JP2006063464A5 - - Google Patents
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- JP2006063464A5 JP2006063464A5 JP2004244891A JP2004244891A JP2006063464A5 JP 2006063464 A5 JP2006063464 A5 JP 2006063464A5 JP 2004244891 A JP2004244891 A JP 2004244891A JP 2004244891 A JP2004244891 A JP 2004244891A JP 2006063464 A5 JP2006063464 A5 JP 2006063464A5
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本発明に係るポリリン酸系難燃剤は、ポリリン酸化合物とシリコーン系樹脂との複合粒子に成り、ポリリン酸化合物粒子の周りにシリコーン系樹脂が固着していることを第１の特徴とする。 Polyphosphate flame retardant according to the present invention, Ri formed in the composite particles of the polyphosphate compound and the silicone-based resin, and the first, characterized in that silicone resin is stuck around the polyphosphate compound particles.
本発明に係るポリリン酸系難燃剤の第２の特徴は、上記第１の特徴に加えて、ポリリン酸化合物の重量平均重合度が２０〜２０００である点にある。 The second feature of the polyphosphoric acid flame retardant according to the present invention is that, in addition to the first feature, the polyphosphoric acid compound has a weight average degree of polymerization of 20 to 2,000 .
本発明に係るポリリン酸系難燃剤の第３の特徴は、上記第１と第２の何れかの特徴に加えて、ポリリン酸化合物がポリリン酸アンモニウムである点にある。 A third feature of the polyphosphate flame retardant according to the present invention is that, in addition to any of the first and second features, the polyphosphate compound is ammonium polyphosphate .
本発明に係るポリリン酸系難燃剤の第４の特徴は、上記第１と第２と第３の何れかの特徴に加えて、シリコーン系樹脂が四官能性モノマーユニットまたは三官能性モノマーユニットを有している点にある。 The fourth feature of the polyphosphate flame retardant according to the present invention is that, in addition to any of the first, second, and third features, the silicone resin contains a tetrafunctional monomer unit or a trifunctional monomer unit. It is in having .
本発明に係るポリリン酸系難燃剤の第５の特徴は、上記第４の特徴に加えて、シリコーン系樹脂が一般式（Ｒ n ＳｉＯ (4-n)/2 ） m （但し、Ｒは、メチル基、アルキル基、フッ素化アルキル基、フェニル基、ビニル基などの置換基，ｎ＝１〜３，ｍ≧２）で表示されるものである点にある。 The fifth feature of the polyphosphate flame retardant according to the present invention is that, in addition to the fourth feature, the silicone resin is represented by the general formula (R n SiO (4-n) / 2 ) m (where R is The substituent is a methyl group, an alkyl group, a fluorinated alkyl group, a phenyl group, a vinyl group, or the like, n = 1 to 3, and m ≧ 2) .
シリコーン系樹脂は、ポリリン酸化合物粒子を被覆するために適用されるのであり、それを溶媒溶液に溶解したシリコーン樹脂溶液として調製することが望ましい。
それをシリコーン樹脂分散液として調製するときは、そのシリコーン樹脂粒子をポリリン酸化合物粒子よりも細かく、その粒径を３〜２５μｍにし、ポリリン酸化合物粒子の表面に付着し易くする。
シリコーン系樹脂の適用量は、ポリリン酸化合物１００重量部に対して２〜２０重量となる程度でよい。
The silicone resin is applied to coat the polyphosphate compound particles, and it is desirable to prepare 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 polyphosphate compound particles, and the particle size thereof is 3 to 25 μm, so that they easily adhere to the surface of the polyphosphate compound particles.
The application amount of the silicone resin may be about 2 to 20 weights per 100 weight parts of the polyphosphate compound .
