JP2826136B2 - Flame retardant composition - Google Patents
Flame retardant compositionInfo
- Publication number
- JP2826136B2 JP2826136B2 JP1265477A JP26547789A JP2826136B2 JP 2826136 B2 JP2826136 B2 JP 2826136B2 JP 1265477 A JP1265477 A JP 1265477A JP 26547789 A JP26547789 A JP 26547789A JP 2826136 B2 JP2826136 B2 JP 2826136B2
- Authority
- JP
- Japan
- Prior art keywords
- antimony pentoxide
- fiber
- tin compound
- flame
- tin
- 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 - Fee Related
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Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、ポリビニルアルコール（以下、単にPVAと
記載することがある）とポリ塩化ビニル（以下、単にPV
Cと記載することがある）を主な構成ポリマーとし、こ
れに特殊な添加剤を特定な量で加えた高難燃性組成物か
らなる繊維を提案するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to polyvinyl alcohol (hereinafter sometimes simply referred to as PVA) and polyvinyl chloride (hereinafter simply referred to as PV).
(May be described as C) as a main constituent polymer, and a fiber made of a highly flame-retardant composition to which a specific additive is added in a specific amount.
かかる高難燃性組成物から公知の混合紡糸により得ら
れる繊維は高度の難燃性を有し、また事実上、難燃性が
ない他繊維素材との混紡、交撚および交織等により、複
合化しても高度の難燃性を保持するため、難燃性の要求
される各種のインテリア製品、作業服、天幕地他に利用
可能である。Fibers obtained by known mixed spinning from such a high flame-retardant composition have a high degree of flame retardancy, and are practically blended with other fiber materials that do not have flame retardancy, by twisting and weaving, etc. Even if it is made to be highly flame-retardant, it can be used for various interior products, work clothes, tents and other places where flame retardancy is required.
＜従来の技術＞ PVAとPVCを主な構成ポリマーとし、これを紡糸した繊
維は難燃ビニロンやポリクラール系繊維として公知であ
る。<Prior Art> PVA and PVC are used as main constituent polymers, and fibers obtained by spinning the same are known as flame-retardant vinylon or polychloral fibers.
ここで、構成ポリマーのみより得られる繊維の難燃性
は、PVCの比率を極めて高率にすればある程度の難燃性
を有する繊維となり得るが、紡糸性が不良であつたり、
あるいは強度、吸湿性に代表される繊維物性が全く実用
に供し得ないものとなる。Here, the flame retardancy of the fiber obtained only from the constituent polymer can be a fiber having a certain degree of flame retardancy if the ratio of PVC is extremely high, but the spinnability is poor,
Alternatively, fiber properties such as strength and hygroscopicity cannot be put to practical use at all.
この様な問題を解決するにはPVC比率をより低率に
し、難燃性を確保する必要があり、その従来技術はメタ
スズ酸、酸化スズに代表される無機系スズ薬剤がポリマ
ーの発火温度低下の比較的低温領域でPVCの脱塩酸を促
進し、またこの塩酸および塩酸とスズの反応物である塩
化スズがPVAの脱水を促進させ、結果として、両ポリマ
ーの炭化を促進させ、難燃性を確保しているのが現状で
ある。In order to solve such problems, it is necessary to lower the PVC ratio and ensure flame retardancy, and the conventional technology uses inorganic tin chemicals represented by metastannic acid and tin oxide to lower the ignition temperature of the polymer. Promotes the dehydrochlorination of PVC in the relatively low temperature range, and the hydrochloric acid and tin chloride, which is a reaction product of hydrochloric acid and tin, promotes the dehydration of PVA. At present.
かかる従来技術によつて得られる難燃性繊維は高度な
難燃性が得られにくいことおよびこの繊維素材と事実上
難燃の繊維素材を混紡、交撚および交織等により併用し
た繊維素材とすると、その難燃性は著しく低下する欠点
を有している。The flame-retardant fiber obtained by such a conventional technique is difficult to obtain a high degree of flame retardancy, and a fiber material obtained by combining this fiber material with a practically flame-retardant fiber material by blending, twisting, weaving, etc. However, it has the disadvantage that its flame retardancy is significantly reduced.
