JP5187992B2 - Non-halogen flame retardant putty composition - Google Patents

Description

【００２５】
作製されたノンハロゲン難燃性パテ組成物を評価は以下の方法で行い、その評価結果を表２に示した。
（１）難燃性の評価は、作製されたノンハロゲン難燃性パテ組成物をＪＩＳ Ｋ７２０１に記載されている酸素指数測定方法に準拠して測定を行い、酸素指数６０以上の値を○、６０より小さい値は×と評価した。
（２）灰化物の強靭性の評価は、作製されたノンハロゲン難燃性パテ組成物を一辺３０ｍｍの立方体に充填し、１０００℃で４時間保持して、灰化したノンハロゲン難燃性パテ組成物を荷重２５Ｎで押しても壊れなかったものを○、壊れたものを×と評価した。
（３）耐熱変形性の評価は、作製されたノンハロゲン難燃性パテ組成物を３０ｍｍ×３０ｍｍ×７０ｍｍの直方体に充填し、２５０℃で３０分保持した時の変形量が１０％未満のものを○、１０％以上のものを×と評価した。
（４）粘着性の評価は、図１に示すような状態で引張試験を実施し評価した。
（イ）４０ｍｍ×４０ｍｍ×５ｍｍの形状に成型した２個のノンハロゲン難燃性パテ組成物２を重ねて、その重なったノンハロゲン難燃性パテ組成物２をポリ塩化ビニルシート１（厚さ２ｍｍ、幅４０ｍｍ、長さ１１０ｍｍ）で挟み込み上部より９．８Ｎの荷重Ｆで１時間押さえつけ、２個のノンハロゲン難燃性パテ組成物２同士を粘着させる。
（ロ）ポリ塩化ビニルシート１をせん断方向へ引張り（引張速度１０ｍｍ／分）その時の最大荷重Ａをノンハロゲン難燃性パテ組成物同士の粘着力として測定し、最大荷重Ａが３Ｎ以上を○、３Ｎより小さいと×と評価した。
【００２６】
【表２】

【００２７】
【発明の効果】
本発明のノンハロゲン難燃性パテ組成物によると、従来の従来の難燃性パテ組成物の難燃性や施工性が同等以上でありかつ、火災が発生してもパテ間の粘着性が高いので、軟化、特に脱落剥離等が生じ難く、燃焼後も強度のある灰化層を形成するノンハロゲン難燃性パテ組成物を提供することができる。
【図面の簡単な説明】
【図１】粘着性を評価する手順を示す略図である。
１ ポリ塩化ビニルシート
２ ノンハロゲン難燃性パテ組成物
Ｆ ポリ塩化ビニルシートとノンハロゲン難燃性パテ組成物とを粘着させるためにかける荷重とその方向
Ａ ポリ塩化ビニルをせん断方向へ引張った時の最大荷重[0001]
[Industrial application fields]
The present invention is a flame-retardant putty composition having excellent flame retardancy that fills the gaps in the through-holes of fire walls of electric wires and cables into the joints of building interior materials, etc. The present invention relates to a non-halogen flame retardant putty composition that forms a strong ashing layer even after combustion.
[0002]
[Prior art]
Non-halogen flame retardant putty compositions conventionally used (for example, JP-A-6-306364) have high flame retardancy and toughness even after combustion in a non-halogen adhesive liquid polymer (form retention) A large amount of flame retardant, inorganic fiber, etc. are added to form an ashed layer. As described above, this non-halogen flame retardant putty composition contains a large amount of flame retardant, inorganic fiber, etc. in order to give good flame retardancy and form retention, so that the liquid polymer is inherently The adhesiveness which it has has fallen. Therefore, when filling such a non-halogen flame-retardant putty composition into the voids of the through-holes of the fire wall of the electric wire / cable, the non-halogen flame-retardant putty composition must be pressed and solidified little by little. Since the properties cannot be compensated for, the non-halogen flame-retardant putty composition is currently filled in the voids so that they are pressed and hardened little by little.