シリコーン系樹脂によってポリリン酸化合物粒子を効果的に被覆するためには、前記特許文献１・２が示すように、ポリリン酸化合物の製造時の原料にシリコーン系樹脂成分を共存させ、或いは、前記特許文献３が示すように、シリコーン系樹脂溶液やシリコーン系樹脂分散液とポリリン酸化合物粉末や分散液を混合・攪拌し、加熱処理するとよい。シリコーン系樹脂溶液やシリコーン系樹脂分散液の溶媒としては、アセトン、酢酸エチル、メチルアルコール等の親水性有機溶剤を用いるとよい。
又、シリコーン系樹脂によってポリリン酸化合物粒子を被覆するためには、平均粒径３〜２５μｍのシリコーン系樹脂粒子の分散液とポリリン酸化合物粉末分散液との混合液や、シリコーン系樹脂微粉末をトルエンその他の有機溶剤に溶解したシリコーン系樹脂溶液にポリリン酸化合物の微粉末を混合した混合液を乾燥して得られるシリコーン系樹脂とポリリン酸化合物との混合物を、ボールミルやジェットミル等の粉砕装置によって粉砕して微粉末にしてもよい。
シリコーン系樹脂は、紫外線吸収剤、抗酸化剤、着色顔料等との混合組成物として調製することが出来る。
ポリリン酸化合物の粒子の表面を被覆するシリコーン系樹脂皮膜の硬質化のためには、シリコーン系樹脂組成物にポリメチルアクリレート樹脂を混用するとよい。
In order to effectively coat the polyphosphate compound particles with the silicone resin, as disclosed in Patent Documents 1 and 2, the silicone resin component is allowed to coexist in the raw material when the polyphosphate compound is produced, or the patent As document 3 shows, it is preferable to mix and stir a silicone resin solution or silicone resin dispersion, and a polyphosphate compound powder or dispersion, 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 compound particles with a silicone resin, a mixed solution of a dispersion of a silicone resin particle having an average particle diameter of 3 to 25 μm and a polyphosphate compound powder dispersion, or a silicone resin fine powder is used. Grinding equipment such as ball mill and jet mill for the mixture of silicone resin and polyphosphate compound obtained by drying a mixed solution of polyphosphate compound fine powder mixed with silicone resin solution dissolved in toluene or other organic solvent May be pulverized into 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 covers the surface of the particles of the polyphosphoric acid compound, a polymethyl acrylate resin may be mixed with the silicone resin composition.
ポリリン酸化合物の粒子とシリコーン系樹脂に成るシリコーン付加ポリリン酸系難燃剤は、バインダー樹脂に配合して使用される。
バインダー樹脂には、アクリル系樹脂エマルジョン、ウレタン系樹脂エマルジョン、エチレン・酢酸ビニル系樹脂エマルジョン等の樹脂エマルジョンが使用される。
シリコーン付加ポリリン酸系難燃剤を繊維製品の難燃化処理に適用する場合、アクリル系樹脂エマルジョンをバインダー樹脂に適用することが推奨される。
当然のことながら、本発明の目的からして、バインダー樹脂には、ハロゲン成分やホルムアルデヒド成分を含有しないものを使用する。
Silicone-added polyphosphoric acid flame retardant comprising polyphosphoric acid compound particles and silicone resin is used by blending with 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.
ポリリン酸化合物としては、重量平均重合度２０〜２０００のポリリン酸アンモニウムが推奨される。
重量平均重合度が２０未満のものは水溶性を示し、重量平均重合度が２０００を越えるものは、重合時間が長く、コスト高になるので実用性を欠く。
As the polyphosphate compound, 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.
