JP4469706B2 - Back retardant resin aqueous composition for backing - Google Patents

Description

  The present invention provides a carpet backing for flooring and decking in automobiles, carpeting for flooring of furniture, offices, etc., and providing them with water barrier properties and strength, while at the same time providing slow flame retardancy. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slow-flammable aqueous resin composition for carpet backing, which does not generate formaldehyde during normal times and does not generate toxic gases such as halogen-containing gases in a fire.

With the recent increase in the number of cars and the concentration of houses, measures against such fires are extremely important. In particular, there is a great demand for flame retardancy for various vehicle and furniture interior materials, and various flame retarding techniques have been proposed. For flame retardants of textile products used in automobile interiors, halogen-containing flame retardant copolymer emulsions such as vinyl chloride and vinylidene chloride are used as a backing material used as a reinforcement for textile products, or A method of making a flame retardant by blending a conventional synthetic rubber-based, acrylic-based, acrylic / styrene-based copolymer emulsion, etc., and blends thereof with a flame retardant and applying it to a textile product. Has been proposed. Examples of such flame retardants include liquid or powder phosphoric acid ester-based, halogenated phosphoric acid ester-based, halogen compound-based organic flame retardants, antimony-based, aluminum-based, boron-based inorganic flame retardants, etc. It is used alone or in combination as appropriate. In addition, these flame retardant copolymers and other copolymer emulsions may be copolymerized with a methylol group-containing monomer such as N-methylol acrylamide as a crosslinkable monomer that does not lower the retarded flame retardancy (Patent Document 1). In many cases, an aqueous solution of melamine-formaldehyde resin is blended as a crosslinking agent in the flame retardant blend.
Japanese Patent Application Laid-Open No. 10-237764

However, the above halogen-containing flame-retardant copolymer emulsions and halogen-based flame retardants cause toxic gases such as halogen gas during a fire or combustion such as heat recycling, causing serious harm to the human body. It has drawbacks such as contamination and deterioration of the incinerator.
In addition, the use of methylol group-containing monomers such as N-methylol acrylamide, N-methylol methacrylamide, and methylolated diacetone acrylamide, and melamine-formaldehyde resin is a formaldehyde provided with indoor environmental standards due to its harmfulness to the human body. This is the cause of the occurrence of such a situation, and the use is restricted.

In view of the fact that human accidents in the event of a fire in an automobile often cause the person to become addicted by the toxic gas and carbon monoxide that are generated due to the early fire and the opportunity to escape. As a result of earnest research for the first purpose of obtaining a backing material that has a slow retarding property, does not generate formaldehyde, and does not generate harmful gases in a fire, it contains a certain amount of (meth) acrylonitrile (meta A resin aqueous composition obtained by blending a certain amount of an epoxy resin and aluminum hydroxide into an aqueous copolymer emulsion of an acrylic acid alkyl ester monomer or an ethylene carboxylic acid solves this problem. The present invention has been completed.
That is, the present invention
(1) An aqueous emulsion obtained by emulsion polymerization of an acrylic acid alkyl ester, a methacrylic acid alkyl ester or an ethylene carboxylic acid containing 10 to 50% by weight of (meth) acrylonitrile, based on 100 parts by weight of its solid content An epoxy resin solid content of 10 to 50 parts by weight and an aluminum hydroxide 1 to 300 parts by weight of a flame retardant resin aqueous composition for backing,
(2) A slow-retardant carpet having a backing fabric of 50 to 500 g / m ² as a solid content of the backing flame-retardant resin aqueous composition according to (1), and (3) a carpet for automobile interior The carpet according to ( 2 ),
It is.

  The meaning of “slow flammability” here means “slow flammability” used as a flammability category in “Test method for flammability of organic materials for automobile interior” of JIS D 1201. That is, the material once ignited in a windless atmosphere refers to the property of continuing to burn slowly at a combustion speed of 100 mm / min or less even after the ignition source is removed. This JIS D 1201 flammability test method is based on a combustion test defined in the Federal Motor Vehicle Safety Standard FMVSS-302.