この高度な難燃性が得られにくいのは、スズ系薬剤に
よるPVC,PVA両ポリマーの比較的低温領域における炭化
促進効果によるものを主体とする難燃効果があるため、
その炭化促進効果はスズ系薬剤の添加率に影響し、当然
添加率が大であるほど好ましいが、紡糸性、繊維物性へ
の悪影響のため添加率は制約を受け、また繊維物性をあ
る程度犠牲にしてもスズ系薬剤の添加率をさらに増加し
てもその効果の発現性には限界があるためである。This high flame retardancy is difficult to obtain because the tin-based chemical has a flame retardant effect mainly due to the carbonization promoting effect of both PVC and PVA polymers in a relatively low temperature region,
The effect of promoting carbonization affects the addition rate of tin-based chemicals. Naturally, the higher the addition rate, the better. However, the addition rate is restricted due to the adverse effect on spinnability and fiber properties, and the fiber properties are sacrificed to some extent. This is because even if the addition rate of the tin-based drug is further increased, there is a limit in the manifestation of the effect.
また、事実上、未難燃繊維素材と併用した場合難燃が
著しく低下するのは従来技術の難燃化の主体が固相にあ
り、基本的には他素材の事実上未難燃素材を混ぜると、
その混ぜた繊維材料に対する燃焼力の抑制効果の発現性
に乏しいためと考えられている。In addition, the fact that the flame retardancy is significantly reduced when used in combination with an unflammable fiber material is mainly due to the fact that the flame retardant of the prior art is in the solid phase. When mixed,
It is considered that the effect of suppressing the combustion power on the mixed fiber material is poor.
＜発明が解決しようとする課題＞ 本発明は、従来技術の問題点の解消を計つたもので、
PVCの比率を高めなくても、また、繊維物性の悪影響の
ほとんどない添加剤量率でも、従来技術では達成し得な
かつた高度な難燃性と、また、事実上の未難燃繊維素材
を混ぜても難燃度の低下の少ないPVA/PVC系の難燃素材
を提案するものである。<Problems to be Solved by the Invention> The present invention aims to solve the problems of the prior art.
Even if the ratio of PVC is not increased, and even if the amount of additives has almost no adverse effect on the physical properties of fibers, the high flame retardancy that cannot be achieved by the conventional technology and the virtually unflammable fiber material The present invention proposes a PVA / PVC-based flame-retardant material that has a small decrease in flame retardancy even when mixed.
＜課題を解決するための手段＞ すなわち、本発明は、ポリビニルアルコールとポリ塩
化ビニルを主な構成ポリマーとし、これにスズ化合物と
五酸化アンチモンが配合されており、かつ以下の（ａ）
〜（ｄ） （ａ） ポリビニルアルコール／ポリ塩化ビニルの配合
重量比＝85/15〜35/65、 （ｂ） スズ化合物と五酸化アンチモンの総配合量が全
ポリマー量に対して２〜10重量％、 （ｃ） スズ化合物／五酸化アンチモンの配合重量比が
1/5〜5/1、 （ｄ） スズ化合物および五酸化アンチモンの平均粒子
径が共に３μｍ以下 を全て満足していることを特徴とする難燃性繊維である
（但し、上記スズ化合物の配合量は酸化スズ（SnO2）換
算の量である）。<Means for Solving the Problems> That is, in the present invention, polyvinyl alcohol and polyvinyl chloride are used as main constituent polymers, and a tin compound and antimony pentoxide are blended therein, and the following (a)
(D) (a) the blending weight ratio of polyvinyl alcohol / polyvinyl chloride = 85/15 to 35/65, (b) the total blending amount of the tin compound and antimony pentoxide is 2 to 10 wt. %, (C) the compounding weight ratio of tin compound / antimony pentoxide is
1/5 to 5/1, (d) a flame-retardant fiber characterized in that the tin compound and antimony pentoxide both have an average particle size of 3 μm or less. The amount is a tin oxide (SnO 2 ) equivalent amount).