シリコーン系樹脂エマルジョン（樹脂成分；オルガノポリシロキサン２０重量％、明成化学工業株式会社製品名；ＫＲ−５０）（実施例１）と、ウレタン系樹脂エマルジョン（樹脂成分；ポリウレタン３０重量％、大日本インキ化学工業株式会社製品名；ハイドランＨＷ−９３０）（比較例１）と、エチレン・酢酸ビニル系樹脂エマルジョン（樹脂成分；エチレン・酢酸ビニル４５重量％、伸葉株式会社製品名；ＹＳ−９１２）（比較例２）と、アクリル系樹脂エマルジョン（樹脂成分；アクリル樹脂５０重量％、新中村化学工業株式会社製品名；ニューコートＦＨ−４５）（比較例３）と、触媒（住友ケムテックス株式会社製品名；スミテックスアクセラレーターＡＣＸ）を配合したメラミン系樹脂エマルジョン（樹脂成分；メラミン樹脂７５重量％、住友ケムテックス株式会社製品名；スミテックスレジンＭ−３）（比較例４）の各樹脂エマルジョン１００重量部に、水を２００重量部加え、８０℃に加熱して２０分間攪拌し、その各樹脂エマルジョンを主成分とする５種類の樹脂溶液を調製する。
次いで、その各樹脂溶液に平均粒径８μｍのポリリン酸アンモニウム粒子を、それらの各樹脂溶液の含有する樹脂分に対するポリリン酸アンモニウム粒子の配合比率が等しくなるように配合して５種類のポリリン酸アンモニウム粒子分散溶液を調製する。
又、上記５種類の樹脂溶液とは別に、実施例２として、シリコーン系樹脂（オルガノポリシロキサン、信越化学工業株式会社製品）６重量部とトルエン１００重量部とからなる樹脂溶解溶液に、平均粒径８μｍのポリリン酸アンモニウム粒子（１００重量部）を、その配合比率が上記の５種類のポリリン酸アンモニウム粒子分散溶液の含有する樹脂分に対するポリリン酸アンモニウム粒子の配合比率と等しくなるように、配合してポリリン酸アンモニウム粒子分散溶液を調製する。更に、実施例３として、シリコーン系樹脂（オルガノポリシロキサン、信越化学工業株式会社製品）６重量部とトルエン１００重量部とからなる樹脂溶解溶液に、平均粒径２０μｍのポリリン酸アンモニウム粒子（１００重量部）を、実施例２と同様に、その配合比率が上記の５種類のポリリン酸アンモニウム粒子分散溶液の含有する樹脂分に対するポリリン酸アンモニウム粒子の配合比率と等しくなるように、配合してポリリン酸アンモニウム粒子分散溶液を調製する。
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) ; Sumitex Accelerator ACX) melamine resin emulsion blended with (resin component; melamine 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.
上記合計７種類のポリリン酸アンモニウム粒子分散溶液を加熱して溶媒（水・トルエン）を除去し、樹脂で被覆され、ポリリン酸アンモニウム粒子に対する被覆樹脂の付着量が５．７重量％の乾燥した７種類の樹脂被覆ポリリン酸アンモニウム粒子を調製し、（１） それらの合計７種類の乾燥した樹脂被覆ポリリン酸アンモニウム粒子の各１００重量部と、樹脂に被覆されないブランクの未処理ポリリン酸アンモニウム粒子（比較例５）１００重量部に、それぞれ水（６０℃）１００重量部を加えて１分間攪拌して調製された樹脂被覆ポリリン酸アンモニウム粒子と未処理ポリリン酸アンモニウム粒子の加湿粉末のヌメリ感と、（２） それらの合計７種類の樹脂被覆ポリリン酸アンモニウム粒子と未処理ポリリン酸アンモニウム粒子をそれぞれ個別に臭い袋（近江オドエァーサービス株式会社製）に５ｇｆ装填して密封し、その臭い袋に空気を２０００ｍｌ（ｃｃ）注入して８０℃にて２時間加熱して発生するホルムアルデヒドの濃度をガステック検知管（株式会社ガステック製品名；ホルムアルデヒド検知管Ｎｏ．９１Ｌ）によって測定すると共に、（３）
それらの合計７種類の樹脂被覆ポリリン酸アンモニウム粒子と未処理ポリリン酸アンモニウム粒子の各２０重量部をアクリル系樹脂エマルジョン（樹脂成分；アクリル樹脂５０重量％、新中村化学工業株式会社製品名；ニューコートＦＨ−４５）に混合した分散溶液中のポリリン酸アンモニウム粒子の分散状態を調べ、下記〔表１〕の上段に示す結果を得た。
The total 7 types of ammonium polyphosphate particle dispersions were heated to remove the solvent (water / toluene), coated with a resin, and dried 7 % by weight of the coating resin adhering to the ammonium polyphosphate particles. (1) 100 parts by weight of each of these 7 types of dried resin-coated ammonium polyphosphate particles and blank untreated ammonium polyphosphate particles that are not coated with resin (comparison) Example 5) 100 parts by weight of water (60 ° C.) and 100 parts by weight of water (60 ° C.) respectively, and stirring for 1 minute, the slime feeling of the humidified powder of resin-coated ammonium polyphosphate particles and untreated ammonium polyphosphate particles, 2) A total of 7 types of resin-coated ammonium polyphosphate particles and untreated ammonium polyphosphate particles The odor bag (Omi Odore Service Co., Ltd.) was individually charged with 5 gf and sealed, and 2000 ml (cc) of air was injected into the odor bag and heated at 80 ° C. for 2 hours to determine the concentration of formaldehyde generated. Measured with a gas-tech detector tube (Gastech product name; formaldehyde detector tube No. 91L) and (3)
20 parts by weight of each of 7 kinds of resin-coated ammonium polyphosphate particles and untreated ammonium polyphosphate particles (acrylic resin emulsion; resin component: 50% by weight of acrylic resin, Shin-Nakamura Chemical Co., Ltd., product name: New Coat) The dispersion state of ammonium polyphosphate particles in the dispersion solution mixed with FH-45) was examined, and the results shown in the upper part of [Table 1] below were obtained.
