured product. In a field where a soft texture is required, it is preferable to use an ethylene monomer having a glass transition point of 0 ° C. or less of the cured product. The aqueous ethylene polymer emulsion of the present invention is generally prepared by adding one or more ethylene monomers appropriately selected from the above monomer group in the presence of a surfactant and / or a protective colloid. A single polymer emulsion obtained by emulsion polymerization in an aqueous medium, or a blend of a plurality of these polymer emulsions. Examples of the surfactant include polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, glycerin fatty acid esters, and polyoxyalkylene alkyl esters. Nonionic surfactants such as oxyethylene / polyoxypropylene / block copolymers, for example, fatty acid salts, alkylaryl sulfonates, alkyl sulfur ester salts, alkyl sulfosuccinate salts and derivatives thereof, polyoxyalkylene alkyl ether sulfate Ester salts, anionic surfactants such as polyoxyalkylene alkylaryl ether sulfate salts, such as alkylamine salts, quaternary ammonium salts,
Cationic surfactants such as polyoxyethylalkylamines and amphoteric surfactants such as alkyl betaines are mentioned. Reactive surfactants can also be used.

The surfactant is usually used in an amount of about 0.1 to 10% by weight based on the total amount of the ethylene monomer, and is suitable for the reaction of emulsion polymerization, the stability of the obtained resin aqueous emulsion and the water resistance. In view of the above, it is preferable to use about 0.5 to 7% by weight. Examples of the protective colloid that can be used in the present invention include polyvinyl alcohols and cellulose derivatives, and these can be used alone or in combination.
The amount used can be appropriately selected, and for example, about 0.5 to 10% by weight based on the total amount of the ethylene monomer used can be exemplified. The solid content of the aqueous ethylene polymer emulsion used in the present invention is not particularly limited, but is preferably about 30 to 65% by weight from the viewpoint of productivity and ease of production. In the present invention, an epoxy resin is blended with the aqueous ethylene polymer emulsion. The epoxy resin used in the present invention is not particularly limited, and generally includes an epoxy resin having a glycidyl group at a terminal group. Examples of the epoxy resin having a glycidyl group in a terminal group include bisphenol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, bisphenol A novolak type epoxy resin, and methylresorcinol. Type epoxy resin, resorcinol novolak type epoxy resin, and the like, and bisphenol type epoxy resin is usually preferable in terms of excellent heat resistance. The epoxy resin used in the present invention may be directly blended with the aqueous ethylene polymer emulsion, or may be blended as an aqueous epoxy resin solution, or in the presence of a surfactant, a single emulsion obtained by emulsification in an aqueous medium, Alternatively, it can be formulated as a blend of a plurality of emulsions. Examples of the surfactant include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, chrysin fatty acid esters, Non-ionic surfactants such as oxyethylene / polyoxypropylene / block copolymers, for example, fatty acid salts, alkylaryl sulfonates, alkyl sulfates, alkyl sulfosuccinates and derivatives thereof, polyoxyalkylene alkyl ether sulfates Ester salts, anionic surfactants such as polyoxyalkylene alkylaryl ether sulfate salts and the like, and these may be used alone or as a mixture of a plurality of them. You can use.

[0008] The amount of the epoxy resin used is 1 to 50 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the solid content of the aqueous ethylene polymer emulsion. If the amount is less than 1 part by weight, JIS D 1201 _-1977
In the flammability test for organic materials used in automobile interiors, the combustion speed exceeds 100 mm / min, and the material becomes flammable. Also,
If the amount is more than 50 parts by weight, the storage stability of the composition of the present invention is lowered, and the composition becomes expensive. The aqueous backing flame retardant resin composition of the present invention may contain a crosslinking agent in addition to the aqueous ethylene polymer emulsion and the epoxy resin to improve the physical properties. Examples of the crosslinking agent include an aqueous solution or aqueous dispersion of zinc oxide, an aqueous solution or aqueous dispersion of blocked isocyanate, and melamine-
An aqueous solution or aqueous dispersion of a formaldehyde resin is exemplified. The amount of these crosslinking agents is usually 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the solid content of the aqueous ethylene polymer emulsion. Further, a flame retardant can be used in combination with the aqueous flame retardant resin composition of the present invention within a use range that does not impair the excellent effects of the present invention. Examples of the flame retardant include flame retardants that do not normally cloud glass and the like and do not generate toxic gas at the time of fire, such as antimony compounds, boron compounds, aluminum compounds, magnesium compounds, and zirconium compounds. Can be Of these, aluminum compounds, particularly aluminum hydroxide, are preferred. The amount of the flame retardant to be used is, for example, about 1 to 250 parts by weight based on 100 parts by weight of the solid content of the aqueous ethylene polymer emulsion. In addition, in the use range not hindering the excellent effects of the present invention, inorganic fillers, dispersants, thickeners, wetting agents, foaming agents, foaming agents, defoamers, pigments,
Dyes, plasticizers, antioxidants, ultraviolet absorbers, preservatives and the like can be used.

