JP2020164715A - Flame-retardant resin composition - Google Patents

Abstract

To provide a flame-retardant resin composition that does not use halogen compounds, maintains excellent flame retardancy equal to or higher than that of conventional products, suppresses appearance defects that occur when wet, and provides a resin film having excellent elasticity.SOLUTION: A flame-retardant resin composition contains (b) an emulsified dispersion of liquid phosphorus-type flame retardant using alkali-soluble acrylic polymer as dispersant by 50 to 500 pts.wt. and (c) a melamine cyanurate by 50 to 500 pts.wt. with respect to 100 pts.wt. of (a) an urethane resin emulsion.SELECTED DRAWING: None

Description

The present invention relates to a flame-retardant resin composition, and more particularly to the improvement of flame-retardant property when a textile product is processed and the suppression of appearance defects that occur when wet with water.

Conventionally, polyester fibers have been used for automobile interior materials such as seats and floor mats. Since automobile interior materials are required not to burn easily in the event of a fire, flame retardancy is imparted by treating the fibers with a flame-retardant resin composition to which a flame-retardant material is added.
Decabromdiphenyl oxide (DBDPO) and antimony trioxide (Sb ₂ O ₃ ) have been used as typical flame retardants, but halogen compounds may generate harmful substances such as dioxins in the event of a fire. It is designed to be avoided. In addition, since antimony contains heavy metals such as lead as impurities, its use can be avoided as well.

Therefore, various phosphorus compounds have attracted attention as a promising option and are actually widely used. Among them, ammonium polyphosphate is used as a flame retardant for textile products for automobile interiors because it has excellent flame retardancy, is safer than other phosphorus compounds, and is difficult to bleed out.

On the other hand, if the sheet is placed under hot and humid conditions, or if water or hot water is spilled on the sheet, ammonium polyphosphate will elute on the surface due to its water solubility, causing stains and slime called "wrinkles". Sometimes. In addition, there are problems such as color transfer in which the dye used for dyeing the fiber fabric adheres to the clothes of the occupant and the yarn is easily frayed.

In Patent Document 1, the present inventors have at least one resin emulsion (a), a polyester resin emulsion (b), a liquid phosphorus flame retardant (c), and an aromatic group selected from an acrylic resin emulsion and a urethane resin emulsion. We have proposed a flame-retardant resin composition characterized by containing the surfactant (d) having the above, and have been able to impart excellent flame retardancy while reducing wrinkles. On the other hand, since a surfactant is used to disperse the liquid phosphorus flame retardant, the resin film becomes hydrophilic, and there is a limit to the suppression of wrinkles that occur when wet, and there is room for improvement.
Japanese Patent Application No. 2016-195072

The subject of the present invention is flame retardancy, which does not use a halogen compound, maintains excellent flame retardancy equal to or higher than that of the conventional product, suppresses appearance defects that occur when wet, and obtains a resin film having excellent elasticity. The purpose is to provide a sex resin composition.

The present invention contains (a) at least one resin emulsion selected from an acrylic resin emulsion and a urethane resin emulsion, and (b) an emulsified dispersion of a liquid phosphorus-based flame retardant containing an alkali-soluble acrylic polymer as a dispersant. It is a flame-retardant resin composition characterized by.

The flame-retardant resin composition of the present invention can suppress appearance defects that occur when wet, and can form a film having excellent elasticity, while maintaining flame retardancy equal to or higher than that of conventional products without using a halogen compound. Therefore, it is suitable for processing textile products that require flame retardancy, such as automobile interior seats.

The flame-retardant resin composition of the present invention contains at least one resin emulsion selected from (a) acrylic resin emulsion and urethane resin emulsion as a binder component. The acrylic resin emulsion is obtained by a method such as emulsion polymerization of an acrylic monomer in the presence of an emulsifier. The urethane resin emulsion can be obtained by reacting a polyol compound such as a polyester polyol, a polyether polyol, or a polycarbonate polyol with a polyhydric isocyanate compound in an organic solvent, and then inversion emulsifying into an aqueous phase.

The flame-retardant resin composition of the present invention contains (b) an emulsified dispersion of a liquid phosphorus-based flame retardant containing an alkali-soluble acrylic polymer as a dispersant. The liquid phosphorus flame retardant is a flame retardant that contains phosphorus and is liquid at room temperature. Although not particularly limited, organic phosphorus compounds are preferable, and among them, aromatic phosphate ester monomers and aromatic phosphate ester condensates containing 0.1% by weight or more of phosphorus in the molecule are preferable. preferable. Among the aromatic phosphate ester condensates, phenol, 4,4'-(propane-2,2-disyl) diphenol and trichlorophosphine oxide reaction product (BDP) are more preferable.

