WO2004033585A1

WO2004033585A1 - Flame-retardant and method for production thereof, and flame retardant fiber fabric

Info

Publication number: WO2004033585A1
Application number: PCT/JP2003/012811
Authority: WO
Inventors: Masahisa Kitano; Norihiro Moriuchi; Masayuki Mori; Kenjiro Iwamoto
Original assignee: Suminoe Textile Co., Ltd.; Meisei & Co., Ltd.; Air Water Chemical Inc.
Priority date: 2002-10-08
Filing date: 2003-10-07
Publication date: 2004-04-22
Also published as: AU2003275544A1; JP2006077035A; AU2003275544A8

Abstract

A flame-retardant which comprises an expandable graphite and, applied on at least a part of the surface thereof, a phosphate ester and a surfactant. It is preferred that the surface of the graphite is coated with a surfactant layer via a phosphate ester layer. The preferred flame-retardant can be produced by a method comprising applying an organic solvent containing a phosphate ester dissolved therein on an expandable graphite, and then applying an organic solvent containing a surfactant dissolved therein, followed by drying. The flame-retardant can impart satisfactory flame retardancy, and also is excellent in dispersion stability and application stability.

Description

Flame retardant, method for producing the same, and flame-retardant fiber cloth This application claims priority of Japanese Patent Application No. 2002-29474, filed on October 8, 2000. And the disclosure content constitutes a part of the present application as it is. Technical field

The present invention relates to a flame retardant having excellent dispersion stability in a liquid such as an aqueous synthetic resin emulsion and a flame retardant fiber cloth using the same. Background art

Vehicle interior materials, such as automotive sheet skin materials and automotive floor mats, are required to have excellent flame retardancy to enhance safety in the event of a fire. In order to respond to such demands for flame retardancy, it has been customary to incorporate a flame retardant into a synthetic resin backing layer provided on the back surface of an automobile floor mat. As such a flame retardant, for example, a flame retardant having a halogen such as a chlorine atom or a bromine atom in a chemical structure (halogen-based flame retardant) has been widely used (for example, see Patent Document 1).

However, such halogen-based flame retardants are known to generate harmful substances such as hydrogen chloride gas and halogen gas in the event of a fire, and are not preferable from the viewpoint of ensuring passenger safety. It has been pointed out that various harmful substances are generated during disposal, which is not preferable from the viewpoint of global environmental protection.

Therefore, heat is used as a flame retardant in the aqueous synthetic resin emulsion forming the backing layer. It has been proposed to add expandable graphite (see Patent Document 2). According to this technology, sufficient flame retardancy can be imparted, and no harmful substances are generated during a fire or incineration.

Patent Document 1

Japanese Patent Application Laid-Open No. 6-161618 (Claim 1, Paragraph 019)

Patent Document 2

SUMMARY OF THE INVENTION However, the problem that the thermally expandable graphite has poor dispersion stability in an aqueous synthetic resin emulsion. There was. Since the dispersion stability is not good, it is difficult to apply the thermally expandable graphite in a uniformly dispersed state when applied to the back surface of the fiber fabric, and the liquid stability of the emulsion is poor, and the dispersion is relatively short. The tendency of the heat-expandable graphite to agglomerate and settle and separate was strong.

In addition, the application was not smooth enough when applied to the back surface of the fiber fabric, and the coating stability was not sufficient.

In addition, the inclusion of heat-expandable graphite tends to reduce the flexibility of the fiber fabric.

The present invention has been made in view of such technical background, and can provide sufficient flame retardancy, does not generate toxic gas at the time of fire or incineration, and has excellent dispersion stability and coating stability. An object of the present invention is to provide an excellent flame retardant, a method for producing the flame retardant, and a flame retardant fiber fabric using the flame retardant.

Other objects of the present invention will be made clear by the embodiments of the present invention described below. Disclosure of the invention

The above object is achieved by a flame retardant (first invention) characterized in that at least a part of the surface of the heat-expandable graphite is coated with a phosphate ester and a surfactant. Achieved.

Further, the above object is attained by a flame retardant (second invention) characterized in that a surfactant layer is coated on at least a part of the surface of the heat-expandable graphite via a phosphate layer. Is done.