ここで、本発明の最大の特長であるスズ化合物と五酸
化アンチモンをPVAとPVCを主構成とするポリマー中に添
加する理由はこの両者（酸化スズ水和物と五酸化アンチ
モン）を併用添加することにより、極めて顕著なポリマ
ーの難燃化に対する相乗効果が得られ、かつ、他の事実
上、未難燃の繊維素材を混ぜても、その難燃性の低下が
少ないためである。Here, the reason why the tin compound and antimony pentoxide, which are the greatest features of the present invention, are added to the polymer mainly composed of PVA and PVC is that both (tin oxide hydrate and antimony pentoxide) are added together. This is because a very remarkable synergistic effect on the flame retardancy of the polymer is obtained, and the flame retardancy of the non-flame-retardant fiber material is less reduced even when other non-flame-retardant fiber materials are mixed.
ここで、PVA/PVCの重量比を85/15〜35/65としたの
は、PVAが85重量％を越えるとPVCの比率が極めて低率と
なり、スズ化合物、五酸化アンチモンをいかに多量に配
合しても、繊維組成中のハロゲン（塩素）が少なすぎる
効果として、得られる難燃度は低いものとなるためであ
り、逆にPVAが35％未満の場合は、難燃性は良好で問題
ないが、強度等の繊維物性面で劣るためである。Here, the reason that the weight ratio of PVA / PVC is 85/15 to 35/65 is that if the PVA exceeds 85% by weight, the ratio of PVC becomes extremely low, and how much tin compound and antimony pentoxide are mixed However, as the effect of too little halogen (chlorine) in the fiber composition, the obtained flame retardancy is low. Conversely, if the PVA is less than 35%, the flame retardancy is good and there is no problem. However, this is because fiber properties such as strength are inferior.
スズ化合物と五酸化アンチモンの総配合量率が全ポリ
マーに対し２重量％未満である場合には、難燃性の発現
性に問題があり、また10重量％を越える場合には難燃性
における向上効果がそれほどないため必要性がないこ
と、および繊維物性に対する悪影響が顕著になるため好
ましくない。When the total compounding ratio of the tin compound and antimony pentoxide is less than 2% by weight based on the total polymer, there is a problem in the manifestation of flame retardancy. It is not preferable because there is not much improvement effect and there is no necessity, and the adverse effect on the physical properties of the fiber becomes remarkable.
また、スズ化合物／五酸化アンチモンの重量比におい
て、1/5〜5/1の範囲を外れると、両添加薬剤の難燃化に
対する相乗効果が不充分となり、結果として難燃性に問
題を生じるため好ましくない。なお上記スズ化合物に関
しての配合量、すなわち五酸化アンチモンとの総配合量
および五酸化アンチモンとの配合量比に関しては酸化ス
ズ（SnO2）で換算した値である。If the weight ratio of the tin compound to antimony pentoxide is out of the range of 1/5 to 5/1, the synergistic effect of the two additives on the flame retardancy becomes insufficient, resulting in a problem in the flame retardancy. Therefore, it is not preferable. Note that the compounding amount of the tin compound, that is, the total compounding amount with antimony pentoxide and the compounding ratio with antimony pentoxide are values converted with tin oxide (SnO 2 ).
さらに、スズ化合物と五酸化アンチモンの平均粒子径
は、難燃性、繊維物性および紡糸性に影響を与え、共に
３μｍを越える粒子径の場合は、好ましくない。本発明
で言う平均粒子径とはメジアン径を意味している。Furthermore, the average particle size of the tin compound and antimony pentoxide affects flame retardancy, fiber properties and spinnability, and it is not preferable that the average particle size exceeds 3 μm. The average particle diameter in the present invention means a median diameter.