The have it water-emulsion in the present invention, (meth) surfactant one or more of acrylonitrile comprises 10 to 50 wt% (meth) acrylic acid alkyl ester monomer or ethylene-based carboxylic acid and A single or a plurality of aqueous polymer emulsions obtained by emulsion polymerization in an aqueous medium in the presence or absence of a protective colloid or by post-emulsification of a polymer polymerized by a method other than emulsion polymerization. This is a blend of polymer emulsions, and is usually a polymer emulsion alone or a blend of polymer emulsions obtained by emulsion polymerization of ethylene monomers for reasons such as ease of production and economy. Is preferred.

The acrylic acid alkyl ester monomer, for example, methyl acrylate, ethyl acrylate, n- butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n- octyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate, methacrylic Examples of the acid alkyl ester monomer include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. Examples of the ethylene carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and citraconic acid. , Itaconic acid, maleic acid, fumaric acid and the like.

In this (meth) acrylic acid alkyl ester monomer, instead of the conventionally used methylol group-containing monomer such as N-methylolacrylamide, (meth) acrylonitrile is contained as an essential component, but the mixing ratio Is 10 to 50 % by weight based on the total amount of monomer (solid content). If (meth) the amount of acrylonitrile is less than the range, less effect on the slow-retardant, if more than the range, copolymerizable model Nomar is lowered.

The kind and amount of the acrylic acid alkyl ester, methacrylic acid alkyl ester or ethylene-based carboxylic acid are not particularly limited, and may be appropriately selected according to various required physical properties of the carpet fabric to be subjected to flame retardant processing. Can do. For example, in a field requiring a floor or deck section such relatively hard handle of an automobile, the glass transition point (Tg) of Ru der 10 ° C. or more monomers are preferred.

The aqueous emulsion of alkyl acrylate, alkyl methacrylate or ethylene carboxylic acid according to the present invention usually contains an ethylene monomer appropriately selected from the monomer group as a surfactant and / or protective agent. A copolymer emulsion obtained by emulsion polymerization in an aqueous medium in the presence of a colloid, or a blend of these copolymer emulsions.

  The surfactant is not particularly limited as long as it is used in ordinary emulsion polymerization, and conventionally known ordinary surfactants are used. Specifically, for example, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyalkylene alkylphenol ethers, polyoxyethylene / polyoxypropylene block polymers, such as sodium lauryl sulfate, sodium alkylbenzene sulfonate, alkyl Anionic surfactants such as sulfosuccinic acid ester salts and derivatives thereof, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkyl allyl ether sulfates, such as alkylamine salts, quaternary ammonium salts, polyoxyethyl Examples include cationic surfactants such as alkylamines and amphoteric surfactants such as alkylbetaines. A reactive emulsifier can also be used.

The surfactant is usually used in an amount of 0.1 to 10% by weight with respect to the total amount of the alkyl acrylate, alkyl methacrylate and ethylene carboxylic acid. It is preferable to use about 0.5 to 7% by weight from the viewpoint of stability and water resistance.

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 selected appropriately, for example, it can be exemplified usage of about 0.5 to 10% by weight relative to the total amount of that use monomers. The solid content of the ethylene copolymer aqueous 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.

Examples of the polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, organic peroxides such as benzoyl peroxide, and azo compounds such as 2,2-azobisisobutyronitrile. . If necessary, these may be combined with a reducing agent and used as a redox initiator.
In the present invention, an epoxy resin is blended in an aqueous emulsion obtained by emulsion polymerization of an ethylenic monomer containing (meth) acrylonitrile.

  There is no limitation in particular as an epoxy resin used in this invention, Generally the epoxy resin which has a glycidyl group in a terminal group is mentioned. Examples of the epoxy resin having a glycidyl group at the terminal group include bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, bisphenol A novolac type epoxy resin, and methyl resorcinol. 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 is a single emulsion obtained by blending directly into an aqueous ethylene copolymer emulsion, blending as an aqueous epoxy resin solution, or emulsifying in an aqueous medium in the presence of a surfactant. Or as a blend of multiple emulsions.
Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyalkylene alkylphenol ethers, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, glycerin fatty acid esters, polyoxy Nonionic surfactants such as ethylene / polyoxypropylene block polymers, such as fatty acid salts, sodium lauryl sulfate, sodium alkylbenzenesulfonate, alkylsulfosuccinate esters and derivatives thereof, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene Anionic surfactants such as alkylallyl ether sulfates can be mentioned, and these can be used alone or as a mixture of a plurality thereof.