Since any of the above flame retardants is coated with a surfactant, it has excellent dispersion stability. For example, even when the flame retardant is contained in an aqueous synthetic resin emulsion, it does not aggregate and precipitate. Therefore, for example, when the water-based synthetic resin emulsion containing the flame retardant is applied to the back surface of the fiber cloth, the heat-expandable graphite can be applied to the fiber cloth in a uniformly dispersed state, and it is easy to apply. It is also excellent in engineering stability. Further, since the phosphoric acid ester is coated, it is possible to improve the fixing stability of the surfactant and to impart sufficient flexibility to the fiber cloth. In addition, since it contains heat-expandable graphite and phosphate ester, sufficient flame retardancy can be imparted, and no toxic gas is generated during a fire or incineration because no halogen-based flame retardant is used. Furthermore, by adopting a configuration in which the phosphate ester is coated on the heat-expandable graphite in this way, compared with a system in which the heat-expandable graphite and the phosphate ester are simply mixed, the same flame-retardant performance is obtained. Also, there is an advantage that the amount of the heat-expandable graphite used to obtain the above-mentioned is small, that is, the amount can be reduced.

Further, in the flame retardant of the second invention, since the surfactant layer is coated on at least a part of the surface of the heat-expandable graphite via the phosphate layer, the removal of the surfactant is effective. And excellent dispersion stability can be ensured over a long period of time.

In the flame retardant of the present invention, the coating amount of the ester phosphate is 5 to 50 parts by weight and the coating amount of the surfactant is 0.5 to 100 parts by weight of the heat-expandable graphite. It is preferred to employ a configuration in the range of up to 10 parts by weight. As a result, there is an advantage that the dispersion stability as a flame retardant can be improved and the sticking stability of the surfactant can be improved. It is preferable that the average particle size of the heat-expandable graphite is 50 to 100 m. This makes it possible to secure more excellent flame retardancy while ensuring sufficient dispersion stability. As the surfactant, an anionic surfactant is preferably used. As a result, release of the surfactant (release of the coating state) can be reliably prevented. Further, the method for producing a flame retardant according to the present invention comprises: a first coating step of applying an organic solvent containing a phosphoric acid ester to heat-expandable graphite; and a heat-expandable graphite after the first coating step. And a second application step of applying a solvent in which a surfactant is dissolved and contained. According to this production method, the flame retardant of the second invention can be produced with high production efficiency.

In this manufacturing method, it is preferable to perform a drying treatment after the second coating step. Thereby, the phosphate and the surfactant can be firmly fixed to the heat-expandable graphite.

In the first coating step, an organic solvent containing a phosphate ester dissolved therein is applied to the agitated thermally expandable graphite by a spray method, while in the second coating step, a solvent containing a surfactant dissolved therein is stirred. When applied to the heat-expandable graphite by the spray method, there is an advantage that the phosphate ester and the surfactant can be fixed to the heat-expandable graphite in a more uniform state.

The flame-retardant fiber fabric according to the present invention is obtained by applying an aqueous synthetic resin emulsion containing the flame retardant according to any one of the above constitutions to the back surface of the fiber fabric and drying.

Further, another flame-retardant fiber fabric of the present invention is obtained by applying an aqueous synthetic resin emulsion containing a flame retardant produced by any one of the above-mentioned production methods to the back surface of the fiber fabric and drying. is there.

Any of the above flame-retardant fiber fabrics can ensure excellent flame retardancy because the heat-expandable graphite can be applied to the fiber fabric in a uniformly dispersed state. The above emulsion is light in application and excellent in coating stability, so that the quality as a fiber fabric can be improved. Also Since the heat-expandable graphite is also coated with a phosphate ester, sufficient flexibility can be secured as a fiber fabric. No toxic gas is generated during a fire or incineration. BEST MODE FOR CARRYING OUT THE INVENTION

The flame retardant of the first invention is characterized in that at least a part of the surface of the heat-expandable graphite is coated with a phosphate ester and a surfactant. Since this flame retardant is coated with a surfactant, it has excellent dispersion stability. Therefore, for example, even when the aqueous synthetic resin emulsion is contained in the aqueous synthetic resin emulsion, it does not aggregate and precipitate and separate.For example, when the aqueous synthetic resin emulsion containing the flame retardant is applied to the back surface of the fiber cloth, There is an advantage that the heat-expandable graphite can be applied to the fiber cloth in a uniformly dispersed state, and the application is smooth and the coating stability is excellent. Further, since the phosphoric acid ester is coated, the fixing stability of the surfactant can be improved, and sufficient flexibility can be given to the fiber cloth. In addition, since it contains heat-expandable graphite and phosphate ester, sufficient flame retardancy can be imparted, and since it does not contain halogen-based flame retardants, there is no generation of toxic gas at the time of fire or incineration. It is sufficient if at least a part of the surface of the heat-expandable graphite is coated with a phosphate ester and a surfactant. Of course, not only on the surface but also in the interlayer of the heat-expandable graphite. It may be put on.

A preferred embodiment is a configuration in which at least a part of the surface of the heat-expandable graphite is coated with a surfactant layer via a phosphate ester layer (second invention). With the phosphate phosphate layer interposed in the intermediate layer, detachment of the surfactant is more effectively prevented, so that excellent dispersion stability can be maintained over a long period of time.