本発明において、アンチモン化合物として五酸化アン
チモンが用いられるがこの理由は代表的な酸化アンチモ
ンである三酸化アンチモンは、とくにアルカリ性溶液に
溶解する特性があり、アルカリ浴を紡糸浴とする場合あ
るいは本発明の難燃繊維を綿等と混紡した布帛等に対
し、マーセライズ加工等の濃厚アルカリ浴で処理する際
溶出し、難燃性が低下することとなるのに対し、五酸化
アンチモンはかかるアルカリに対し溶出しないことより
好ましいものである。In the present invention, antimony pentoxide is used as the antimony compound. This is because antimony trioxide, a typical antimony oxide, has the property of dissolving in an alkaline solution in particular. When the flame-retardant fiber is mixed with cotton or the like, it is eluted when treated in a concentrated alkaline bath such as mercerizing, and the flame retardancy is reduced. It is more preferable not to elute.
本発明においてPVAおよびPVCポリマーとは事実上ほぼ
完全なホモ・ポリマーであつても、あるいはビニルアル
コール単位あるいは塩化ビニル単位を分子中に85モル％
以上含有した共重合体であつてもよく、さらにPVA、PVC
以外の第３成分のポリマーを全ポリマー成分に対し、10
重量％を越えない範囲で添加してもよい。In the present invention, the PVA and PVC polymers may be virtually completely homopolymers, or may contain vinyl alcohol units or vinyl chloride units in an amount of 85 mol% in the molecule.
It may be a copolymer containing the above, further PVA, PVC
The polymer of the third component other than the
You may add in the range which does not exceed weight%.
本発明の特長であるスズ化合物とは、IIおよびIV価の
スズ化合物、例えば、酸化スズ、メタスズ酸等を意味
し、五酸化アンチモンはＶ価のアンチモンの酸化物すな
わちSb2O5を意味し、また、本発明のスズ化合物および
五酸化アンチモンには、その水和物も含まれる。なお、
本発明のポリマー成分に対する添加率２〜10重量％には
水和物を除外した無水和物に換算したものを意味する。With features tin compound is present invention, II and IV valent tin compounds, for example, tin oxide, means metastannic acid, antimony pentoxide means oxides i.e. Sb 2 O 5 of the V-valent antimony The tin compound and antimony pentoxide of the present invention also include hydrates thereof. In addition,
An addition ratio of 2 to 10% by weight based on the polymer component of the present invention means a value calculated as an anhydrate excluding hydrates.
＜作用＞ 本発明によるPVA/PVC系繊維は従来技術のものに比較
し、卓越した難燃度を確保し、かつ、事実上未難燃の酸
素指数値25以下の繊維素材、例えば綿、レーヨン等を本
発明の繊維素材と混紡等により混ぜ合せて布帛等の製品
を作つてもその難燃性の低下の少ない良好な難燃性を保
持する特性を有している。<Function> The PVA / PVC fiber according to the present invention has an excellent flame retardancy as compared with that of the prior art, and is a non-flammable fiber material having an oxygen index value of 25 or less, such as cotton or rayon. And the like are mixed with the fiber material of the present invention by blending or the like to produce a product such as a fabric.
これらの作用機構は必らずしも明解ではないが、スズ
系化合物の卓越した固相におけうポリマーの炭化促進作
用と五酸化アンチモンによる気相における活性ラジカル
補促作用が共にバランスよく働き、結果として本発明の
繊維が上記の優れた性能を呈したと考えられる。Although the mechanism of action is not always clear, the excellent carbonization promoting action of the polymer in the solid phase of the tin-based compound and the active radical promoting action in the gas phase by antimony pentoxide work in a well-balanced manner, As a result, it is considered that the fiber of the present invention exhibited the excellent performance described above.
なお本発明の組成物には必要により、他の有機・無機
物質が添加されていてもよい。The composition of the present invention may contain other organic or inorganic substances, if necessary.