The amount of the epoxy resin used is 10 to 50 parts by weight with respect to 100 parts by weight of the solid content of the ethylene copolymer aqueous emulsion. When the amount used is less than 1 part by weight, the burning rate exceeds 100 mm / min in the flammability test of the organic material for automobile interior according to JIS D 1201, and it becomes flammable. Moreover, when it exceeds 50 weight part, since the storage stability of this invention substance falls and it becomes high price, since a problem arises also on economical efficiency, it is unpreferable.

  In addition to the ethylene-based copolymer aqueous emulsion and the epoxy resin, the carpet-backing slow-flammable resin aqueous composition of the present invention may contain a crosslinking agent for improving 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 the like. The compounding amount of these crosslinking agents is usually 1 to 20 parts by weight, preferably 2 to 15 parts by weight in terms of solid content with respect to 100 parts by weight of solid content of the ethylene copolymer aqueous emulsion.

Furthermore, a flame retardant can be used in the slow-flammable resin aqueous composition of the present invention within the range of use that does not hinder the excellent effects of the present invention. Examples of the flame retardant include an antimony compound, a boron compound, an aluminum compound, a magnesium compound, a zirconium compound, and the like, such as a flame retardant that does not normally fog glass or the like and does not generate a harmful gas in a fire. Of these, aluminum compounds, particularly aluminum hydroxide, are preferred. The amount of these flame retardants used may be, for example, about 1 to 300 parts by weight with respect to 100 parts by weight of the solid content of the copolymer emulsion of the ethylene monomer.
In addition, within the usage range that does not hinder the excellent effects of the present invention, inorganic fillers, dispersants, thickeners, wetting agents, foaming agents, foam stabilizers, antifoaming agents, pigments, dyes, plasticizers, anti-aging agents UV absorbers, preservatives and the like can be used.

  The solid content, pH and viscosity of the delayed flame retardant resin aqueous composition of the present invention obtained as described above are not particularly limited, but from the viewpoint of sedimentation stability and the like of the composition, Generally, the solid content is 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 15000 mPa · s, preferably 1000 to 10000 mPa · s. s

  By using the present invention as a backing layer for carpet fabric, it is possible to obtain a carpet having excellent retarding properties. The carpet fabric used in the present invention is not particularly limited as long as it does not generate fire harmful gases and uses a treatment agent that does not produce formaldehyde as a fiber treatment agent such as a shrink-proofing agent. Absent. Examples thereof include synthetic fibers such as polyester, polypropylene, nylon, and acrylic, natural fibers such as wool, and blends thereof. In addition, in order to improve the moldability and water barrier properties of the needle punch carpet on the floor of the automobile interior, the needle punch carpet having the composition as a backing layer is subjected to a melt extrusion laminate backing with a thermoplastic resin such as polyethylene. Even if it is, it has slow-flammability.

The coating amount of the composition as a backing layer is 50 to 500 g / m ² (solid content), preferably 50 to 250 g / m ² , and the carpet coated with the composition is used for the above-mentioned JIS D 1201 automotive interior. Shows the slow flammability used as a combustion classification in the combustion test method of organic materials.
If the coating amount is less than 50 g / m ² , the hard texture and slow flame retardance are insufficient, and if it exceeds 250 g / m ² , powder falling occurs, and economical problems also occur.

  The aqueous flame retardant resin composition for carpet lining of the present invention, for example, when it is lined on carpets on floors and decks in automobiles, carpets on floors in furniture, offices, etc., provides water shielding and strength to them. At the same time, it imparts slow flame retardancy, does not generate normal formaldehyde, and does not generate toxic gases such as halogen-containing gases in the event of a fire.

Hereinafter, the present invention will be described in more detail with reference to Examples , Reference Examples and Comparative Examples.
[ Reference Example 1]