Claims (5)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004244891A JP2006063464A (en) | 2004-08-25 | 2004-08-25 | Polyphosphoric acid-based flame retarder |
| US11/661,162 US7611771B2 (en) | 2004-08-25 | 2005-08-22 | Polyphosphate flame retardant |
| PCT/JP2005/015199 WO2006022219A1 (en) | 2004-08-25 | 2005-08-22 | Polyphosphoric acid type flame retardant |
| CN 200580028561 CN101014684A (en) | 2004-08-25 | 2005-08-22 | Polyphosphoric acid type flame retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004244891A JP2006063464A (en) | 2004-08-25 | 2004-08-25 | Polyphosphoric acid-based flame retarder |
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| Publication Number | Publication Date |
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| JP2006063464A JP2006063464A (en) | 2006-03-09 |
| JP2006063464A5 true JP2006063464A5 (en) | 2007-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2004244891A Pending JP2006063464A (en) | 2004-08-25 | 2004-08-25 | Polyphosphoric acid-based flame retarder |
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| JP (1) | JP2006063464A (en) |
| CN (1) | CN101014684A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5058687B2 (en) * | 2006-08-02 | 2012-10-24 | 本田技研工業株式会社 | Flame retardant composition having deodorizing effect and flame retardant fabric |
| JP5204472B2 (en) * | 2007-02-02 | 2013-06-05 | 富士ゼロックス株式会社 | Resin composition, resin molded body and method for producing the same |
| KR20110048339A (en) * | 2009-11-02 | 2011-05-11 | 엘에스전선 주식회사 | Highly flame-retardant, halogen-free colored heat-shrink tubing |
| CN101885860B (en) * | 2010-03-24 | 2012-05-16 | 中南林业科技大学 | Expansible composite flame retardant and flame retardant material containing same |
| CN101921432A (en) * | 2010-09-29 | 2010-12-22 | 东莞市柏百顺石油化工有限公司 | Low-smoke halogen-free flame-retardant polypropylene cable material and preparation method thereof |
| JP6363376B2 (en) * | 2014-04-03 | 2018-07-25 | アイカ工業株式会社 | Hydrophobic resin-ammonium polyphosphate complex |
| JP6463196B2 (en) * | 2014-10-30 | 2019-01-30 | アイカ工業株式会社 | Hydrophobic resin-ammonium polyphosphate complex |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10204212A (en) * | 1997-01-16 | 1998-08-04 | Chisso Corp | Flame retardant and thermoplastic resin composition containing the same |
| JP2001262466A (en) * | 2000-03-15 | 2001-09-26 | Chisso Corp | Flame-retardant fiber product and flameproofing agent |
| JP2003171878A (en) * | 2001-12-03 | 2003-06-20 | Aisin Chem Co Ltd | Flame-retardant backing material |
| JP2006028488A (en) * | 2004-06-14 | 2006-02-02 | Nisshin Chem Ind Co Ltd | Coating composition for vehicular interior finishing material and the vehicular interior finishing material |
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2004
- 2004-08-25 JP JP2004244891A patent/JP2006063464A/en active Pending
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2005
- 2005-08-22 CN CN 200580028561 patent/CN101014684A/en active Pending
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