JPH0320514B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical Field of the Invention) The present invention relates to a flame-retardant artificial leather-like structure that is water resistant and flexible. (Prior art and its problems) In recent years, composite materials made of synthetic fibers such as artificial leather and resin have been widely used for clothing, interior materials, industrial materials, etc. As a material, it is applied to seats, curtains, wall coverings, etc. in vehicles such as aircraft, ships, trains, and automobiles, as well as in hotels and hospitals. The characteristics of artificial leather are also utilized in things such as shoes and bags. However, when applied to interior materials, clothing, industrial materials, etc., there are strict legal regulations due to the large amount of human damage caused by fire, and only those that pass these regulations cannot be put to practical use. For example, for automobile interior materials,
FMVSS-302 or JIS・D-1201, for wall covering materials
JIS A-1321, aircraft interior materials have laws and regulations such as the FAA, and must pass these regulations. Additionally, automakers often set their own standards that are stricter than legal regulations. Generally, various kinds of flame-retardant fiber products are known, but flame-retardant products made of composite materials made of synthetic fibers and resins have the following problems, so they lose their value as luxury products. It has not been possible to easily impart flame retardancy without adding flame retardance. (1) Synthetic fibers and resins have different combustion mechanisms, and there was no material that could satisfactorily achieve flame retardancy for both. (2) In order to satisfy flame retardancy, it is necessary to contain a large amount of flame retardant, which results in disadvantages such as rough hardening of the texture, decrease in color fastness, and even a sticky feeling. . (3) The flame retardant easily migrates, causing a sticky feeling and oozing of the dye, which has the disadvantage of impairing the surface quality. (4) When immersed in water or when sweat or wet clothing comes into contact with the product, the flame retardant elutes, causing problems such as decreased flame retardancy and poor quality. Known examples of flame-retardant artificial leather-like structures include JP-A-54-127002, JP-A-56-85478, and JP-A-58-13786, but none of them have water resistance.
Its use was subject to considerable restrictions. (Object of the invention) The present invention is based on JIS D-1201, FMVSS-302,
FAA, etc. as well as JIS/L-1091, DOC-FF-5
A flame-retardant artificial leather-like structure can be provided that exhibits excellent flame retardancy that meets the flame retardant standards stipulated in ``-74'' and can achieve unprecedented water resistance and flexibility. It is. (Structure of the Invention) In an artificial leather-like structure made of polyurethane and fibers, a mixed composition of at least one compound selected from the following groups A, B, C, and D4 mainly on the back surface of the structure. 1. A flame-retardant artificial leather-like structure, in which 10 to 100% by weight of the compound is added to the structure. A: A halogenated phosphate ester that has fluidity at a temperature of 40°C or lower and has a solubility in water of 1% or lower at the same temperature or lower. B: A bromine-containing compound having a solubility in water of 1% or less in the range of 0°C to 40°C, a melting point of 110°C or more, and a bromine content of 30% or more. C: Antimony oxide D: Water-insoluble organic resin having a hardness of 2H or less in a pencil scratch test based on JIS K-5400. (Description of structure) The artificial leather-like structure as used in the present invention refers to ultrafine fibers (mainly 1 denier or less) made of polyester, nylon, or polyacrylonitrile fibers.