(1 ) Preparation of copolymer emulsion In a reactor equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 330 parts by weight of ion-exchanged water and 0.2 parts by weight of sodium dodecylbenzenesulfonate were added. And dissolved by heating at 50 ° C. After replacing the inside of the container with nitrogen, the temperature was raised to 80 ° C., and while maintaining the temperature, 157.5 parts by weight of ethyl acrylate (EA), 270 parts by weight of methyl methacrylate (MMA), 13.5 parts by weight of acrylonitrile (AN) Monomer emulsion 599 obtained by stirring and mixing an aqueous solution in which 9 parts by weight of polyoxyethylene lauryl ether sulfate was dissolved in 140 parts by weight of ion exchange water and a monomer mixture of 9 parts by weight of methacrylic acid (MAA). Part by weight and 50 parts by weight of a 2.5% aqueous potassium persulfate solution were continuously added dropwise over 4 hours to carry out emulsion polymerization. Furthermore, the polymerization was completed by maintaining at the same temperature for 2 hours. Copolymer emulsion obtained was neutralized with 12.5% aqueous ammonia, solid content 45%, pH 7.5, milky white emulsion having a viscosity of 40mPa · s (25 ℃, 30rpm ), ethylene copolymer The Tg of this was 47 ° C.

(2) Preparation of epoxy emulsion To 100 parts by weight of Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.), 5 parts by weight of polyoxyethylene lauryl ether, 0.5 parts by weight of sodium dodecylbenzenesulfonate, and 70 parts by weight of water should be added. The mixture was stirred and mixed to obtain a stable epoxy emulsion.

(3) a copolymer aqueous emulsion and an epoxy resin emulsion obtained in the preparation of samples for burn testing (1) were mixed at a ratio shown in Table 1, and the slow-retardant resin aqueous composition.
100 g / m ² (solid content) of the obtained flame retardant resin aqueous composition was applied to a needle punch carpet (weighing 380 g / m ² ) made of polyester and dried at 150 ° C. for 10 minutes. This was cut into 350 mm × 200 mm and left for 24 hours in an atmosphere of 20 ° C. and 65% RH as a sample.

(4) Combustion test According to FMVSS-302, the prepared sample was subjected to a combustion test by the horizontal method. The test was performed 10 points and displayed as an average burning rate. The results are shown in Table 1.
[ Reference Example 2]

A resin aqueous composition was prepared in the same manner as in Reference Example 1 except that methyl methacrylate and acrylonitrile were in accordance with the formulation shown in Table 1, a sample for combustion test was prepared, and the same combustion test was performed. The obtained results are also shown in Table 1.

A resin aqueous composition was prepared in the same manner as in Reference Example 1 except that methyl methacrylate and acrylonitrile were in accordance with the formulation shown in Table 1, a sample for combustion test was prepared, and the same combustion test was performed. The obtained results are also shown in Table 1.

A resin aqueous composition was prepared in the same manner as in Reference Example 1 except that methyl methacrylate and acrylonitrile were in accordance with the formulation shown in Table 1, a sample for combustion test was prepared, and the same combustion test was performed. The obtained results are also shown in Table 1.
When the sample obtained in Example 2 was further subjected to 250 g / m ² laminate backing of polyethylene and subjected to the same combustion test as in Reference Example 1, the burning rate was 53 mm / min.

A resin aqueous composition was prepared in the same manner as in Reference Example 1 except that methyl methacrylate and acrylonitrile were in accordance with the formulation shown in Table 1, a sample for combustion test was prepared, and the same combustion test was performed. The obtained results are also shown in Table 1.

A resin aqueous composition was prepared in the same manner as in Reference Example 1 except that methyl methacrylate and acrylonitrile were in accordance with the formulation shown in Table 1, a sample for combustion test was prepared, and the same combustion test was performed. The obtained results are also shown in Table 1.

A resin aqueous composition was prepared in the same manner as in Reference Example 1 except that methyl methacrylate and acrylonitrile were in accordance with the formulation shown in Table 1, a sample for combustion test was prepared, and the same combustion test was performed. The obtained results are also shown in Table 1.

A resin aqueous composition was prepared in the same manner as in Example 2 except that acrylonitrile was changed to methacrylonitrile, a combustion test sample was prepared, and the same combustion test was performed. The obtained results are also shown in Table 1.
[Comparative Example 1]

A resin aqueous composition was prepared in the same manner as in Reference Example 1 except that methyl methacrylate and acrylonitrile were in accordance with the formulation shown in Table 1, a sample for combustion test was prepared, and the same combustion test was performed. The obtained results are also shown in Table 1.