The heat-expandable graphite used in the present invention can be produced, for example, by subjecting natural graphite powder or particles to a reaction treatment with sulfuric acid and an oxidizing agent, followed by acid removal, water washing (neutralization), and drying. It is not limited to those manufactured by a simple manufacturing method. No. The method for producing the heat-expandable graphite is also described in, for example, Japanese Patent Publication No. Sho 60-34492. In general, it is known that when heat-expandable graphite is heated at about several hundred to 100 ° C., the distance between the layers expands from tens to hundreds of times.

The average particle diameter (normal temperature state) of the thermally expandable graphite is preferably 50 to 100 m. If it is less than 50 m, it is not preferable because sufficient flame retardant performance cannot be obtained, and if it is more than 100 m, the dispersion stability is lowered and it is easy to fall off from the fiber cloth, which is not preferable. Above all, the average particle size (normal temperature state) of the heat-expandable graphite is more preferably in the range of 80 to 500 m, and particularly preferably in the range of 120 to 330 m.

In the present invention, the coating amount of the phosphate ester is 5 to 50 parts by weight and the coating amount of the surfactant is 0.5 to 10 parts by weight based on 100 parts by weight of the heat-expandable graphite. It is preferably in the weight part range.

If the coating amount of the phosphoric acid ester is less than the above lower limit, it is not preferable because the fixation stability of the surfactant is lowered. On the other hand, if the coating amount exceeds the above upper limit, the effect cannot be expected and only the amount used is increased unnecessarily. Is not preferred.

When the coating amount of the surfactant is below the lower limit, the dispersion stability tends to decrease, and when it exceeds the upper limit, the window glass tends to be clouded.

In particular, the coating amount of the phosphate ester is preferably in the range of 5 to 30 parts by weight, and the coating amount of the surfactant is preferably in the range of 0.5 to 5 parts by weight, based on 100 parts by weight of the heat-expandable graphite. preferable.

The phosphate ester is not particularly limited, but preferably has a molecular weight of 400 to 1500. If the molecular weight is less than 400, volatility and sublimability increase, which tends to cause fogging of window glass and the like, which is not preferable. If the molecular weight exceeds 1500, the solubility in the solvent and the It is not preferable because the dispersion stability is lowered. Among them, it is particularly preferable to use a phosphoric acid ester having a molecular weight of 500 to 1000.

Examples of the phosphoric acid ester having a molecular weight of 400 to 1500 are not particularly limited, and include, for example, resorcinol bisdiphenyl phosphate, bisphenol-A bisdiphenyl phosphate, Examples include aromatic condensed phosphate, isopropyl triphenyl phosphate, butyl triphenyl phosphate, polyaryl phosphate, and the like.

Further, it is preferable to use a phosphate ester having a viscosity of 500 to 80 OmPa · s (25 ° C.).

The surfactant is not particularly limited, and examples thereof include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant. Among these, it is preferable to use an anionic surfactant. In this case, the adhesion of the surfactant to the heat-expandable graphite can be improved, and the release of the surfactant can be reliably prevented.

Examples of the anionic surfactant include, but are not particularly limited to, alkyl benzene sulfonate, alkyl naphthalene sulfonate, polyoxyethylene alkyl ether sulfate, secondary higher alcohol ethoxy sulfate, and polyoxyethylene aryl. One or two members selected from the group consisting of phenyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether phosphate, and polyoxyethylene alkyl phenyl ether phosphate It is preferable to use more than one kind of anionic surfactant. When these specific compounds are used, the adhesion of the surfactant to the heat-expandable graphite can be further improved.

The flame retardant of the first invention can be produced, for example, by applying an organic solvent in which a phosphate ester and a surfactant are dissolved and contained to heat-expandable graphite and then drying. Next, an example of the method for producing the flame retardant of the second invention will be described. First, an organic solvent containing a dissolved phosphate ester is applied to the heat-expandable graphite (first application step).

. At this time, it is preferable to apply the heat-expandable graphite while stirring, so that the phosphate ester can be fixed to the heat-expandable graphite in a more uniform state. For example, the thermally expandable graphite is applied from above while stirring in a mixer. The coating is preferably performed by a spray method, whereby the phosphate ester can be fixed to the heat-expandable graphite in a more uniform state.