The nonwoven fabric is impregnated with mainly polyurethane as a polymeric elastic material. In addition to polyurethane, various rubber materials such as natural rubber, chloroprene rubber, SBR, acrylic rubber, and silicone rubber materials may be used in combination. Additives such as matting agents, pigments, and stabilizers are appropriately used in these elastic polymers. Artificial leather-like structures include suede-like artificial leather with a raised surface and artificial leather for shoes, bags, and jackets whose surface is coated with an elastic polymer, and the present invention is applicable to both forms. . The artificial leather-like structure may have a woven or knitted fabric adhered to the back side for shape retention or physical reinforcement. The mixed composition is applied to the back side of the artificial leather-like structure by coating, printing, impregnation, or other methods. It is important to keep the distribution of the mixed composition within 2/3 of the thickness of the artificial leather-like structure, especially within 1/2 or less, in order to maintain surface quality, color fastness, dye oozing, stickiness, etc. Preferable from this point of view. The mixed composition of the present invention, that is, the flame retardant has the above-mentioned A,
This is a composition consisting of compounds of four groups B, C, and D, and at least one compound selected from each group. Group A is 40℃
Halogenated phosphate esters that are fluid at the following temperatures and have a solubility in water of 1% or less at the same temperature or below, such as tris dibromopropyl phosphate, tris dichloropropyl phosphate, tris chloroethyl phosphate, mono It is a water-insoluble compound that is liquid at room temperature, such as 2,3 dichloropropyl bis 2,3 dibromopropyl phosphate and trischloroethyl phosphide. Preferably, it is a halogenated phosphate ester that is a liquid material that has fluidity even at 0°C or lower and does not vaporize at 180°C or lower. The compounds of group A have a plasticizing effect on the polymeric elastomer constituting the artificial leather-like structure, and further act as softeners for the resins of group D. Usually, the halogenated phosphate ester is prepared as an emulsion and then mixed with other compounds to form a uniform mixed composition. In particular, 1,3 dichloropropyl phosphate is preferably used because it has a great softening effect. The compound of Group B of the present invention has a solubility in water of 1% or less at a temperature of 40°C or lower, and a melting point of 110°C.
It is a bromine-containing compound which is above and has a bromine content of 30% or more. The compound consisting of this group B is the main component of the mixed composition of the present invention,
Those with a high bromine content are preferably used. Compounds with a bromine content of less than 30% do not exhibit sufficient flame retardancy. Particularly preferred are decabromodiphenyl ether and hexabromocyclododecane, which have a high bromine content. It is preferable that the melting point is 110°C or higher; if it is lower than 110°C, color fastness decreases, bleeding occurs, and the quality deteriorates. Examples of Group B compounds include the following. Decabromodiphenyl ether (melting point: 290℃,
Bromine pigment; 82%), tetrabromobisphenol A (melting point: 178°C, bromine content: 58%) and its derivatives, tetrabromobisphenol S (melting point: 280
°C, bromine content; 56%) and its derivatives, tetrabromophthalic anhydride (melting point; 269
°C, bromine content: 67%), hexabromobenzene (melting point: 325 °C, bromine content: 86%), hexabromocyclododecane (melting point: 172 °C, bromine content: 72
%), pentabromotoluene (melting point: 280°C, bromine content: 81%), pentabromophenyl acrylic ether (melting point: 165°C, bromine content: 74%), and other water-insoluble powders. Group C of the present invention is antimony oxide, and when this compound is used in combination with the bromine compound of Group B, flame retardancy with a high synergistic effect can be obtained. Examples of antimony oxide include antimony trioxide, antimony tetroxide, and antimony pentoxide, and antimony trioxide is particularly preferably used because it combines with bromine compounds during combustion and exhibits high flame retardancy. Antimony oxide is 20-80% compared to bromine compounds
It is blended. Preferably, it is blended in an amount of 30 to 50%. Group D is a water-insoluble organic resin whose resin film alone has a hardness of 2H or less as measured by the pencil scratch test method according to JIS K5400 6.14. The resin consisting of group D is a flexible film-forming resin that can contain flame-retardant compounds of groups A to C, especially compounds of groups B and C during film formation, and preferably has a hardness of 2B to 6B. preferable. Furthermore, resins that form a film in the temperature range of 80 to 120°C are preferably used. Examples include resins such as polyvinyl chloride, polyurethane, polyacrylate, and polyester. In particular, ethyl acrylate, butyl acrylate,