An alkali-soluble acrylic polymer is used as the dispersant to emulsify and disperse the liquid phosphorus flame retardant. The alkali-soluble acrylic polymer has alkali-soluble because it has many carboxyl groups in the molecule. By using this polymer in an alkaline atmosphere, the liquid phosphorus flame retardant can be emulsified and dispersed.
Further, the weight average molecular weight of the alkali-soluble acrylic polymer is preferably 5,000 to 1,000,000. When the molecular weight is in this range, the dispersibility of the liquid phosphorus flame retardant is excellent, and there is no possibility of affecting the wrinkles when the flame retardant resin composition is processed into a textile product. The alkali-soluble acrylic polymer preferably contains acrylic acid or methacrylic acid and has an acid value of 200 or more.
At the time of emulsification and dispersion, it is preferable to use 2 to 10 parts by weight of the alkali-soluble acrylic polymer with respect to 100 parts by weight of the liquid phosphorus flame retardant.

The blending amount of the emulsified dispersion of the liquid phosphorus flame retardant is preferably 50 to 500 parts by weight with respect to 100 parts by weight of the resin emulsion (a) based on the solid content. When used in this range, the flame-retardant resin composition has excellent flame retardancy, and there is no risk of wrinkling when processed into a textile product.

The flame-retardant resin composition of the present invention preferably further contains (c) melamine cyanurate. By containing melamine cyanurate, sufficient flame retardancy can be obtained even when the amount of the emulsified dispersion of the liquid phosphorus flame retardant used is small.
The blending amount of melamine cyanurate is preferably 50 to 500 parts by weight with respect to 100 parts by weight of the urethane resin emulsion based on the solid content.

In addition to the above-mentioned compounding components, various additives can be further added to the flame-retardant resin composition of the present invention as long as the excellent effects of the present invention are not impaired. Examples thereof include flame retardants other than melamine cyanurate such as aluminum hydroxide, boron compounds and zirconium compounds, cross-linking agents such as isocyanate compounds, and thickeners.
Further, inorganic fillers, dispersants, thickeners, wetting agents, foaming agents, foam stabilizers, antifoaming agents, pigments, dyes, plasticizers, antiaging agents, ultraviolet absorbers, preservatives and the like can be used.

The solid content, pH and viscosity of the flame-retardant resin composition of the present invention obtained as described above are not particularly limited, but are generally used from the viewpoint of sedimentation stability and the like of the composition. The solid content is 30 to 70% by weight, preferably 30 to 60% by weight, the pH is 5 to 10, preferably 6 to 10, and the viscosity (BH type viscometer, 20 ° C., 10 rpm) is 10,000 to 60,000 mPa. s, preferably 10,000 to 40,000 mPa · s.

By using the flame-retardant resin composition of the present invention as a backing layer for a fiber material such as a car seat fabric, a car seat having excellent flame retardancy can be obtained. The car seat fabric is not particularly limited as long as it does not generate harmful gas in the event of a fire and uses a treatment agent that does not generate formaldehyde as a treatment agent such as a shrink-proof processing agent. For example, synthetic fibers such as polyester, polypropylene, nylon and acrylic, natural fibers such as wool or blends thereof can be mentioned.

The coating amount of the flame-retardant resin composition of the present invention as a backing layer is 10 to ²⁰⁰ g / m ² in terms of solid content, preferably 20 to 150 g / m ² . If the coating amount is less than 10 g / m ² , the flame retardancy may be insufficient, and if it exceeds 200 g / m ² , the texture is impaired, which is economically unfavorable.

Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples and Comparative Examples, but these are specific examples and are not particularly limited thereto.

Preparation of emulsified dispersion of liquid phosphorus-based flame retardant using alkali-soluble acrylic polymer as dispersant 20% by weight of 25% ammonia aqueous solution in 100 parts by weight of JONCRYL693 (BASF, average molecular weight 6000, trade name) which is an alkali-soluble acrylic polymer. Water was added to the portion and the solid content so that the solid content was 30%, and the mixture was stirred at room temperature for 10 minutes, the temperature of the mixed solution was raised to 60 ° C., and the mixture was stirred for 30 minutes to prepare an alkali-soluble acrylic polymer solution.
FP-600 (trade name, manufactured by ADEKA Corporation), which is a reaction product of phenol, 4,4'-(propane-2,2-disyl) diphenol and trichlorophosphine oxide as a liquid phosphorus flame retardant, is placed in a reaction vessel. 100 parts by weight of the solid content and 4 parts by weight of the alkali-soluble acrylic polymer solution were added, and the mixture was stirred and mixed at room temperature for 30 minutes. Then, water was added to adjust the solid content to 65%, and an emulsified dispersion was prepared.