The organic solvent is not particularly limited, but includes, for example, methanol, ethanol, acetone, methyl ethyl ketone and the like. Among them, it is preferable to use methanol. Use of methanol has the advantage of shortening the drying time. A solvent containing a surfactant dissolved therein is applied to the heat-expandable graphite after the first application step (second application step). At this time, it is preferable to apply the heat-expandable graphite while stirring, so that the surfactant can be fixed to the heat-expandable graphite in a more uniform state. For example, heat-expandable graphite is applied from above while stirring in a mixer. Further, the coating is preferably performed by a spray method, whereby the surfactant can be fixed to the thermally expandable graphite in a more uniform state. Examples of the solvent include, but are not particularly limited to, water, methanol, ethanol, acetone, methyl ethyl ketone, and the like. Among them, it is preferable to use methanol. Use of methanol has the advantage of shortening the drying time.

Next, a drying treatment is performed to volatilize the organic solvent in the first coating step, the solvent in the second coating step, and the like, to obtain a dried flame retardant. By performing such a drying treatment, the phosphate ester surfactant can be firmly fixed to the heat-expandable graphite.

In the above manufacturing method, a drying step is not provided between the first coating step and the second coating step, but a drying step may be provided here.

In the above manufacturing method, application is performed by a spray method. It may be performed by a diving method, for example.

The above-described production method is only a preferred example, and the flame retardant of the present invention is not particularly limited to the one produced by the above-described production method.

Next, the flame-retardant fiber fabric according to the present invention will be described. This flame-retardant fiber fabric is obtained by applying an aqueous synthetic resin emulsion containing the flame retardant to the back surface of the fiber fabric and drying.

The synthetic resin constituting the water-based synthetic resin emulsion is not particularly limited. For example, an acrylic resin, an EVA (ethylene-vinyl acetate copolymer) resin, a urethane resin, a synthetic rubber resin, Examples include polyester resin, silicone resin, silicone / acrylic resin, and the like. Above all, it is preferable to use an acrylic resin, and in this case, there is an advantage that the adhesive stability to the fiber cloth can be improved.

The compounding weight ratio of the flame retardant and the synthetic resin in the aqueous synthetic resin emulsion is preferably in the range of flame retardant / synthetic resin = 10/90 to 90.10. If the compounding ratio of the flame retardant is below the above lower limit, it is not preferable because sufficient flame retardancy cannot be imparted to the fiber fabric, and if the compounding ratio of the flame retardant exceeds the above upper limit, the flexibility as the fiber fabric decreases. Is not preferred. Above all, it is particularly preferable that the blending weight ratio of the flame retardant and the synthetic resin in the aqueous synthetic resin emulsion is in the range of flame retardant / synthetic resin = 20/80 to 40/60.

The amount of the emulsion to be applied to the back surface of the fiber fabric is preferably in the range of 30 to 300 g / m ² in terms of solid content. Exceeding the above upper limit is not preferable because it is difficult to secure the lightness of the fiber fabric, while lowering the above lower limit is not preferable because sufficient flame retardancy cannot be provided.

The method of applying the emulsion to the back surface of the fiber cloth is not particularly limited, and examples thereof include a doctor-knife method, a roll coating method, a padding method, and a spray method. The emulsion may contain various additives such as an antioxidant, an ultraviolet absorber, a stabilizer, a pigment, and a dye, if necessary, in addition to water, a synthetic resin, and a flame retardant. Is not particularly limited, for example, force? And the like.

It should be noted that the flame retardant of the present invention is not limited to the use (flame-retardant fiber cloth) exemplified above, but can be applied to any use.

Next, specific examples of the present invention will be described.

Example 1

"Phoscon 903 N Conc A" (trade name, manufactured by Meisei Chemical Industry Co., Ltd., aromatic condensed phosphate ester, molecular weight 512, viscosity at 25 ° C 65 OmPas) The methanol solution containing 0% by weight of the methanol solution was spray-coated from above onto thermally expandable graphite (average particle size: 300 m, manufactured by Sumikin Air Water Chemical Co., Ltd.) stirred in the mixer. Subsequently, the heat-expandable graphite is sufficiently stirred and mixed in a mixer, and then “Phoscon 903 N Conk B” (trade name, manufactured by Meisei Chemical Industry Co., Ltd., polyoxyethylene aryl, an anionic surfactant). A methanol solution containing 50% by weight of phenyl ether sulfate) was spray-coated from above onto the stirred thermally expandable graphite, and then the thermally expandable graphite was sufficiently stirred and mixed in a mixer. did. Next, a drying treatment was performed at 100 to 120 ° C. to obtain a flame retardant. This flame retardant was obtained by coating 6.7 parts by weight of a phosphate ester and 1.4 parts by weight of a surfactant with respect to 100 parts by weight of thermally expandable graphite.

