JPS60215878A - Flame-retardant artificial leather structure - Google Patents

Abstract

PURPOSE:To obtain a soft flame-retardant artificial leather, by treating an artificial leather structure composed of polyurethane and fibers, with a mixture of compounds selected from specific halogenated phosphoric acid esters, bromine- containing compounds, antimony oxides, and water-insoluble organic resins. CONSTITUTION:The back face of an artifical leather structure made of ultrafine synthetic fibers and a polymeric elastomer such as polyurethane, is treated and impregnated with a mixture of (A) one or more halogenated phosphoric acid esters having fluidity at <=40 deg.C, and a water-solubility of <=1% at <=40 deg.C, e.g. 1,3-dichloropropyl phosphate, (B) one or more bromine-containing compounds having a water-solubility of <=1% at 0-40 deg.C, a melting point of >=110 deg.C and a bromine-content of >=30%, e.g. decabromodiphenyl ether, (C) antimony oxides, and (D) one or more water-insoluble organic resins having a pencil hardness (JIS K-5400) of <=2H. The impregnation is processed to 1/2 of the thickness by coating, etc.

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 it is virtually impossible to put it into practical use unless it passes the regulations.

For example, FMVSS-302 or JIS-D-12,01 is used for automobile interior materials, and J15-A-1 is used for wall covering materials.
321, aircraft interior materials have laws and regulations such as the FAA.
It must pass the 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 has been no material that satisfactorily achieves 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 causing a sticky feeling. Ta.

(3) The flame retardant easily migrates, causing dye oozing along with a sticky feeling, which has the disadvantage of impairing surface quality.

(4) When immersed in water or when sweat or wet clothing comes into contact, the flame retardant is eluted, resulting in problems such as decreased flame retardancy and poor quality.

Known examples of flame retardancy for artificial leather-like structures include JP-A-54-1270Q2, JP-A-56-85478, and JP-A-58-1378.6, but none of them are water resistant and cannot be used for that purpose. had to be subject to considerable restrictions.

(Object of the invention) The present invention is based on J Is'-D-1201, FMVSS-30
2. JIS-L-1091, DOC- in the history of FAA etc.
We provide a flame-retardant artificial leather-like structure that exhibits excellent flame retardancy that meets the flame retardant standards stipulated by FF-5-74, and also achieves unprecedented water resistance and flexibility. That's what I got.

(Structure of the Invention) In an artificial leather-like structure made of polyurethane and fibers, the following A,
A mixed composition of at least one compound selected from Groups B, C, and D4 is added in an amount of 10 to 100% by weight based on the structure.
A flame-retardant artificial leather-like 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 less at the same temperature or lower.

The solubility in water is 1% or less in the range of Boo°C to 40°C, the melting point is 110°C or higher, and the bromine content is 3%.
A bromine-containing compound that is 0% or more.

C: Antimony oxide D: Water-insoluble organic resin having a hardness of 2H or less according to a pencil scratch test based on JIS-5400.

(Description of structure) The artificial leather-like structure as used in the present invention refers to a nonwoven fabric of ultrafine fibers (mainly 1 denier or less) made of polyester, nylon, or polyacrylonitrile fibers, and mainly containing polyurethane as a polymeric elastic material. It is impregnated.

In addition to polyurethane, natural rubber, chloroprene rubber, S
B R,' Various rubber materials such as 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 jumpers 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 coated on the back side of the artificial leather-like structure.
It is applied by printing, impregnation, etc.

The mixed composition is applied to 2/3 of the thickness of the artificial leather-like structure from the back side.
It is preferable to keep the distribution within a range of 1/2 or less, especially from the viewpoint of surface quality, color fastness, dye exudation, stickiness, etc.