実施例１ 平均重合度1700、鹸化度98.2％のPVAに、重合度1000
のPVAエマルジヨン、平均粒子径0.8μｍの酸化スズ、及
び平均粒子径0.03μｍの五酸化アンチモンゾルをそれぞ
れ第１表の組成になるように添加した紡糸原液を、20g/
の水酸化ナトリウムと350g/の硫酸ナトリウムを含
む温度40℃の凝固浴の中へ、孔径0.08mm、孔数6000の口
金を通して押し出して、糸条形成した後、100g/の硫
酸と300g/の硫酸ナトリウムを含む温度35℃の処理浴
を通して中和し、水洗、乾燥を経た後、総延伸倍率が10
倍になるように乾燥延伸を行なつた。この延伸済みの繊
維に油剤処理及び機械捲縮を付与した後、38mmに切断し
て原綿を得た。この原綿からホームスパンにより糸を形
成してニツト地を作成して酸素指数値を評価した。また
形成した繊維の物性はフアイバー強伸度を測定して評価
した。Example 1 PVA having an average polymerization degree of 1700 and a saponification degree of 98.2% was added to a polymerization degree of 1000.
Of a PVA emulsion, tin oxide having an average particle diameter of 0.8 μm, and antimony pentoxide sol having an average particle diameter of 0.03 μm, each having the composition shown in Table 1, were added at 20 g /
Extruded into a coagulation bath containing sodium hydroxide and 350 g / sodium sulfate at a temperature of 40 ° C through a die with a pore size of 0.08 mm and a number of holes of 6000, and after forming a thread, 100 g / sulfuric acid and 300 g / sulfuric acid Neutralized through a treatment bath containing sodium at a temperature of 35 ° C., washed with water, dried, and then subjected to a total draw ratio of 10%.
Dry stretching was performed so as to double the size. After applying an oil treatment and mechanical crimping to the drawn fiber, the fiber was cut into 38 mm to obtain a raw cotton. A yarn was formed from the raw cotton by a homespun to prepare a knitted fabric, and the oxygen index value was evaluated. The physical properties of the formed fibers were evaluated by measuring the fiber elongation.
実施例２ 実施例１と同一のPVA、PVCを用い第２表に示す粒子径
の異なる酸化スズと五酸化アンチモンを配合した組成と
し、実施例１と同一条件により繊維を形成し、そのフア
イバー強度、酸素指数値を実施例１と同様測定した。 Example 2 Using the same PVA and PVC as in Example 1, a composition was used in which tin oxide and antimony pentoxide having different particle diameters as shown in Table 2 were blended, and a fiber was formed under the same conditions as in Example 1; The oxygen index value was measured in the same manner as in Example 1.
なおPVA/PVC重量比は60/40、メタスズ酸と五酸化アン
チモンの配合率はPVA、PVCポリマー計に対し、それぞれ
３％／ポリマーとした。The weight ratio of PVA / PVC was 60/40, and the compounding ratio of metastannic acid and antimony pentoxide was 3% / polymer for the PVA and PVC polymer, respectively.
実施例３ 実施例１の第１表No.3とNo.6（本発明例と従来技術
例）により生産した38mmカツト品をエジプト綿と混紡、
スフ紡績法により、綿が30重量％となる20番手の糸を紡
出した。 Example 3 A 38 mm cut product produced according to Table 1 No. 3 and No. 6 of Example 1 (Example of the present invention and prior art) was blended with Egyptian cotton,
The 20th yarn with 30% cotton by weight was spun by the swoof spinning method.
この糸を双糸に撚糸、平織組織で打込密度経方向53本
/in、緯方向42本/inの180g/m2の基布を製織した。This yarn is twisted into a twin yarn, with a plain weave design, and a driving density of 53 yarns in the warp direction.
A 180 g / m 2 base fabric of / in and a weft direction of 42 fibers / in was woven.
