JP2006063125A - Flame retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant resin composition having no change in moisture absorption/deterioration, easily blended with a resin composition and a flame retardant treating liquid, generating no halogen gas and formaldehyde gas, presenting no waxy feeling when applied to flame retardant treatment of fiber strands, ropes, strings, woven fabrics, knit fabrics, nonwoven fabric, fiber webs, nonwoven fabric-like fiber lamination cushion materials and the like and inducing no sick house syndrome. <P>SOLUTION: A polyphosphate-based flame retardant agent is constituted by a polyphosphate compound and a silicone-based resin, blended with an elastomer resin and applied to flame retardant treatment of fiber products. The silicone-based resin is fixed around particles of the polyphosphate compound. As the polyphosphate compound, ammonium polyphosphate having 20-2000 weight average degree of polymerization is applied. As the silicone-based resin, the resin having tetra-functional monomer units or tri-functional monomer units is applied. As the elastomer resin, an acrylic resin emulsion is applied. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to polyphosphate compounds such as ammonium polyphosphate, polyphosphate amide, polyphosphate carbamate, sodium tripolyphosphate, potassium polyphosphate, potassium polyphosphate, ammonium potassium phosphate, guanidine polyphosphate, etc. It is related to a resin composition flame-retarded by “flammant”.

Conventionally, halogen-based flame retardants containing halogen as a main component have been widely used to make resin compositions and textiles flame-retardant. However, resin compositions and textile products that have been flame-retarded with halogen-based flame retardants generate harmful halogen gas during combustion, causing secondary disasters due to gas poisoning in the event of a fire, and causing pollution problems during incineration. Provoke.
For this reason, recently, a polyphosphoric flame retardant containing no halogen has attracted attention.
However, the polyphosphoric acid flame retardant tends to be dampened, thereby causing variations in the flame retardant performance of the flame retardant resin composition, and the flame retardant resin composition is damp and feels wet. However, it is easy to induce rust of metal instruments that touch it and deterioration and discoloration of textiles.

As a method of suppressing the hygroscopicity of the polyphosphate flame retardant, (1) a method of adding melamine to the polyphosphate flame retardant in the presence of melamine or melamine urea as a raw material at the time of production (see, for example, Patent Document 1) (2) In the flame retardant treatment using the melamine-added polyphosphoric flame retardant, a method for imparting water resistance by adding melamine phosphate to the blended treatment liquid (see, for example, Patent Document 2), (3 ) A method of blending a melamine / formaldehyde resin into a raw material at the time of production of a polyphosphate flame retardant or a dispersion after production, encapsulating the polyphosphate flame retardant into microcapsules, and forming stable particles that are difficult to hydrolyze (for example, , Patent Document 3), (4) A silane coupling agent is allowed to coexist with a melamine-added polyphosphoric flame retardant, and the polyphosphoric acid from the fire-retardant processed product to which it is applied A method for suppressing bleeding of an acid flame retardant (see, for example, Patent Documents 4, 5, and 6) is known.
JP 49-061099 (JP 61-15478) JP 51-023312 (JP-B 52-39930) JP-A 61-103962 Japanese Patent Laid-Open No. 02-263851 (Japanese Patent Publication No. 06-18944) Japanese Unexamined Patent Publication No. 03-020342 (Japanese Patent Publication No. 06-04735) Japanese Patent Laid-Open No. 03-056547 (Japanese Patent Publication No. 06-06655)

However, formaldehyde residual gas is generated from the resin composition treated with the melamine-added polyphosphate flame retardant treated by these methods, thereby causing sick house syndrome.
Therefore, it is necessary to suppress the hygroscopicity by encapsulating the polyphosphate flame retardant with resins such as urethane resin, ethylene vinyl acetate resin, acrylic resin, polymethyl methacrylate resin and the like that do not generate formaldehyde residual gas. Various attempts were made.
However, urethane resin, ethylene vinyl acetate resin, and acrylic resin are easy to adjust to water, give a slimy feeling, and, like a non-moisture-proof untreated polyphosphoric acid flame retardant, the particles agglomerate and become enlarged, As a result, the flame-retardant treatment effect is likely to vary, and when it is used with stirring, the resin film is cracked and peeled off to expose the polyphosphate compound, thereby impairing the moisture-proof effect of the resin film.
And although polymethylmethacrylate resin is comparatively hard and does not give a slimy feeling, a resin film tends to crack in the dispersion process to a resin composition or a flame-retardant treatment liquid, and the moisture-proof effect by the resin film is impaired.