Next, an aqueous acryl resin emulsion consisting of 56 parts by weight of water, 22 parts by weight of an acrylic resin, 18 parts by weight of the above-described flame retardant, and 4 parts by weight of ammonium polyphosphate was prepared, and this emulsion was used for automobiles by the doctor knife method. Coating amount (solid content) on the back of skin material (fiber cloth) 70 g After applying Zm ² , drying at 150 ° C is difficult. A flammable fiber fabric was obtained.

Examples 2 to 9

A flame-retardant fiber fabric was obtained in the same manner as in Example 1, except that the flame retardant and the emulsion were prepared under the conditions (compounding amounts and the like) shown in Tables 1 and 2.

Example 10 0 '

A flame-retardant fiber cloth was obtained in the same manner as in Example 1 except that alkylnaphthalenesulfonate was used instead of “phoscon 903 N conc B” as an anionic surfactant.

Example 11

A flame-retardant fiber fabric was obtained in the same manner as in Example 1, except that polyoxyethylene alkyl ether sulfate was used instead of “phoscon 903 N conc B” as an anionic surfactant.

Example 1 2

A flame-retardant fiber fabric was obtained in the same manner as in Example 1 except that “phoscon 903 N conc B” was replaced with a secondary higher alcohol ethoxy sulfate as an anionic surfactant.

Example 13

A flame-retardant fiber fabric was obtained in the same manner as in Example 1, except that polyoxyethylene alkylphenyl phenyl ether sulfate was used instead of “phoscon 903 N conc B” as an anionic surfactant.

Example 14

A flame-retardant fiber fabric was obtained in the same manner as in Example 1, except that polyoxyethylene alkyl ether phosphate was used instead of “phoscon 903 N conc B” as an anionic surfactant.

Example 15

As an anionic surfactant, instead of "phoscon 903 N conc B", polio A flame-retardant fiber cloth was obtained in the same manner as in Example 1 except that xylene ethylenephenyl ether phosphate was used.

Example 16

Example 1 was repeated except that bisphenol A bisdiphenyl phosphate (molecular weight: 692, viscosity at 25 ° C: 50 OmPas) was used instead of “phoscon 903N conc A” as the phosphate ester. Similarly, a flame-retardant fiber fabric was obtained.

Example 17

The same procedure as in Example 1 was repeated except that instead of “phoscon 903N conc A”, an aromatic condensed phosphoric acid ester (molecular weight: 748, viscosity at 25 ° C .: 3500 OmPa · s) was used as the phosphoric acid ester. A flame-retardant fiber fabric was obtained.

Example 18

A flame-retardant fiber fabric was prepared in the same manner as in Example 1, except that polyaryl phosphate (molecular weight: 350, viscosity at 25 ° C: 61 mPa · s) was used instead of “phoscon 903N conc A” as the phosphate ester. Got.

Example 19

A flame-retardant fiber fabric was obtained in the same manner as in Example 1, except that alkylphosulfonate was used instead of “phoscon 903N conc B” as an anionic surfactant.

Comparative Example 1

Water-based acrylic resin emulsion consisting of 56 parts by weight of water and 22 parts by weight of acrylic resin, 16.5 parts by weight of thermally expandable graphite, phoscon 903N conc A (ester phosphate) 1.25 parts by weight, phoscon 903N conc B ( Anionic surfactant) 0.25 parts by weight and 4 parts by weight of ammonium polyphosphate were added, and this was applied to the back surface of the skin material for automobiles by the doctor knife method at a coating amount (solid content) of 70 gZm ² . After that, a drying treatment was performed at 150 ° C. to obtain a flame-retardant fiber fabric.

Reference example 1 Water-based acrylic resin emulsion consisting of 55 parts by weight of water and 25 parts by weight of acryl resin was prepared by adding 20 parts by weight of antimony with decab mouth as a halogen-based flame retardant. After coating on the back surface of the material at a coating amount (solid content) of 70 g Zm ² , a drying treatment was performed at 150 ° C. to obtain a flame-retardant fiber fabric. “Dekabu mouth antimony” is a trade name and is a halogen-based flame retardant consisting of a mixture of decabromobiphenyl ether and antimony trioxide.

Reference Example 2

A flame-retardant fiber fabric was obtained in the same manner as in Reference Example 1, except that the coating amount was changed to 35 g Zm ² . '' Reference Example 3

A flame-retardant fiber fabric was obtained in the same manner as in Reference Example 1, except that the emulsion composition was changed to the conditions shown in Table 2.

Various evaluations were performed on the emulsions and fiber cloths obtained as described above based on the following evaluation methods. Tables 1 to 4 show these results.

(Flame retardancy evaluation method)

The flammability was confirmed based on JISD1201-1997 F_MVSS302, and the combustion speed (mm / min) was measured.

