JPS5818393B2 - Flame retardant for polyurethane resin consisting of hydrated inorganic hollow particles - Google Patents
Flame retardant for polyurethane resin consisting of hydrated inorganic hollow particlesInfo
- Publication number
- JPS5818393B2 JPS5818393B2 JP49143883A JP14388374A JPS5818393B2 JP S5818393 B2 JPS5818393 B2 JP S5818393B2 JP 49143883 A JP49143883 A JP 49143883A JP 14388374 A JP14388374 A JP 14388374A JP S5818393 B2 JPS5818393 B2 JP S5818393B2
- Authority
- JP
- Japan
- Prior art keywords
- flame retardant
- hollow particles
- inorganic hollow
- polyurethane resin
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000002245 particle Substances 0.000 title claims description 17
- 239000003063 flame retardant Substances 0.000 title claims description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 12
- 229920005749 polyurethane resin Polymers 0.000 title claims description 7
- 229920003169 water-soluble polymer Polymers 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000499 gel Substances 0.000 description 7
- 229910001562 pearlite Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019362 perlite Nutrition 0.000 description 2
- 239000010451 perlite Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】
本発明は含水率の高いゲル状物を無機質中空粒の空隙に
含有した含水無機質中空粒からなるポリウレタン樹脂用
難燃剤（以下、単に難燃剤という〕に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame retardant for polyurethane resins (hereinafter simply referred to as flame retardant) comprising hydrous inorganic hollow particles containing a gel-like material with a high water content in the voids of the inorganic hollow particles.
従来から水溶性ポリマーをゲル化する手法はよく知られ
ている。Techniques for gelling water-soluble polymers have been well known.
しかし、これを無機質中空粒の空隙に含有（存在）して
防火剤として使用することは全くなかった。However, it has never been used as a fire retardant by containing (existing) in the voids of inorganic hollow particles.
本発明は新規な難燃剤を提案するものであり、概略説明
すれば、無数の気孔（貫通孔）を有する堅牢な殻によっ
て包囲された大きな中空（空隙）を有すると共に不燃で
あるパーライト粒などの気孔および空隙に全重量のほぼ
９割以上が水分である水溶性ポリマーをゲル化した状態
で存在させてポリウレタン樹脂の可燃性を改善するため
の難燃剤である。The present invention proposes a new flame retardant, which can be summarized as pearlite grains, which have a large hollow (void) surrounded by a strong shell with countless pores (through holes), and are nonflammable. This is a flame retardant that improves the flammability of polyurethane resin by allowing a gelled water-soluble polymer, which is approximately 90% or more of the total weight of water, to exist in the pores and voids.
以下に、本発明に係る難燃剤について詳細に説明する。Below, the flame retardant according to the present invention will be explained in detail.
すなわち、本発明において無機質中空粒（以下、単に粒
子という）とは、パーライト粒、シラスバルーンなどで
ある。That is, in the present invention, inorganic hollow particles (hereinafter simply referred to as particles) include pearlite particles, shirasu balloons, and the like.
また、含水架橋ゲルとは水溶性ポリマーで、例えばポリ
ビニールアルコール（ＰＶＡ）、カルボキシメチルセル
ロース（ＣＭＣ）などである。Further, the water-containing crosslinked gel is a water-soluble polymer, such as polyvinyl alcohol (PVA) and carboxymethyl cellulose (CMC).
さらに、無機質中空粒の空隙に含水架橋ゲルを含有させ
るには、水溶性ポ；リマーを加熱して粘度を低減し、粒
子の気孔からその空隙内に充填する。Furthermore, in order to contain the hydrous crosslinked gel in the voids of the inorganic hollow particles, the water-soluble polymer is heated to reduce its viscosity, and then filled into the voids through the pores of the particles.
そして、粒子内に上記ポリマーが充填されたならば、こ
れを取り出して、上記水溶性ポリマーを空隙内で反応さ
せて含水架橋ゲルに成牛ずる。Once the particles are filled with the polymer, they are taken out and the water-soluble polymer is reacted within the voids to form a hydrous crosslinked gel.
なお、含水架橋ゲルの生成力・法には、（イ）シアルデ
ィトによる方法、（ロ）過硫酸塩による方法、（・ラ
放射線による方法などの周知方法がある。In addition, the formation power and method of hydrous crosslinked gel include (a) method using sialdite, (b) method using persulfate, and (・ra) method.
There are well-known methods such as radiation methods.
また、難燃化する合成樹脂としては、ポリウレタン樹脂
である。Further, the synthetic resin that is flame retardant is polyurethane resin.
次に実施例につき説明する。Next, an example will be explained.
配合比
（ａ） 水溶性ポリマー（ＰＶＡ）８５重量部（ｂ）
水 １０００重量部（ｃ）
粒子（パーライト粒で平均粒径５ｍｍφ）２３０重量部
そこで、（ａ）、（ｂ）の２物質を混合、攪拌すること
によってＰＶＡを水に溶解する。Blending ratio (a) Water-soluble polymer (PVA) 85 parts by weight (b)
Water 1000 parts by weight (c)
230 parts by weight of particles (perlite particles, average particle size 5 mmφ) Then, the two substances (a) and (b) are mixed and stirred to dissolve PVA in water.
次に、この溶液を約７０〜１００℃に加熱し、これに（
Ｃ）のパーライト粒を投入し、２〜３分間ゆっくりと攪
拌する。Next, this solution was heated to about 70-100°C and added to (
Add the perlite particles from C) and stir slowly for 2 to 3 minutes.
そしてパーライト粒の空隙から空気が追い出され、それ
に代ってＰＶＡの溶液が充填された状態、すなわち、空
気とＰＶＡ溶液が完全に置換した状態になったところで
ザルなどの道具を介してパーライト粒を採取する。Then, when the air is expelled from the voids of the pearlite grains and filled with PVA solution, that is, the air and PVA solution are completely replaced, the pearlite grains are removed through a colander or other tool. Collect.