However, as is apparent from the fact that silicone resins are used in water repellency, antifouling agents and caulking agents, they are hydrophobic and do not absorb moisture, and their resin films are flexible and difficult to crack.
In particular, a silicone resin comprising a tetrafunctional monomer unit or a trifunctional monomer unit is tough and excellent in heat resistance, and the polyphosphoric acid flame retardant particles encapsulated in the resin film are composed of the blended resin composition. The resin film does not crack in the stirring process, and the dispersed state is stably maintained without being precipitated or aggregated and separated during storage.

  The present invention has been completed on the basis of such findings, and the object of the present invention is that the dispersion state of the polyphosphate flame retardant is kept stable without aggregation and precipitation separation during storage. The object is to obtain a flame retardant resin composition that does not generate residual gas.

  The flame retardant resin composition according to the present invention comprises a polyphosphoric acid flame retardant comprising composite particles of a polyphosphoric acid compound and a silicone resin, if necessary in the liquid, using an auxiliary agent or directly blended into the resin. This is the first feature.

  A second feature of the flame retardant resin composition according to the present invention is that, in addition to the first feature, a polyphosphoric acid flame retardant is adhered to a silicone resin around the particles of the polyphosphoric acid compound. is there.

  A third feature of the flame retardant resin composition according to the present invention is that, in addition to any of the first and second features, the polyphosphoric acid compound has a weight average degree of polymerization of 20 to 2,000.

  A fourth feature of the flame retardant resin composition according to the present invention is that, in addition to any of the first, second, and third features, the polyphosphate compound is ammonium polyphosphate.

  The fifth feature of the flame retardant resin composition according to the present invention is that, in addition to any of the first, second, third and fourth features, the silicone-based resin is a tetrafunctional monomer unit or trifunctional. In that it has a monomer unit.

  A sixth feature of the flame-retardant resin composition according to the present invention is that, in addition to any of the first, second, third, fourth, and fifth features, the resin is an elastomer resin. .

  A seventh feature of the flame retardant resin composition according to the present invention is that, in addition to any of the first, second, third, fourth, fifth and sixth features, the elastomer resin is an acrylic resin. In that point.

The silicone resin does not generate halogen gas or formaldehyde gas, has water repellency, is hydrophobic and does not absorb moisture, and its resin film is flexible and difficult to crack.
For this reason, the particles of the polyphosphoric acid flame retardant surrounded by the silicone resin film are kept in a stable dispersed state for a long time without moisture absorption, aggregation and sedimentation in the resin composition. The silicone resin film does not crack during the stirring process.

The silicone resin is applied to coat the particles of the polyphosphate flame retardant, and it is desirable to prepare it as a silicone resin solution in which it is dissolved in a solvent solution.
When it is prepared as a silicone resin dispersion, the silicone resin particles are finer than the polyphosphoric flame retardant particles, and the particle size is 3 to 25 μm, making it easy to adhere to the surface of the polyphosphoric flame retardant particles. To do.
The application amount of the silicone resin may be about 2 to 20 weights with respect to 100 parts by weight of the polyphosphoric acid flame retardant.

The silicone resin has a general formula (R _n SiO _{(4-n) / 2} ) _m (where R is a substituent such as a methyl group, an alkyl group, a fluorinated alkyl group, a phenyl group or a vinyl group, n = 1) ˜3, m ≧ 2).
The silicone resin is composed of a monofunctional monomer unit represented by the composition formula (CH ₃ ) ₃ SiO _1/2 and a tetrafunctional monomer unit represented by the composition formula SiO ₂ , and the composition formula (CH ₃ ) A rigid resinous silicone resin with a trifunctional monomer unit represented by SiO _3/2 is also recommended in terms of toughness and heat resistance.
Silicone resin of monofunctional monomer unit represented by composition formula (CH ₃ ) ₃ SiO _1/2 , silicone resin of bifunctional monomer unit represented by composition formula (CH ₃ ) ₂ SiO, or these A silicone resin in the form of oil or gum, such as a combination silicone resin in which a monofunctional monomer unit and a bifunctional monomer unit are combined, is not preferable.