The mixed composition of the present invention, that is, the fuel agent is 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 a halogenated phosphate ester that is fluid at a temperature of 40°C or lower and has a solubility in water of 1% or lower at the same temperature or lower, such as tris-dibromopropyl phosphate, tris-dichloropropyl phosphate, and tris-chloro. Ethyl phosphate mono 2
, dichloropropyl bis-2.3 dibromopropyl phosphate, trischloroethyl phosphite, and other water-insoluble compounds that are liquid at room temperature. Preferably 0℃
The halogenated phosphoric acid ester is also a liquid material with fluidity and does not vaporize at temperatures below 180°C.

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 large softening effect.

The compound of Group B of the present invention is a bromine-containing compound that has a solubility in water of 1% or less at a temperature of 40°C or lower, a melting point of 110°C or higher, and a bromine content of 30% or higher. Compounds of Group B are the main components of the mixed composition of the present invention, and those with a high bromine content are preferably used. Compounds with a bromine content of less than 30% do not exhibit sufficient flammability. Particularly preferred are decabromodiphenyl ether and hexabromocyclododecane, which have a high bromine content. It is preferable that the melting point is IIO'C or higher; if it is lower than 110C, color fastness decreases, bleeding occurs, and the quality deteriorates.

Examples of Group B compounds include the following.

Decabromodiphenyl ether (melting point: 290°C, bromine pigment: 82%), tetrabromobisphenol A (melting point: 178°C, bromine content: 58%) and its derivatives, tetrabromobisphenol S (melting point: 280°C, bromine m): 56%) OJ: U derivative, tetrabromophthalic anhydride (melting point: 269°C,
Bromine content: 67%), hexabromobenzene (melting point: 3
25°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
℃, bromine content near 4%) 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 to 8 compared to bromine compounds.
Contains 0%. 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-5400 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, 80~
A resin that forms a film in a temperature range of 120°C is preferably used. Examples include resins such as polyvinyl chloride, polyurethane, polyacrylate, and polyester. In particular, it is preferably used in terms of uniformity, compatibility, and flexibility, consisting of a 3-copolymer of ethyl acrylate, butyl acrylate, and 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 of the present invention containing the compounds of the four groups A to D as main components is prepared as a hydrogen dispersion or a solvent-based liquid and is usually adjusted to have an active ingredient content of 30 to 70 Mff1%.

The mixed composition is applied to the back side of the artificial leather-like structure by coating or the like, and is applied in an amount of 10 to 100% by weight after drying to obtain the desired flame retardancy. 1 for automobile interior materials
0-30%, 30-7 for wall covering materials and aircraft interior materials
When added to 0%, it exhibits favorable flame retardancy and sufficient water resistance.

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 take advantage of the characteristics of each group. Compounds from group A are softeners, compounds from group B are main flame retardants,
The compounds of Group C maximize their synergistic effect with the bromine compound as flame retardant aids, and the compounds of Group D maximize their role as flexible binders. The preferred mixing ratio is as follows.

Compounds of group A 10-30 parts B 〃 20-60 II C〃 10-3011 D I '5-30 parts More preferably J based on the total weight of compounds of groups A, B and C
This is a mixed composition in which the mixing ratio of Group D compounds is 30% or less and 5% or more.

(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 the fuel ratio of the artificial leather-like structure. . The compound of group A is the only liquid among the flame-retardant compounds, and this compound acts as a flame-retardant plasticizer for artificial leather-like structures J3 and organic resins selected from group D. Adds gender.

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 retardancy, 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 group A to C to the artificial leather-like structure. The flame retardant dispersed in a mixed composition of compounds with different properties imparts viscosity, wettability, and moisture permeability to the dispersion, thereby improving the moisture permeability of the flame retardant compound to the artificial leather-like structure. This makes it possible to adjust the adhesion distribution state.

(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 at a low amount.

Hereinafter, the present invention will be further explained with reference to Examples.

Example 1 A human varnish needle made of polyurethane-impregnated thermoplastic synthetic fiber with a thickness of 1.1 mm ("Ecsaine°" manufactured by Toshi).