The solid content, pH and viscosity of the aqueous flame-retardant resin composition of the present invention obtained as described above are not particularly limited, and the solid content, pH and viscosity of the composition are not particularly limited. From the viewpoint, the solid content is generally 30 to 70% by weight, preferably about 35 to 60% by weight, the pH is 4 to 10, preferably 6 to 10, and the viscosity (20 ° C, 12 rpm) is 1000 to 15%.
000 mPa · s, preferably 1,000 to 10,000 mPa · s. In the present invention, by using the composition as a backing agent for a sheet-like fiber product, a sheet-like fiber product having excellent flame retardancy can be obtained. The fabric of the sheet-like fiber product used in the present invention is not particularly limited as long as it does not generate harmful gas at the time of fire.For example, polyester, polypropylene, nylon, synthetic fibers made from acrylic and the like, wool and the like Natural fibers and blended fibers of synthetic fibers and natural fibers are exemplified. The sheet-like fiber product lined with the aqueous flame-retardant resin composition of the present invention is particularly preferably used as an interior material for automobiles, for example, as a surface covering material for ceilings, doors and seats, or as a carpet material for decks and floors. Is done. In addition, in order to improve the moldability of the needle punch carpet on the floor, and to improve the water shielding, the needle punch carpet having the composition as a backing layer,
Even when a melt-extruded laminating backing made of a thermoplastic resin such as polyethylene is applied, a sufficient retardation property is exhibited. The coating amount of the composition as a backing layer,
50-500 g / m ² (solid content), preferably 50-2
At 50 g / m ² , the sheet-like fiber product coated with the composition exhibits a delayed flammability used as a flammability category in the flammability test method for organic materials for automobile interiors described in JIS D _1201-1977. . If the coating amount of the composition is less than 50 g / m ² , the texture and retardation of the hardness are insufficient, and the
If it exceeds m ² , powder drop occurs and an economical problem occurs.

[0010]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. Example 1 400 g of ion-exchanged water and 0.2 g of sodium dodecylbenzenesulfonate were placed in a reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser.
Heat to dissolve. After the inside of the container was replaced with nitrogen, the temperature was raised to 60 ° C., and while maintaining the temperature, ethyl acrylate 1 was added.
97 g, a mixture of 223 g of methyl methacrylate and 13 g of methacrylic acid, an aqueous solution obtained by dissolving 1.5 g of sodium dodecylbenzenesulfonate, 18 g of polyoxyethylene nonylphenyl ether and 13 g of N-methylolacrylamide in 120 g of deionized water, 25 g of a 4% aqueous ammonium persulfate solution 25 g of 2% aqueous sodium bisulfite solution
The emulsion was continuously added over a period of time to perform emulsion polymerization. Neutralized with aqueous ammonia, the resulting ethylene copolymer emulsion had a solid content of about 45%, a pH of 7.5, and a viscosity of 80 mPa · s (25 m
(30 ° C., 30 rpm), and the Tg of the ethylene copolymer was 33 ° C. Epikote 828
5 parts by weight of polyoxyethylene nonylphenyl ether, 0.5 parts by weight of sodium dodecylbenzenesulfonate, and 70 parts by weight of water were added to 100 parts by weight (manufactured by Yuka Shell Epoxy Co., Ltd.). A resin emulsion was obtained. The above ethylene copolymer emulsion 1
100 parts by weight (solid content) of epoxy resin emulsion 10
Parts by weight (solid content), and further add aluminum hydroxide 20
0 parts by weight, water and a thickener are added and mixed, and the solid content is 50%, p
An aqueous slow-flammable resin composition having an H of 8.5 and a viscosity of 2000 mPa · s (20 ° C., 12 rpm) was obtained. 1) Preparation of Sample An aqueous slow-flammable resin composition was applied to a needle punch carpet (having a basis weight of 300 g / m ² ) made of polyester and polypropylene at 150 g / m ² (solid content) and dried at 150 ° C. for 10 minutes. . This is 350mm ×
A sample cut to 200 mm and left in an atmosphere of 20 ° C. and 65% RH for 24 hours was used as a sample. 2) Combustion test According to FMVSS-302, the produced sample was subjected to a combustion test by a horizontal method. The test was performed at 10 points, and indicated by the average burning rate. The results are shown in [Table 1].

Example 2 A test was conducted in the same manner as in Example 1 except that the amount of the epoxy resin emulsion was changed to 20 parts by weight (solid content). The obtained results are shown in [Table 1]. Example 3 A test was performed in the same manner as in Example 1 except that polyethylene was further backed with 200 g / m ² . The weight of the needle punch carpet is 400 g / m ^2.
Met. Example 4 The amount of the ethylene monomer was changed to ethyl acrylate 152.
g, butyl acrylate 67 g, and 201 parts of methyl methacrylate were used in the same manner as in Example 1 to obtain an aqueous resin composition (Tg 19 ° C.), and a test was conducted in the same manner. The obtained results are shown in [Table 1]. Example 5 An aqueous resin composition (Tg4) was prepared in the same manner as in Example 1 except that the amount of the ethylene copolymer used was 108 g of butyl acrylate and 312 g of styrene.
1 ° C.) and tested in the same manner. The obtained results are shown in [Table 1].