[0003]
However, in spite of adopting the above-mentioned filling method, softening of non-halogen flame retardant putty due to high temperature during fire (due to heat deformation) due to low adhesiveness between non-halogen flame retardant putty compositions And also called shape retention, and peeling of the putty due to a decrease in toughness of the ashed layer occurred.
[0004]
[Problems to be solved by the present invention]
The present invention is a non-halogen flame retardant putty composition, without sacrificing the flame retardancy and shape retention, heat-resistant deformation of the non-halogen flame retardant putty composition at the time of fire, especially the non-halogen flame retardant property at the time of combustion An object of the present invention is to make it difficult for exfoliation of the putty composition to occur, that is, to improve the tackiness, heat distortion resistance, and toughness of the ashed layer formed after combustion.
[0005]
[Means for solving the problems]
The present invention provides a non-halogen flame retardant putty composition having conventional flame retardancy and workability, and sufficient tackiness, heat distortion resistance and toughness of an incinerated layer formed by combustion. Is.
[0006]
That is, per 100 parts by weight of the non-halogen liquid polymer, the metal hydrate is 200 to 700 parts by weight, the tackifier is 5 to 30 parts by weight, the clay component is 1 to 20 parts by weight, and the heat-resistant fiber is 20 to 100 parts by weight. The non-halogen liquid polymer comprises liquid polybutadiene and liquid polybutene, and the liquid polybutene is 0 to 80 parts by weight with respect to 100 to 20 parts by weight of the liquid polybutadiene. It is a putty composition.
[0007]
The non-halogen liquid polymer of (a) is blended for imparting tackiness to the non-halogen flame retardant putty composition of the present invention, and there is no problem if it is a known one that is liquid at room temperature and does not contain halogen, For example, polybutadiene, polyisoprene, polybutene, and ethylene propylene may be applied, but it is not always necessary to apply one kind. For example, liquid polybutadiene having a relatively low viscosity is mixed with high-viscosity liquid polybutene to cause adhesion. The blend is preferably from 0 to 80 parts by weight of polybutene with respect to 100 to 20 parts by weight of liquid polybutadiene, and when the amount of polybutene exceeds 80 parts by weight, the flame retardancy tends to deteriorate.
[0008]
The metal hydrate (b) is blended to impart flame retardancy to the non-halogen flame retardant putty composition of the present invention. For example, at least one kind of known aluminum hydroxide or magnesium hydroxide is used. What is necessary is just to apply, and if those shapes mix | blend 200-700 weight part with respect to 100 weight part of the non-halogen liquid polymer of the average particle diameter of 100 micrometers or less, flame retardance will be obtained, Furthermore, in order to improve the dispersion in the non-halogen liquid polymer and improve the flame retardancy, a mixture of two or more kinds of metal hydrates having an average particle diameter of 100 μm or less and different in average particle diameter is applied. Preferably, the optimum metal hydrate is blended in an amount of 50 to 20 metal hydrates having an average particle size of 10 μm or less with respect to 100 parts by weight of the metal hydrate having an average particle size of 10 μm and 100 μm or less. 0 parts by weight.
[0009]
The tackifier (c) is blended to impart tackiness to the non-halogen flame retardant putty composition of the present invention, and is not particularly limited, and known ones are used. For example, coumarone / indene resin, phenol / formaldehyde resin, naphthalene / formaldehyde resin, xylene / formaldehyde resin, hydrogenated terpene resin, polyterpene resin, terpene-phenol resin, low molecular weight styrene resin (weight average molecular weight (Mw) is 100) ˜3000), petroleum-based hydrocarbon resins, rosin esters, and the like, and terpene-phenol resins, hydrogenated terpene resins, and polyterpene resins are preferred because of their high tackifying effect.
[0010]
Optimal tackifier content is 5 to 30 parts by weight with respect to 100 parts by weight of the non-halogen liquid polymer. If it is less than 5 parts by weight, the adhesive strength between the non-halogen flame-retardant putty compositions will be reduced, and at the time of fire The problem arises that the non-halogen flame-retardant putty peels off at high temperatures. When the amount is more than 30 parts by weight, the kneading processability becomes worse and the workability tends to be lowered.