この基布について、JIS K7201法による酸素指数値
（LOI）およびJIS Ｌ−1091 Ａ−１法による防炎性テ
ストを実施し、第３表の結果を得た。The base fabric was subjected to an oxygen index value (LOI) according to the JIS K7201 method and a flame resistance test according to the JIS L-1091 A-1 method, and the results shown in Table 3 were obtained.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭49−62728（ＪＰ，Ａ) 特開 昭60−259678（ＪＰ，Ａ) 特開 昭63−46291（ＪＰ，Ａ) 特開 昭49−32943（ＪＰ，Ａ) 特公 昭49−6486（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.6，ＤＢ名) C08L 29/04,27/04 - 27/08 C08K 3/16,3/22,7/18 D01F 8/10──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-62728 (JP, A) JP-A-60-259678 (JP, A) JP-A-63-46291 (JP, A) 32943 (JP, A) JP 49-6486 (JP, B1) (58) Fields investigated (Int. Cl. 6 , DB name) C08L 29/04, 27/04-27/08 C08K 3/16, 3 / 22,7 / 18 D01F 8/10
Claims (1)
主な構成ポリマーとし、これにスズ化合物度と五酸化ア
ンチモンが配合されており、かつ以下の（ａ）〜
（ｄ）： （ａ）ポリビニルアルコール／ポリ塩化ビニルの配合重
量比＝85/15〜35/〜65, （ｂ）スズ化合物／五酸化アンチモンの総配合量が全ポ
リマー量に対して２〜10重量％， （ｃ）スズ化合物／五酸化アンチモンの配合重量比が1/
5〜5/1, （ｄ）スズ化合物および五酸化アンチモンの平均粒子径
が共に３μｍ以下 を全て満足していることを特徴とする難燃性繊維（但
し、上記スズ化合物の配合量は酸化スズ換算の量であ
る）。(1) Polyvinyl alcohol and polyvinyl chloride are used as main constituent polymers, which are mixed with a tin compound and antimony pentoxide.
(D): (a) the blending weight ratio of polyvinyl alcohol / polyvinyl chloride = 85/15 to 35 / -65, (b) the total blending amount of tin compound / antimony pentoxide is 2 to 10 with respect to the total polymer amount. Wt%, (c) tin compound / antimony pentoxide compounding weight ratio is 1 /
5 to 5/1, (d) flame-retardant fiber, characterized in that the tin compound and antimony pentoxide both have an average particle diameter of 3 μm or less (however, the amount of the tin compound is tin oxide Conversion amount).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1265477A JP2826136B2 (en) | 1989-10-11 | 1989-10-11 | Flame retardant composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1265477A JP2826136B2 (en) | 1989-10-11 | 1989-10-11 | Flame retardant composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03126749A JPH03126749A (en) | 1991-05-29 |
| JP2826136B2 true JP2826136B2 (en) | 1998-11-18 |
Family
ID=17417720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1265477A Expired - Fee Related JP2826136B2 (en) | 1989-10-11 | 1989-10-11 | Flame retardant composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2826136B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083499C (en) * | 1997-10-07 | 2002-04-24 | 可乐丽股份有限公司 | Flame-retardant polyvinyl alcohol base fiber |
| JPWO2006087983A1 (en) * | 2005-02-21 | 2008-07-03 | 株式会社クラレ | Flame retardant polyvinyl alcohol fiber |
| JP2008101293A (en) * | 2006-10-19 | 2008-05-01 | Kuraray Co Ltd | Polyvinyl alcohol-based flame-retardant fiber having excellent smoke-reducing performance |
| CN105419189A (en) * | 2015-12-03 | 2016-03-23 | 江阴市和润精密钢管有限公司 | Environment-friendly formaldehyde-free plastic plate and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5429711B2 (en) * | 1972-03-29 | 1979-09-26 | ||
| JPS4962728A (en) * | 1972-10-18 | 1974-06-18 | ||
| JPS60259678A (en) * | 1984-05-31 | 1985-12-21 | 住友化学工業株式会社 | Fire retardant backing composition |
| CA1296463C (en) * | 1986-08-12 | 1992-02-25 | Larry G. Eskind | Fire retardant compositions and use thereof |
-
1989
- 1989-10-11 JP JP1265477A patent/JP2826136B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03126749A (en) | 1991-05-29 |
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