MMA: Methyl methacrylate EA: Ethyl acrylate AN: Acrylonitrile MAN: Methacrylonitrile MAA: Methacrylic acid

As is apparent from Table 1, the samples lined with a slow-flammable resin aqueous composition (Examples 1 to 6) containing a copolymer emulsion containing acrylonitrile or methacrylonitrile as a monomer component and an epoxy resin emulsion, The burning rate was remarkably reduced as compared with that backed by a slow-flammable resin aqueous composition (Comparative Example 1) composed of a copolymer emulsion and an epoxy resin emulsion in which neither acrylonitrile nor methacrylonitrile was used as a monomer component.
[ Reference Example 3]

(1) Preparation of copolymer emulsion A copolymer emulsion was prepared in the same manner as in Reference Example 1 except that the amount of monomer used was as specified in Table 2.
(2) Preparation of epoxy emulsion
In the same manner as in Reference Example 1, an epoxy emulsion was prepared.
(3) Preparation of sample for combustion test A sample for combustion test was prepared in the same manner as in Reference Example 1 except that the mixing ratio of the copolymer emulsion and the epoxy emulsion was as prescribed in Table 2. The same combustion test was conducted. The results are shown in Table 2.
[Reference Example 4]

A sample was prepared and a combustion test was conducted in the same manner as in Example 6 except that the usage ratio of the copolymer emulsion and the epoxy resin emulsion was set as shown in Table 2. The obtained results are shown in Table 2.

A sample was prepared and a combustion test was conducted in the same manner as in Example 6 except that the usage ratio of the copolymer emulsion and the epoxy resin emulsion was set as shown in Table 2. The obtained results are shown in Table 2.

A sample was prepared and a combustion test was conducted in the same manner as in Example 6 except that the usage ratio of the copolymer emulsion and the epoxy resin emulsion was set as shown in Table 2. The obtained results are shown in Table 2.

A sample was prepared and a combustion test was conducted in the same manner as in Example 6 except that the usage ratio of the copolymer emulsion and the epoxy resin emulsion was set as shown in Table 2. The obtained results are shown in Table 2.

A sample was prepared and a combustion test was conducted in the same manner as in Example 6 except that the usage ratio of the copolymer emulsion and the epoxy resin emulsion was set as shown in Table 2. The obtained results are shown in Table 2.

A sample was prepared and a combustion test was conducted in the same manner as in Example 6 except that the use ratio of the copolymer emulsion and the epoxy resin emulsion was set as shown in Table 2. The obtained results are shown in Table 2.
[Comparative Example 2]

A sample was prepared and a combustion test was conducted in the same manner as in Example 6 except that the usage ratio of the copolymer emulsion and the epoxy resin emulsion was set as shown in Table 2. The obtained results are shown in Table 2.

MMA: Methyl methacrylate EA: Ethyl acrylate AN: Acrylonitrile MAA: Methacrylic acid needle punch carpet:
Polyester fiber 380 g / m ²
Resin adhesion amount 100 g / m ²

As is clear from Table 2, a copolymer emulsion and an epoxy resin emulsion slow-retardant resin aqueous composition containing the sample lined (Examples 7-11) are not to have been blended with an epoxy resin emulsion (comparative The burning rate was significantly reduced compared to that backed in Example 2).

  By using the composition of the present invention as a backing layer of carpet fabric, for example, a carpet excellent in retarding property can be obtained. Examples of the carpet fabric include synthetic fibers such as polyester, polypropylene, nylon, and acrylic, natural fibers such as wool, and blends thereof. In addition, in order to improve the moldability and water barrier properties of the needle punch carpet on the floor of the automobile interior, the needle punch carpet having the composition as a backing layer is subjected to a melt extrusion laminate backing with a thermoplastic resin such as polyethylene. Even if it is, it has slow-flammability.

Claims (3)

An aqueous emulsion obtained by emulsion polymerization of (meth) acrylic acid alkyl ester, methacrylic acid alkyl ester or ethylene-based carboxylic acid containing 10 to 50% by weight of (meth) acrylonitrile, based on 100 parts by weight of its solid content An aqueous slow-flammable resin composition for backing comprising 10 to 50 parts by weight of an epoxy resin as a solid content and 1 to 300 parts by weight of aluminum hydroxide . A slow-flammable carpet having a backing material of 50 to 500 g / m ² as a solid content of the backing flame-retardant resin aqueous composition for backing according to claim 1. The carpet according to claim 2 , wherein the slow-flammable carpet is an automobile interior carpet.