[0011]
The clay component (d) is blended in order to impart heat-resistant deformation to the non-halogen flame retardant putty composition of the present invention. For example, clay, talc, siliceous earth, bentonite, etc. are applied. preferable. As the bentonite, various montmorillonites mainly composed of SiO2 and Al2O3 (for example, montmorillonite, magnesia montmorillonite, tetsu montmorillonite, tectum magnesia montmorillonite, beidellite, aluminian beidellite, nontronite, aluminian nontron Nite, savorite, aluminian savorite, hectorite, soconite, bolcon scoreite, etc.) are used as the main components, but in addition to montmorillonite, protein stones, buffalo stones, fluorite, volcanic glass, etc. What is contained, organic bentonite in which an exchangeable base such as Na, Ca, Mg, etc. contained in bentonite is substituted with an organic amine can also be applied.
[0012]
The blending amount of the clay component is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the non-halogen liquid polymer, and if it is less than 1 part by weight, the heat distortion resistance tends to decrease, and if it exceeds 20 parts by weight, the putty is produced. There is a tendency for the kneading processability of the steel to decrease.
[0013]
The heat resistant fiber of (e) is blended to impart toughness of the incinerated layer after combustion of the non-halogen flame retardant putty composition of the present invention, for example, inorganic fiber, metal fiber, or heat distortion temperature. An organic polymer fiber having a temperature of 250 ° C. or higher is applied. Specific examples of the inorganic fiber include glass fiber, rock wool, ceramic fiber, and various whiskers (for example, potassium titanate). Specific examples of the metal fiber include iron, copper, and tungsten. Specific examples of the organic polymer fiber include carbon fiber, phenol fiber, polyimide fiber, and polyamideimide fiber. These fibers may be used alone or in admixture of two or more.
[0014]
The blending amount of the heat resistant fiber is preferably 20 to 100 parts by weight with respect to 100 parts by weight of the non-halogen liquid polymer, and if it is less than 20 parts by weight, the toughness of the ashed layer after combustion tends to be lowered, and from 100 parts by weight. If the amount is too large, the kneadability during the production of putty tends to decrease.
[0015]
The non-halogen flame retardant putty composition of the present invention may be added with a liquid functional silicone oligomer or silicone fine powder to improve flame retardancy, and may further contain other additives such as a plasticizer as necessary. Stabilizers, lubricants, colorants and the like may be added.
[0016]
The liquid functional silicone oligomer is blended in order to improve the flame retardancy of the non-halogen flame retardant putty composition of the present invention, has a molecular weight of 100 to 3000, particularly about 300 to 2500, and is liquid at 25 ° C. (Viscosity of 30 to 300 cps) and those having at least one functional group such as hydroxyl group, methoxy group and vinyl group in the molecule are applied. For example, a functional silicone oligomer composed of vinyl siloxane such as vinyl alkoxysiloxane or a functional silicone oligomer composed of vinylsilanol is applied.
[0017]
The functional silicone oligomer composed of the above-mentioned vinyl siloxane is one in which silicon at the end of the siloxane bond or silicon at the end of the side chain has an alkoxy group such as methoxy group, ethoxy group, propoxy group, etc. Examples thereof include those having a vinyl group at the silicon site and two bonds of silicon in the molecule substituted with hydrogen, methyl group, phenyl group, and other hydrophobic substituents at an arbitrary ratio.