In order to effectively coat the particles of the polyphosphate flame retardant with the silicone resin, as shown in Patent Documents 1 and 2, the silicone resin component is allowed to coexist in the raw material when the polyphosphate flame retardant is produced. Alternatively, as shown in Patent Document 3, a silicone resin solution or silicone resin dispersion and a polyphosphoric acid flame retardant powder or dispersion may be mixed and stirred, followed by heat treatment.
As a solvent for the silicone resin solution or the silicone resin dispersion, a hydrophilic organic solvent such as acetone, ethyl acetate, or methyl alcohol may be used.
In addition, in order to coat the polyphosphate flame retardant particles with a silicone resin, a mixture of a dispersion of silicone resin particles having an average particle size of 3 to 25 μm and a polyphosphate flame retardant powder dispersion, or silicone A mixture of a silicone resin and a polyphosphate flame retardant obtained by drying a mixed solution in which a fine powder of a polyphosphate flame retardant is mixed with a silicone resin solution obtained by dissolving a glass resin fine powder in toluene or another organic solvent. Alternatively, the powder may be pulverized by a pulverizer such as a ball mill or a jet mill to form a fine powder.
The silicone resin can be prepared as a mixed composition with an ultraviolet absorber, an antioxidant, a color pigment and the like.
In order to harden the silicone resin film that coats the surface of the polyphosphoric acid flame retardant particles, a polymethyl acrylate resin may be mixed with the silicone resin composition.

The silicone-added polyphosphoric acid flame retardant comprising the polyphosphoric acid flame retardant particles and the silicone resin is used by blending with the binder resin.
As the binder resin, a resin emulsion such as an acrylic resin emulsion, a urethane resin emulsion, or an ethylene / vinyl acetate resin emulsion is used.
When applying the silicone-added polyphosphate flame retardant to the flame retardant treatment of textile products, it is recommended to apply an acrylic resin emulsion to the binder resin.
As a matter of course, for the purpose of the present invention, a binder resin containing no halogen component or formaldehyde component is used.

As the polyphosphate flame retardant, ammonium polyphosphate having a weight average polymerization degree of 20 to 2000 is recommended.
Those having a weight average degree of polymerization of less than 20 are water-soluble, and those having a weight average degree of polymerization of more than 2000 lack practicality because of a long polymerization time and high cost.

Textile products that are flame-retardant treated with a silicone-added polyphosphoric flame retardant include fiber yarn, rope, string, woven fabric, knitted fabric, nonwoven fabric, woven pile fabric, knitted pile fabric, tufted pile fabric, raised fabric, electrostatic As long as the main material is a fiber such as a flocked fabric, a fiber web, or a nonwoven fiber laminated cushion material, the entangled structure and use of the fiber are not particularly limited.
Textile products that are used by touching the skin only on one side such as chairs, ceilings / walls, carpets (fiber flooring, rugs), especially woven pile fabrics, knitted pile fabrics, tufted pile fabrics, brushed fabrics Further, in a thick fabric such as an electrostatic flocking fabric, a silicone-added polyphosphate-based flame retardant is preferably applied to the back surface that does not directly touch the skin even in order to ensure the surface texture.