次に、このパーライト粒の空隙に存在するＰＶＡ溶液を
０９の方法によりゲル化する。Next, the PVA solution existing in the voids of the pearlite grains is gelled by the method of 09.
その結果、パーライト粒の空隙に存在するＰＶＡは架橋
反応を起し、塊状の含水架橋ゲルとなる。As a result, the PVA present in the voids of the pearlite grains undergoes a crosslinking reaction and becomes a blocky hydrous crosslinked gel.
換言するとパーライト粒内に存在したＰＶＡ溶液は上記
のようにゲル化し、溶液中の水がＰＶＡと結合してゲル
状となり、この粒子から溶液が漏洩することもな（、か
つ乾燥により含水率が低下することもなくなる。In other words, the PVA solution existing inside the pearlite grains gels as described above, and the water in the solution combines with PVA to form a gel, and the solution does not leak from the particles (and the water content decreases by drying). It will no longer decrease.
次に、このようにして製造した難燃剤はポリウレタンフ
ォームの難燃化にどの程度寄与するかを実験した。Next, an experiment was conducted to determine the extent to which the flame retardant thus produced contributed to flame retardation of polyurethane foam.
まずポリウレタン樹脂としてはポリオール（Ａ液）とし
てに−３３４２（第一工業製薬社製）を６０重量部、ポ
リイソシアネート（Ｂ液）としてミリオネ−１・ＭＲ−
１００（日本ポリウレタン社製）を１１０重量部、発泡
剤としてトリクロロモノフルオロメタン（Ｒ−１１）４
８重量部、触媒としてトリエチレンジアミンＤａｂｃｏ
３３ Ｌ Ｖを１重量部、気泡安定剤としてシロキサ
ン−オキシアルキレン共重合体５Ｈ−１９３（東しシリ
コーン社製）を１重量部用意し、ポリオール成分に発泡
剤、触媒、気泡安定剤を混合してＡ液とした。First, as a polyurethane resin, 60 parts by weight of -3342 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a polyol (liquid A), and Millione-1/MR- as a polyisocyanate (liquid B).
100 (manufactured by Nippon Polyurethane Co., Ltd.) and 110 parts by weight of trichloromonofluoromethane (R-11) as a blowing agent.
8 parts by weight, triethylenediamine Dabco as catalyst
Prepare 1 part by weight of 33 L V and 1 part by weight of siloxane-oxyalkylene copolymer 5H-193 (manufactured by Toshi Silicone Co., Ltd.) as a foam stabilizer, and mix the foaming agent, catalyst, and foam stabilizer with the polyol component. This was used as liquid A.
そこで、Ａ液とＢ液をワンショット法によりミキサーで
混合し、この際に１００重量部の難燃剤も同時に添加し
て混合し、下型上に吐出し、その後で上型をのせ、約８
０℃で５分間加熱し、加圧して厚さ１０ｍｍの板体を製
造した。Therefore, liquids A and B were mixed in a mixer using a one-shot method, and at this time, 100 parts by weight of flame retardant was also added and mixed, and the mixture was discharged onto the lower mold, and then the upper mold was placed on it.
It was heated at 0° C. for 5 minutes and pressurized to produce a plate with a thickness of 10 mm.
次に、このポリウレタンフォームに対し、パンスルーテ
ストを行なったところ、ポリウレタンフォーム単体より
約２倍の時間となった。Next, when we performed a pan-through test on this polyurethane foam, it took about twice as long as the polyurethane foam alone.
なお、パンスルーテストとはＢｕｒｅａｕ ｏｆＭｉｎ
ｅｓ 、 Ｒｅｐｏｒｔ ｏｆ Ｉｎｖｅｓｔｉｇａｔ
ｉｏｎ Ａ６３６６（１９６４）の方法である。Furthermore, the pan-through test is the Bureau of Min.
es, Report of Investigat
ion A6366 (1964).
上述したように本発明に係る難燃剤は、ポリウレタン樹
脂内に水分を大量にカプセル化した状態で分布したと同
様の難燃効果を発揮できる特徴がある。As described above, the flame retardant according to the present invention is characterized in that it can exhibit the same flame retardant effect as when a large amount of moisture is distributed in a polyurethane resin in an encapsulated state.
Claims (1)
性ポリマーの含水架橋ゲルを含有せしめたことを特徴と
する含水無機質中空粒からなるポリウレタン樹脂用難燃
剤。1. A flame retardant for polyurethane resins comprising hydrous inorganic hollow particles, characterized in that the voids of the inorganic hollow particles contain a hydrous crosslinked gel of a water-soluble polymer produced by a crosslinking reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49143883A JPS5818393B2 (en) | 1974-12-13 | 1974-12-13 | Flame retardant for polyurethane resin consisting of hydrated inorganic hollow particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49143883A JPS5818393B2 (en) | 1974-12-13 | 1974-12-13 | Flame retardant for polyurethane resin consisting of hydrated inorganic hollow particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5169547A JPS5169547A (en) | 1976-06-16 |
| JPS5818393B2 true JPS5818393B2 (en) | 1983-04-12 |
Family
ID=15349226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP49143883A Expired JPS5818393B2 (en) | 1974-12-13 | 1974-12-13 | Flame retardant for polyurethane resin consisting of hydrated inorganic hollow particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5818393B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0644995B2 (en) * | 1989-04-18 | 1994-06-15 | 三田工業株式会社 | Method for producing hydrous microcapsules |
-
1974
- 1974-12-13 JP JP49143883A patent/JPS5818393B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5169547A (en) | 1976-06-16 |
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