It is preferably used in terms of uniformity, compatibility, and flexibility, consisting of a 3-copolymer of 2-ethylhexyl arylate. The mixed composition of the present invention may be mixed with dispersants, thickeners, colorants, phosphorus-containing compounds, etc. as appropriate. The mixed composition containing the compounds of the four groups A to D of the present invention as main components is prepared as a hydrogen dispersion or a solvent-based liquid and is usually adjusted to contain 30 to 70% by weight of the active ingredients. The mixed composition is applied to the back side of the artificial leather-like structure by a coating method, etc., and the weight after drying is 10 ~
100% and obtain the desired flame retardancy. Preferred flame retardancy was exhibited and sufficient water resistance was obtained when it was applied at 10 to 30% for automobile interior materials and at 30 to 70% for wall covering materials and aircraft interior materials. The performance of the mixed composition of the present invention can be further optimized by combining the compounds of groups A to D. In other words, it is important to utilize the characteristics of each group. Compounds from group A are used as softening agents, compounds from group B are used as main flame retardants, and compounds from group C are used as flame retardant aids in combination with bromine compounds. The synergistic effect and group D compounds maximize their role as flexible binders. The preferred mixing ratio is as follows. Compound of group A 10 to 30 parts B 20 to 60 C 10 to 30 D 5 to 30 parts More preferably, the mixing ratio of the compound of group D to the total weight of the compounds of groups A, B, and C is 30 % or less 5%
This is the above mixed composition. (Mechanism of action of the invention) The flame retardant according to the invention is a dispersion of compounds consisting of the above four groups A to D, each of which is essential for flame retardation of artificial leather-like structures. . The compound of group A is the only liquid among flame-retardant compounds, and this compound acts as a flame-retardant plasticizer for artificial leather-like structures and organic resins selected from group D, and improves flexibility. Grant. Both compounds of Groups B and C combine during combustion, exhibiting a synergistic effect of bromine and antimony, and achieving high flame retardancy. In particular, compounds with a high bromine content have an effective effect on flame retardation, making it possible to achieve flame retardancy with a low amount of adhesion. Furthermore, the non-aqueous organic resin of group D has the effect of fixing the flame-retardant compounds of groups A to C to the artificial leather-like structure. The flame retardant, which is a dispersion of a mixed composition of compounds with different properties, imparts viscosity, wettability, and moisture permeability to the dispersion, thereby improving the moisture permeability and adhesion of the flame retardant compound to artificial leather-like structures. Adjustment of the distribution state is enabled. (Effects of the Invention) The present invention has realized a highly flame-retardant artificial leather-like structure that has a softener and water resistance by combining a specific water-insoluble flame-retardant compound and a resin. By taking advantage of the characteristics of each compound that has a specific performance, we have achieved an improvement in flame retardancy due to a synergistic effect, making it possible to impart flame retardancy with a low amount of adhesion. Hereinafter, the present invention will be further explained with reference to Examples. Example 1 Artificial suede made of polyurethane-impregnated thermoplastic synthetic fiber with a thickness of 1.1 mm (“Ecsaine” manufactured by Toray Industries)
A polyester fabric having a basis weight of 80 g/m ² was heat-sealed to the back side of the fabric as a backing fabric using a low melting point polyamide resin adhesive. Next, a water-dispersed flame retardant consisting of the following water-insoluble flame retardant compound and acrylic resin was prepared. The viscosity was 3000 CPS (25°C). Tris-dichloropropyl phosphate 10 parts Decabromodiphenyl ether 20 Antimony trioxide 10 Acrylic resin 4 (Nippon Reichhold, Boncourt WP-210) Dispersant 2 parts (ethylene oxide adduct of alkylphenol) Thickening Agent (CMC) 1 Water 53 Total 100 parts To prepare a flame retardant, an emulsified version of tris dichloropropyl phosphate was mixed with a dispersion of decabromodiphenyl ether and antimony trioxide. Next, the acrylic resin and the thickener were added and mixed while stirring. This mixed composition was applied to the artificial suede lining fabric using a round blade knife coater, and then heated at 110°C for 15 minutes.