Silicone resin emulsion (resin component: 20% by weight of organopolysiloxane, Meisei Chemical Co., Ltd. product name: KR-50) (Example 1) and urethane resin emulsion (resin component; polyurethane 30% by weight, Dainippon Ink) Chemical Industry Co., Ltd. product name; Hydran HW-930) (Comparative Example 1) and ethylene / vinyl acetate resin emulsion (resin component; ethylene / vinyl acetate 45% by weight, Shinba Co., Ltd. product name; YS-912) ( Comparative Example 2), acrylic resin emulsion (resin component; acrylic resin 50% by weight, Shin-Nakamura Chemical Co., Ltd. product name; New Coat FH-45) (Comparative Example 3), and catalyst (Sumitomo Chemtex Co., Ltd. product name) ; Epoxy resin emulsion containing Sumitex Accelerator ACX (resin component; epoxy resin) 5 wt%, Sumitomo Chemtex Co., Ltd. product name; Sumitex Resin M-3) (Comparative Example 4) 100 parts by weight of each resin emulsion, 200 parts by weight of water was added, heated to 80 ° C. and stirred for 20 minutes, Five types of resin solutions containing each resin emulsion as a main component are prepared.
Next, ammonium polyphosphate particles having an average particle diameter of 8 μm are blended in each resin solution so that the blending ratio of the ammonium polyphosphate particles to the resin content contained in each resin solution is equal to each other. A particle dispersion solution is prepared.
In addition to the above five types of resin solutions, as Example 2, a resin solution containing 6 parts by weight of a silicone resin (organopolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 parts by weight of toluene was mixed with an average particle. Ammonium polyphosphate particles (100 parts by weight) having a diameter of 8 μm were blended so that the blending ratio would be equal to the blending ratio of ammonium polyphosphate particles with respect to the resin content contained in the above five types of ammonium polyphosphate dispersions. To prepare a dispersion of ammonium polyphosphate particles.
Furthermore, as Example 3, ammonium polyphosphate particles having an average particle size of 20 μm (100 wt.%) Were added to a resin solution containing 6 wt. Parts of a silicone resin (organopolysiloxane, Shin-Etsu Chemical Co., Ltd.) and 100 wt. Part) in the same manner as in Example 2 so that the blending ratio is equal to the blending ratio of the ammonium polyphosphate particles to the resin content contained in the five types of ammonium polyphosphate particle dispersions. An ammonium particle dispersion solution is prepared.

  The above seven types of ammonium polyphosphate particle dispersion solutions were heated to remove the solvent (water / toluene), and prepared seven types of resin-coated ammonium polyphosphate particles coated with resin and dried, (1) 100 parts by weight of water (60 ° C.) each for 100 parts by weight of a total of 7 kinds of dried resin-coated ammonium polyphosphate particles and 100 parts by weight of blank untreated ammonium polyphosphate particles (Comparative Example 5) not coated with resin Of the humidified powder of resin-coated ammonium polyphosphate particles and untreated ammonium polyphosphate particles prepared by stirring for 1 minute and (2) a total of seven types of resin-coated ammonium polyphosphate particles and untreated 5gf of poly (ammonium polyphosphate) particles are individually loaded in a smell bag (Omi Odore Service Co., Ltd.). The concentration of formaldehyde generated by injecting 2000 ml (cc) of air into the sachet bag and heating at 80 ° C. for 2 hours is measured with a GASTEC detector tube (Gastech product name; Formaldehyde detector tube No. 91L). ) And (3) 20 parts by weight of each of these 7 types of resin-coated ammonium polyphosphate particles and untreated ammonium polyphosphate particles were added to an acrylic resin emulsion (resin component; acrylic resin 50% by weight, Shin-Nakamura) The dispersion state of ammonium polyphosphate particles in the dispersion solution mixed with Chemical Industry Co., Ltd. product name: New Coat FH-45) was examined, and the results shown in the upper part of [Table 1] below were obtained.

In the data regarding ammonium polyphosphate particles shown in the upper part of [Table 1] below,
(1) Regarding the presence or absence of formaldehyde, “○” is displayed when the concentration of formaldehyde is not detected by the gas-tech detector tube, and “×” is displayed when the concentration of formaldehyde is detected. (Unit: ppm) is appended.
(2) Concerning the slime feeling, “◎” if the hand picking ammonium polyphosphate particles does not slip, “○” if the hand slips slightly, “△” if the hand slips frequently, and hand slipping. In this case, “X” is displayed.