(Evaluation method for dispersion stability of thermally expandable graphite in emulsion)

The emulsion was allowed to stand in the vessel, and the presence or absence of sedimentation of the heat-expandable graphite was observed.If sedimentation was observed within 24 hours, `` x '' was evaluated for 24 to 96 hours. `` △ '' indicates sedimentation separation, `` 〇 '' indicates sedimentation between 96 hours and 15 days, and no sedimentation phenomenon was observed even after 15 days Those were marked with “◎”.

(Coating property evaluation method)

The applicability was evaluated according to the JISK540 film applicator coating method. Resin and graphite flakes applied uniformly The coated sample was marked "△", and the one that was difficult to apply uniformly was marked "X". (Method of evaluating softness of fabric)

The length (mm) over which the test piece moved was determined in accordance with the rigid-soft 45 ° cantilever method of JIS L I 096.

(Fogging rate measurement method)

50 cm ² of the fabric sample was placed in a glass container having a capacity of 50 OmL, covered with a glass plate and sealed. The entire container was immersed in an oil bath at 100 ° C and kept warm for 20 hours in this state. Thereafter, the glass plate was removed and put in an integrating sphere type light transmittance measurement device, the amount of incident light (Tt), the total amount of transmitted light (T _2), scattered light amount by the device (T _3), from the test piece scattered light of (T ₄₎ was measured, to calculate the clouding rate from the following equation.

Clouding rate = (Td / T t) x 100

Td = {(T4-T2X T3 / T1) / Ύι] x 100

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Flame retardant Thermal expansive graphite (average particle size 3 OO ^ m) 1 0 0 1 0 0 1 0 0 1 0 0 1- Composition of heat-expandable graphite (average particle size: 150〃m) ― ― ― 1 1 0 0 1 0 0 1 0 0 (parts by weight) Coty phosphate ester (molecular weight 5 1 2) 5 6. 7 6. 7 6. 7 Anionic surfactant 1.4 1.4 1.4 1.4 0.35 5 Water 5 6 5 6 5 6 5 6 5 6 5 6 5 6 John acrylic resin 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Flame retardant 1 8 1 8 1 8 1 8 1 8 1 8 18 (parts by weight) Ammonia polyphosphate 4 4 4 4 4 4 4 Emulsion (Solid content) (g / m ² ) 7 0 7 0 7 0 7 0 7 0 7 0 7 0 Viscosity of emulsion (mPas) 8 0 0 0 8 0 0 0 8 0 0 0 8 0 0 0 8 0 0 0 8 0 0 0 8 0 0 0 Burning speed (mmZ) 0 0 0 9 5 0 0 0 Dispersion stability of graphite in emulsion ◎ 〇 ◎ ◎ ◎ 〇 ◎ ◎ Evaluation Coatability 〇 Δ 〇〇 Δ 〇〇 ) 7 5 8 0 7 0 6 0 7 5 7 5 7 0 Clouding ratio 5 4 5 6 3 9 12 Phosphate ester: Aromatic condensed phosphate ester Anionic surfactant: Polyoxyethylene arylphenyl Ether sulfate

Phosphate ester: Condensed aromatic phosphate ester Anionic surfactant: Polyoxyethylene arylphenyl ether sulfate

* 1) Antimony dekabu used as flame retardant

Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 19 Thermal expansible graphite (average particle size 3 0 0 u rn) 1 0 0 1 0 0 1 0 0 1 0 0 1 0 0 100 0 100 Phosphate ester (molecular weight 5 12) 6.7 6.7 6.7 6.7 6.7 6.7 6.7 Flame retardant Alkyl naphthosulfonic acid 1.4 ― ― ― ― Composition of surface Polyoxyethylene alkyl I-ter sulfate ― 1.4 ― ― ― ― ― ― 2nd higher grade 7-co-luetoxysulf X--― ― 1.4 ― ― ― ― Sex e. Reoxy I-alkylene alkyl phenyl sulfate---1.4-----Agent Polyoxyethylene alkyl I-tellurate-----1.4-Single layer Polyoxyethylene Alkyl phenyl I-tellurate-----1.4-To alkyl-sulfonic acid salt------1.4 Emulsion water 5 6 5 6 5 6 5 6 5 6 5 6 5 6 John acrylic resin 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Composition of flame retardant 1 8 1 8 1 8 1 8 1 8 1 8 1 8