Preparation of flame-retardant resin composition As a resin emulsion, Hydran WLA-210 (DIC Co., Ltd., solid content 30%, trade name), which is a urethane-based resin emulsion, has 100 parts by weight of solid content and melaminesia, which is a nitrogen-based flame retardant. 250 parts by weight of nurate, 250 parts by weight of the emulsified dispersion of the flame retardant as the content of FP-600, and Ultrasol V-280 (manufactured by Aika Kogyo Co., Ltd., solid content 28) which is an acrylic thickener as a thickener. %, Tg 25 ° C., trade name) was blended in 10 parts by weight with a solid content, and water was further added to adjust the solid content to 48% to obtain the flame retardant resin composition of Example 1.

In addition to the materials used in Example 1, JONCRYL690 (BASF, average molecular weight 16500, trade name), which is an alkali-soluble acrylic polymer as a dispersant for liquid phosphorus flame retardants, and Emargen A-60, which is a nonionic surfactant (trade name). Kao Co., Ltd., solid content 100%, trade name), ULA-2 (manufactured by Aika Kogyo Co., Ltd., solid content 46%, Tg60 ° C., trade name) and ULN-3 (manufactured by Aika Kogyo Co., Ltd. Each flame retardant resin composition of Examples 2 to 6 and Comparative Examples 1 and 2 was carried out in the same manner as in Example 1 except that the formulation was changed to Table 1 using 50%, Tg-42 ° C., trade name). Was prepared. The evaluation was performed by the following method.

Each flame-retardant resin composition was applied to a flame-retardant thin fabric (with a basis weight of 200 g / m ² ) with a doctor knife so as to have a dry weight of 50 g / m ² . Then, the test piece was prepared by hot air drying at 140 ° C. to reduce the moisture content to less than 5%, and then curing overnight at 23 ° C. in a 50% RH atmosphere. A sample piece was obtained by cutting the test piece into 35 cm × 20 cm pieces.
In accordance with FMVSS-302, which is a flame retardant standard for automobile interior fields, the prepared sample pieces were subjected to a combustion test by the horizontal method. Six points were tested, and those with an average burning rate (mm / min) and standard deviation (σ) of burning rate + 4σ = 100 or less were accepted.

Wrinkle test Each flame-retardant resin composition was applied to a thin fabric (with a basis weight of 200 g / m ² ) with a doctor knife so as to have a dry weight of 70 g / m ² . Then, the test piece was prepared by hot air drying at 140 ° C. to reduce the moisture content to less than 5%, and then curing overnight at 23 ° C. in a 50% RH atmosphere. The test piece was placed on the urethane foam so that the resin-coated surface (back surface) was on the bottom, and distilled water at room temperature was dripped from the top (front surface). After natural drying for 24 hours at 23 ° C. and 50% RH atmosphere, the presence or absence of stains was visually confirmed from the surface side and evaluated according to the following criteria.
◯: No change in appearance ×: Stain due to getting wet is observed

When each of the flame-retardant resin compositions of Examples 1 and 2 was used, the appearance and flame-retardant performance when wet were good. Further, it was confirmed that Examples 3 to 6 in which the acrylic resin emulsion was used instead of the urethane resin emulsion also had a good appearance when wet, but the flame retardancy was slightly reduced but within the acceptable range. On the other hand, when the flame-retardant resin composition of Comparative Example was used, either performance was insufficient.

Claims (4)

It is characterized by containing (a) at least one resin emulsion selected from an acrylic resin emulsion and a urethane resin emulsion, and (b) an emulsified dispersion of a liquid phosphorus flame retardant containing an alkali-soluble acrylic polymer as a dispersant. Flame retardant resin composition. The flame-retardant resin composition according to claim 1, wherein the resin emulsion (a) contains a urethane resin emulsion. The flame-retardant resin composition according to claim 1 or 2, further comprising (c) melamine cyanurate. Based on the solid content, 50 to 500 parts by weight of the emulsified dispersion of the liquid phosphorus flame retardant containing the alkali-soluble acrylic polymer as the dispersant was added to 100 parts by weight of the resin emulsion (a). c) The flame-retardant resin composition according to claim 3, which contains 50 to 500 parts by weight of melamine cyanurate.