  25 parts by weight of the above-mentioned seven types of resin-coated ammonium polyphosphate particles and untreated ammonium polyphosphate particles (dry powder) and an acrylic resin emulsion (resin component; acrylic resin 50% by weight, Shin-Nakamura Chemical Co., Ltd. product name; New A total of 8 flame-retardant resin compositions (viscosity 7000 mPa · s) were prepared with 100 parts by weight of Coat FH-45) and 2 parts by weight of a thickener (product name of San Nopco Co., Ltd .; Polymer Thickener 612). The dispersion state of the ammonium polyphosphate particles immediately after the preparation, the dispersion state of the ammonium polyphosphate particles after standing for 24 hours, and the change over time in the viscosity of the flame-retardant resin composition were examined, and the results shown in the middle section of [Table 1] below Got.

In the data relating to the flame retardant resin composition shown in the middle of [Table 1] below,
(1) Regarding the dispersed state, “◯” is obtained when the ammonium polyphosphate particles are dispersed without separation, and “△” is obtained when the particles are temporarily dispersed but gradually separated. If it cannot be mixed, “x” is displayed. If ammonium polyphosphate particles are separated and precipitated, “▲” is displayed.
(2) Regarding the viscosity change, when the viscosity after 6 hours of the prepared flame retardant resin composition is not changed, “◯”, when it is thickened, “△”, ammonium polyphosphate particles are separated and precipitated. When the viscosity of the flame retardant resin composition changed in this way cannot be examined, “X” is displayed.

The above 8 types of flame retardant resin compositions (viscosity 7000 mPa · s) were applied to the back of a pile warp knitted fabric with a polyester basis weight of 450 gf / m ² using polyester fibers for both the pile yarn and the ground yarn. A flame retardant pile warp knitted fabric was made by heating and drying at 2 ° C. for 2 minutes, and the results shown in the lower part of [Table 1] below were obtained.

In the data on the flame retardant pile warp knitted fabric shown in the lower part of [Table 1] below,
(1) For flame retardancy, measure the burning rate of a flame retardant pile warp knitted fabric that is horizontally supported in accordance with US Automotive Safety Standards (FMVSS-302), and if the flame does not reach the mark, It is determined as “flame retardant”.
(2) Regarding the presence or absence of formaldehyde, the flame retardant pile warp knitted fabric is cut into 10cm square, sealed in an odor bag (Omi Odore Service Co., Ltd.), and 2000ml of air in the odor bag. (Cc) The concentration of formaldehyde generated by injecting and heating at 80 ° C. for 1 hour was measured with a Gastec detector tube (Gastec product name; Formaldehyde detector tube No. 91L). When no concentration is detected, “◯” is displayed, and when formaldehyde concentration is detected, “×” is displayed and the detected concentration (unit: ppm) is appended.
(3) Regarding the slime feeling, the flame retardant pile warp knitted fabric is cut into 20 cm square to prepare two sample pieces, and the one sample piece is placed in the center of the surface (pile surface), etc. For each of the sample pieces, 5 cc of 60 ° C. warm water is applied to the center of the back surface, and touched with a finger immediately after the application and 5 minutes later. In this case, “◯” is displayed, “Δ” is displayed when a slime is felt, and “X” is displayed when a clear and slime is felt.

Claims (7)

  A flame retardant resin composition comprising a polyphosphoric acid flame retardant comprising composite particles of a polyphosphoric acid compound and a silicone resin, if necessary in the liquid, using an auxiliary agent or directly blended into the resin.   2. The flame retardant resin composition according to claim 1, wherein the polyphosphoric acid flame retardant has a silicone resin fixed around the particles of the polyphosphoric acid compound.   The flame-retardant resin composition according to claim 1 or 2, wherein the polyphosphoric acid compound has a weight average degree of polymerization of 20 to 2,000.   The flame retardant resin composition according to any one of claims 1, 2, and 3, wherein the polyphosphate compound is ammonium polyphosphate.   The flame-retardant resin composition according to any one of claims 1, 2, 3, and 4, wherein the silicone resin has a tetrafunctional monomer unit or a trifunctional monomer unit.   The flame retardant resin composition according to claim 1, wherein the resin is an elastomer resin.   The flame-retardant resin composition according to any one of claims 1 and 2, wherein the elastomer resin is an acrylic resin.