C parts by weight) Ammonia polyphosphate 4 4 4 4 4 4 4 Amount of emulsion 3 (solid content) (g / m ² ) 7 0 7 0 7 0 7 0 7 0 7 0 7 0 Viscosity of emulsion (m P a · s) 8 0 0 0 8 0 0 0 8 0 0 0 8 0 0 0 8 0 0 0 8 0 0 0 8 0 0 0 Burning speed (mm, min) 0 0 0 0 0 0 0 Graphite dispersion stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ Evaluation Coatability 〇〇〇〇 O 〇- 〇 Softness (mm) 7 5 7 5 7 5 7 5 7 5 7 5 7 5 Clouding rate 5 5 5 5 5 5 5

Example 16 Example 17 Example 18 Thermally expansive graphite (average particle size 300 urn) 100 100 100 Flame retardant phosphate (molecular weight 692) 6. 7 ― ― Composition of Coty phosphate (molecular weight 748) 1. 7 ―

(Parts by weight) Phosphate ester (molecular weight: 350) 1-6.7 Surfactant 1.4.1.4.1.4 Emulsion 'water 56 56 56 John Acrylic resin 22 22 22 Composition of flame retardant 18 18 18

(Parts by weight) Ammonia polyphosphate 4 4 4 Amount of emulsion applied (solid content) (g / m ² ) 70 70 70 Viscosity of emulsion (mPa · s) 8000 8000 8000 Burning rate (mm / min) 0 0 0 In emulsion ◎ ◎ ◎ Evaluation Coatability 〇剛 Bending softness. (Mm) 78 80 70 Haze rate 5 2 20

As is clear from the table, the flame retardants of Examples 1 to 19 of the present invention were excellent in the dispersion stability of the thermally expandable graphite in the emulsion and the emulsion was excellent in the coating property. The flame-retardant fiber fabrics of Examples 1 to 19 of the present invention were excellent in flame retardancy. As is clear from the comparison between Reference Example 1 and Example 1, the comparison between Reference Example 2 and Example 8, and the comparison between Reference Example 3 and Example 9, the fiber cloth of the present invention is a conventional halogen-based fiber cloth. The fabric had excellent flame retardancy equal to or higher than that of the fabric constituted by using the flame retardant (the fabric of the reference example).

On the other hand, in Comparative Example 1 in which the heat-expandable graphite, the phosphate ester, and the surfactant were simply mixed in the emulsion, the dispersion stability of the heat-expandable graphite was poor.

In Example 9 and Reference Example 3, the emulsion was foamed and applied three times while the amount of the flame retardant was reduced. In this case, the flame retardant effect was reduced in Reference Example 3 (conventional method). Although greatly reduced, in Example 9 of the present invention, the heat-expandable graphite expands in the space of the foam layer, and the flame-retardant effect can be sufficiently maintained.

According to the flame retardant of the present invention, the flame retardant has excellent dispersion stability in a liquid. Therefore, for example, even when the aqueous synthetic resin emulsion is contained in the aqueous synthetic resin emulsion, the aqueous synthetic resin emulsion containing the flame retardant does not precipitate and separate. Can be applied to the fiber fabric in a uniformly dispersed state, and the effect of easy application and excellent coating stability can be obtained. Further, since the phosphoric acid ester is also coated, the fixing stability of the surfactant can be improved and the fiber cloth can be given sufficient flexibility. In addition, since it contains heat-expandable graphite and phosphate ester, sufficient flame retardancy can be imparted. Since no halogen-based flame retardant is used, no toxic gas is generated during a fire or incineration. In addition, by adopting a configuration in which the phosphate ester is coated on the heat-expandable graphite, the same flame-retardant performance as compared to a system using a simple mixture of the heat-expandable graphite and the phosphate ester. In addition, there is an advantage that the amount of the heat-expandable graphite required to obtain the resin can be reduced, that is, the amount can be reduced. ADVANTAGE OF THE INVENTION According to the flame-retardant fiber fabric of this invention, since heat-expandable graphite can be provided to the fiber fabric in a uniformly dispersed state, excellent flame retardancy can be ensured. The emulsion has a light application and is excellent in coating stability, so that the quality as a fiber fabric can be improved. In addition, since the heat-expandable graphite is also coated with a phosphate ester, sufficient flexibility as a fiber fabric can be secured. No toxic gas is generated during a fire or incineration.

The terms and descriptions used herein are used to describe the embodiments according to the present invention, and the present invention is not limited to these. The present invention allows any design change within the scope of the claims, without departing from the spirit thereof. Industrial applicability

The flame retardant of the present invention can be used as a flame retardant for fiber fabrics because it can impart flame retardancy to the fabric by, for example, applying an aqueous synthetic resin emulsion containing the same to the back surface of the fiber fabric and drying. By incorporating the flame retardant of the present invention into a synthetic resin, it is possible to impart sufficient flame retardancy to the synthetic resin.

Claims

The scope of the claims

1. A flame retardant characterized in that a phosphate ester and a surfactant are coated on at least a part of the surface of the heat-expandable graphite.