) on the back side using a low melting point polyamide resin adhesive,
A polyester fabric of 80 Q'/m2 was heated as a backing fabric for 1! W t! L. 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).

1~Lis-dichloropropyl small sulfate 10 parts Decabromodiphenyl ether 20JI antimony trioxide 1011 Acrylic resin 4 n (Nippon Reichhold, Boncourt WP-210> Dispersant 2 parts (ethylene oxide adduct of alkylphenol) Thickener (CMG) ) 1 Water 53I1 Total 100 parts To prepare the flame retardant, emulsified tris dichloropropyl phosphate was mixed with a dispersion of decabromodiphenyl ether and antimony trioxide.Next, while stirring the acrylic resin and thickener, Add and mix.

This mixed composition was applied to the above-mentioned varnished backing fabric using a round-blade knife coater, and then heat-treated at 110° C. for 15 minutes. The weight ratio of the composition was 24% by weight.

As a comparison, as in the above example, a human varnish needle lined with a fabric was blended with ammonium polyphosphate as a substitute for the flame retardant compound tris dichloropropyl phosphate (Comparative Example 1), and one containing no tris dichloropropyl phosphate was compared. Comparative Example 2) Furthermore, a flame retardant consisting of a mixed composition not containing decabromodiphenyl sekizide (Comparative Example 3) or antimony trioxide (Comparative Example 4) was coated and 23 to 25% adhesion was produced. .

Regarding these, flame retardancy (burning rate) was measured according to the FMVSS-302 standard, and flexibility was measured according to the JIS-L10'79 standard. Water resistance was determined by immersing the sample in water at room temperature for 24 hours (bath ratio 1:300), dehydrating it for 2 minutes using a household method 'a machine, and then drying it. Water resistance was calculated by weight loss rate based on weight change.

The human varnished needle 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 bosphate 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 1 1: 5E10 indicates that the fire extinguished by itself before the starting line ** The higher the number, the harder it is Example 2 A doctor knife was placed on the back side of a human varnish needle with a thickness of Q and 8 mm (“Ecsaine” made by Toshi). The film was coated with a flame retardant and heat treated at 120°C for 10 minutes. The flame retardancy of the obtained flame retardant varnished material was evaluated according to JlS-1-1091 (A-
A combustion test using the vertical method (method 4) was conducted to measure the char length. Water resistance was evaluated by weight change and flammability after washing in hot water at 50°C for 10 minutes in a household soap washing machine. - The state of impregnation distribution of the flame retardant was observed in a cross section at the impregnation depth (mm) from the back surface by coloring with disperse dye.

Tris dichloropropyl phosphate 8 parts Hexabromocyclododecane 24 Antimony trioxide 811 Acrylic resin 5 n (Ultrasol 2635: manufactured by Narita Pharmaceutical) Dispersant 2 (Dowfax 2A; manufactured by Dowtamical) Thickener (CM
C) 1.211 Disperse dye (Foron Red FB) 1 n water 4
9.8 〃 As a comparative example, a material 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, which are not shown in Table 2, the human varnished needle 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 after washing with Washing II, the flame retardance significantly decreased. All commercially available flame retardant compositions were unable to provide sufficient flame retardancy despite having the highest adhesion, and only specific compositions such as those of the present invention were good.

Claims (1)

[Claims] In an artificial leather-like structure made of polyurethane and fibers, the following A and B are applied mainly to the back surface of the structure.
A flame-retardant artificial leather-like structure obtained by adding 10 to 100% by weight of a mixed composition of at least one compound selected from Groups , C, and D4 to the structure. Δ: 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: Solubility in water is 1% in the temperature range of 0°C to 40°C
A bromine-containing compound having a melting point of 110° C. or higher and a bromine content of 30% or higher. C Antimony Dioxide D: Water-insoluble organic resin having a hardness of 2H or less in a pencil scratch test based on JIS-5400.