Example 6 An aqueous resin composition was obtained in the same manner as in Example 1 except that the epoxy resin emulsion was changed to a water-soluble epoxy (Denacol EX-313, manufactured by Nagase Kasei Kogyo Co., Ltd.). went. The obtained results are shown in [Table 1]. Comparative Example 1 A test was performed in the same manner as in Example 1 except that the epoxy resin emulsion was not blended. The obtained results are shown in [Table 1]. Comparative Example 2 In Example 1, the application amount of the aqueous resin composition was 30 g /
The test was performed in the same manner except that m ² (solid content) was changed. The obtained results are shown in [Table 1].

[0013]

[Table 1]

Example 7 In Example 1, 265 g of ethyl acrylate and 15 parts of butyl acrylate were used.
An ethylene polymer emulsion was obtained in the same manner as in Example 1 except for using 5 g (Tg-30 ° C). 10 parts by weight (solid content) of the epoxy resin emulsion used in Example 1 was added to 100 parts by weight (solid content) of the polymer emulsion, and 100 parts by weight of aluminum hydroxide, water and a thickener were further added and mixed. Min 50%, pH 8.0, viscosity 30
An aqueous slow-flammable resin composition of 00 mPa · s (20 ° C., 12 rpm) was obtained. 1) Preparation of sample Car seat cloth made of polyester (with a basis weight of 300 g /
m ² ) was coated with 150 g / m ² (solid content) of the aqueous flame retardant resin composition and dried at 150 ° C. for 10 minutes. This is 3
A sample cut to 50 mm x 200 mm and left in an atmosphere of 20 ° C and 65% RH for 24 hours was used as a sample. 2) Combustion test According to FMVSS-302, the produced sample was subjected to a combustion test by a horizontal method. The test was performed at 10 points, and indicated by the average burning rate. The results are shown in [Table 2]. 3) Fogging test "ISO / DIS (6452) Rubber and plastic covered fabric-WINDSCREEN FOGGIN of organic materials in vehicles
The test was performed according to “Measurement of G”. The results are shown in [Table 2]. "WINDSCREEN FOGGING" refers to the adhesion of oily substances that adhere to the inside of a car window under high temperature conditions. The degree of fogging (FOGGING) was determined as follows. -Place a fixed amount (10 g) of the test specimen on the bottom of the beaker.・ Put the beaker in a water tank whose temperature has been adjusted (90 ° C.). -Place the cleaned glass plate on the beaker and set it so that volatile materials generated from the test piece condense underneath. After a predetermined time (6 hours), the glass plate is taken out and the reflectance is measured by a reflectometer. -Calculate the reflectance ratio (%) between a clean glass plate and a glass plate with a volatile material attached.

Comparative Example 3 A test was conducted in the same manner as in Example 7 except that the epoxy resin emulsion was not blended. The results obtained are shown in [Table 2]. Comparative Example 4 Saran L-1 was used instead of the polymer emulsion of Example 7.
The test was performed in the same manner except that 10A (vinylidene chloride emulsion, manufactured by Asahi Kasei Corporation) was used. The results obtained are shown in [Table 2].

[0016]

[Table 2]

[0017]

The fibers and sheets lined with the aqueous flame-retardant resin composition of the present invention are not self-extinguishing, but have a very low burning rate after ignition, and the JIS D _1201-1977
Shows sufficient slow flammability in the flammability test method. Also,
Among the sheet-like fiber products backed with the composition of the present invention, those having an appropriate hardness are not greatly melted, dropped or spilled due to heat at the time of fire, and are slow-flammable. There is enough time to escape from the original. In addition, no harmful gas such as a halogenated gas is generated during a fire or combustion for a heat cycle, and the amount of generated carbon monoxide is small. Further, no fogging phenomenon of the glass due to the normal volatilization gas occurs. Thus, sheet-like textile products backed with the present composition are particularly suitable for automotive interiors, especially ceilings,
It is suitable as a surface covering of a seat, a floor or a rug for a deck portion.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takanori Takami 960 Gantz Kasei Co., Ltd., Kashiwara-cho, Hikami-gun, Hyogo Prefecture

Claims (5)

[Claims] 1. An aqueous slow-flammable resin composition for backing, comprising 1 to 50 parts by weight of an epoxy resin as a solid content based on 100 parts by weight of a solid content of an aqueous ethylene polymer emulsion. 2. The composition according to claim 1, wherein the composition contains 3 to 30 parts by weight of an epoxy resin as a solid content. 3. The composition according to claim 1, which is used for backing automotive interior materials. 4. The composition according to claim 1, which has a solid content of 50%.
~500g / m ² backing late-retardant sheet-like fibrous products. 5. The fiber sheet product according to claim 4, wherein the fiber sheet material is a car interior material.