2. A flame retardant characterized in that at least a part of the surface of the heat-expandable graphite is coated with a surfactant layer via a phosphate layer.

3. The coating amount of the phosphate ester is in the range of 5 to 50 parts by weight and the coating amount of the surfactant is in the range of 0.5 to 10 parts by weight based on 100 parts by weight of the thermally expandable graphite. 3. The flame retardant according to claim 1 or 2.

4. The coating amount of the phosphate ester is in the range of 5 to 30 parts by weight and the coating amount of the surfactant is in the range of 0.5 to 5 parts by weight with respect to 100 parts by weight of the thermally expandable graphite. 3. The flame retardant according to paragraph 1 or 2.

5. The flame retardant according to claim 1, wherein the average particle size of the thermally expandable graphite is 50 to 100 m. 6. The flame retardant according to claim 1 or 2, wherein the average particle size of the thermally expandable graphite is 80 to 500 m.

7. The flame retardant according to claim 1, wherein the surfactant is an anionic surfactant.

8. Alkyl benzene sulfonate, alkyl Lunaphthalene sulfonate, polyoxyethylene alkyl ether sulfate, secondary higher alcohol ethoxy sulfate, polyoxyethylene aryl phenyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether 8. The flame retardant according to claim 7, wherein one or two or more anionic surfactants selected from the group consisting of a phosphate and a polyoxyethylene alkylphenyl-tellurate are used.

9. The flame retardant according to claim 1 or 2, wherein the phosphoric acid ester has a molecular weight of 400 to 1500.

10. An anionic surfactant layer is coated on at least a part of the surface of the heat-expandable graphite via a phosphate ester layer,

The coating amount of the phosphate ester is in the range of 5 to 50 parts by weight and the coating amount of the anionic surfactant is in the range of 0.5 to 10 parts by weight based on 100 parts by weight of the thermally expandable graphite. A flame retardant, wherein the average particle size of the thermally expandable graphite is 50 to 100 m, and the molecular weight of the phosphate ester is 400 to 150.

1 1. a first coating step of applying an organic solvent containing and dissolving a phosphate ester to the heat-expandable graphite;

A second application step of applying a solvent containing a surfactant to the heat-expandable graphite after passing through the first application step.

12. The method for producing a flame retardant according to claim 11, wherein a drying treatment is performed after the second coating step.

1 3. Stir the organic solvent containing and dissolving the phosphate ester in the first coating step The method of claim 1, wherein the solvent is applied to the thermally expandable graphite in a sprayed state while the solvent containing a surfactant is dissolved and applied to the stirred thermally expandable graphite in the second application step. 11. The method for producing a flame retardant according to item 1. 14. The method for producing a flame retardant according to claim 11, wherein methanol is used as an organic solvent in the first coating step, and methanol is used as a solvent in the second coating step.

15. The method for producing a flame retardant according to claim 11, wherein a phosphate having a molecular weight of 400 to 150 is used as the phosphate.

16. The surfactants include alkyl benzene sulfonate, alkyl naphthalene sulfonate, polyoxyethylene alkyl ether sulfate, second-higher alcohol ethoxysulfate, and polyoxyethylene aryl. One or more selected from the group consisting of phenyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether phosphate, and polyoxyethylene alkyl phenyl ether phosphate The method for producing a flame retardant according to claim 11, wherein the anionic surfactant is used. 1 7. A flame-retardant fiber fabric obtained by applying an aqueous synthetic resin emulsion containing the flame retardant according to claim 1 or 2 to the back surface of the fiber fabric and drying.

1 8. An aqueous synthetic resin emulsion containing the flame retardant produced by the method for producing a flame retardant according to any one of claims 11 to 16 on the back surface of the fiber cloth, Flame retardant fiber cloth obtained by drying.

19. The method according to claim 17 or 18, wherein the weight ratio of the flame retardant and the synthetic resin in the aqueous synthetic resin emulsion is in the range of 10/90 to 90/10 of the flame retardant Z synthetic resin. Flame retardant fiber fabric.

20. The flame retardant according to claim 17 or claim 18, wherein the compounding weight ratio of the flame retardant and the synthetic resin in the aqueous synthetic resin emulsion is as follows: flame retardant / synthetic resin = 20/80 to 4060. Fiber fabric. 19. The flame-retardant fiber fabric according to claim 17, wherein the synthetic resin constituting the water-based synthetic resin emulsion is an acryl-based resin.

22. The flame-retardant fiber according to claim 17, wherein the amount of the emulsion applied to the back surface of the fiber fabric is in the range of 30 to 300 g / m ^{2 in} terms of solid content.