Heat treated for minutes. The amount of the composition deposited was 24% by weight. As a comparison, as in the above example, ammonium polyphosphate was added as a substitute for the flame-retardant compound tris dichloropropyl phosphate to the artificial suede lined with the fabric (Comparative Example 1), and one that did not contain tris dichloropropyl phosphate. (Comparative Example 2) Furthermore, a flame retardant consisting of a mixed composition not containing decabromodiphenyl oxide (Comparative Example 3) or antimony trioxide (Comparative Example 4) was coated, and 23 to 25% of the flame retardant was adhered. was created. Regarding these, flame retardancy (burning rate) was measured according to the FMVSS-302 standard, and flexibility was measured according to the JIS-L1079 standard. Water resistant in water at room temperature
After immersion for 24 hours (bath ratio 1:300), it was dehydrated for 2 minutes in a domestic washing machine and then dried. Water resistance was calculated by weight loss rate based on weight change. The artificial suede of the present invention had high flame retardancy and excellent water resistance. On the other hand, in comparative examples, those containing ammonium polyphosphate as a substitute for tris dichloropropyl phosphate lacked water resistance, and those containing no ammonium polyphosphate lacked flexibility. Those containing no decabromodiphenyl ether or antimony trioxide had poor flame retardancy. The results are shown in Table 1. All data are average values of 5 measurements.

[Table] ** The larger the number, the harder it is Example 2 A flame retardant was coated on the back side of 0.8 mm thick artificial suede (Toray's "Ecsaine") using a doctor knife, and heat treated at 120°C for 10 minutes.
The flame retardancy of the obtained flame retardant artificial suede was determined by JIS L-
A vertical combustion test using 1091 (A-4 method) was conducted to measure the carbonization length. Water resistance is 50℃ in a home washing machine.
After washing in hot water for 10 minutes, the weight change and flammability were evaluated. On the other hand, the impregnated distribution state of the flame retardant was determined by coloring with a disperse dye, and the impregnation depth (mm) from the back surface was observed in a cross section. Tris dichloropropyl phosphate 8 parts Hexabromocyclododecane 24〃 Antimony trioxide 8〃 Acrylic resin 6〃 (Ultrasol 2635; manufactured by Takeda Pharmaceutical) Dispersant 2〃 (Daufu Ax-2A; manufactured by Dow Chemical) Thickener (CMC) 1.2〃 Disperse dye (Foron Red FB) 1〃 Water 49.8〃 Total 100 parts As a comparative example, one coated with a commercially available flame retardant in the same manner as in Example 2 and heat-treated at 120°C for 10 minutes was used. As is clear from the results shown in Table 2, the artificial suede treated with the flame retardant of Example 2 was provided with excellent water resistance and flame retardancy. On the other hand, those treated with a flame retardant in Comparative Examples lacked water resistance, and the flame retardancy significantly decreased after washing in a washing machine. All commercially available flame retardant compositions failed to provide sufficient flame retardancy despite the high coating weight, and only a specific composition such as the one of the present invention was good.

【table】

Claims (1)

[Claims] 1. In an artificial leather-like structure made of polyurethane and fibers, at least one of the following groups A, B, C, and D4 is applied mainly to the back surface of the structure.
1. A flame-retardant artificial leather-like structure obtained by adding 10 to 100% by weight of a mixed composition of selected compounds to the structure. A: A halogenated phosphate ester that has fluidity at a temperature of 40°C or lower and has a solubility in water of 1% or lower at the same temperature or lower. B: A bromine-containing compound having a solubility in water of 1% or less in a temperature range of 0°C to 40°C, a melting point of 110°C or more, and a bromine content of 30% or more. C: Antimony oxide D: Water-insoluble organic resin having a hardness of 2H or less in a pencil scratch test based on JIS K-5400.