[0018]
Examples of the functional silicone oligomer composed of the above vinylsilanol include those having a vinyl group and an OH group at an arbitrary silicon site of a linear or cyclic siloxane bond. When the siloxane bond is a straight chain, the substitution site of the OH group is generally the terminal of the siloxane bond (if the linear siloxane bond has a side chain, the side chain is also included). Such vinylsilanol is obtained, for example, by a bonding reaction of alkylvinylsilane diol R1R2Si (OH) 2 (R1 is an alkyl group, R2 is a vinyl group) itself or a bonding reaction of this with a dialkylsilanediol. Furthermore, as the vinylsilanol used in the present invention, two bonds of silicon in the molecule are substituted with hydrogen, methyl group, phenyl group, or other hydrophobic substituents at an arbitrary ratio, or the above-mentioned Polymers partially condensed with monoalkylsilanetriol or vinylsilanetriol during condensation of alkylvinylsilanediol are included. Specific functional silicone oligomers are exemplified by vinyltriacetoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrissilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, β- Ethyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, amino functional silane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- β-γ-aminopropylmethyldimethoxysilane, γ-propyltrimethoxysilane, N-β-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, methylaminoethoxypropyldi Alkoxysilane and the like.
[0019]
In addition, the liquid functional silicone oligomer described above has an effect of improving not only the flame retardancy of the non-halogen flame retardant putty composition of the present invention, but also the heat distortion resistance such that it does not sag due to heat. Since the functional silicone oligomer is in a liquid state, it can be uniformly dispersed in the non-halogen liquid polymer, and it can improve the flame retardancy and heat distortion resistance without lowering the adhesiveness of the non-halogen liquid polymer. Better.
[0020]
The blending amount of the liquid functional silicone oligomer is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the non-halogen liquid polymer, and if less than 1 part by weight, the toughness of the ashed layer after combustion tends to be low, When the amount is more than 30 parts by weight, the heat distortion resistance tends to decrease.
[0021]
Silicone fine powder is blended in order to improve the flame retardancy of the non-halogen flame retardant putty composition of the present invention, and those having an average particle size of 0.5 μm to 100 μm may be applied. The average particle size for improving the flammability is preferably 10 μm or less. Moreover, the silicone fine powder improves the toughness (shape stability) of the incinerated layer after combustion of the non-halogen flame retardant putty composition of the present invention.
[0022]
[Action]
In the non-halogen flame-retardant putty composition of the present invention, the tackiness of the liquid polymer is improved by adding a tackifier to a conventionally known liquid non-halogen polymer added with a metal hydrate, and further suitable clay By adding components and heat-resistant fibers, the heat distortion resistance and the toughness of the incinerated layer after combustion could be improved.
[0023]
【Example】
In order to clarify the effects of the present invention, a detailed description will be given based on examples and comparative examples. Each component was blended in the proportions shown in Table 1, put into a 2 liter experimental kneader, and kneaded for 40 minutes while controlling the temperature to be in the range of 20 to 80 ° C. A non-halogen flame retardant putty composition of a comparative example was prepared.
[0024]
[Table 1]

[0025]
The produced non-halogen flame retardant putty composition was evaluated by the following method, and the evaluation results are shown in Table 2.
(1) Evaluation of flame retardancy is carried out by measuring the produced non-halogen flame retardant putty composition in accordance with the oxygen index measurement method described in JIS K7201, and a value of oxygen index 60 or more is indicated by ○, 60 Smaller values were evaluated as x.
(2) Evaluation of the toughness of the incinerated product was made by filling the produced non-halogen flame-retardant putty composition into a cube having a side of 30 mm and holding at 1000 ° C. for 4 hours, and ashed halogenated flame-retardant putty composition. Those that were not broken even when pressed with a load of 25 N were evaluated as ◯, and those that were broken as x.
(3) Evaluation of heat distortion resistance was made by filling the produced non-halogen flame retardant putty composition into a 30 mm × 30 mm × 70 mm rectangular parallelepiped and having a deformation amount of less than 10% when held at 250 ° C. for 30 minutes. ○ 10% or more was evaluated as x.
(4) Tackiness was evaluated by conducting a tensile test in the state shown in FIG.
(A) Two non-halogen flame retardant putty compositions 2 molded into a shape of 40 mm × 40 mm × 5 mm are stacked, and the non-halogen flame retardant putty composition 2 is overlapped with a polyvinyl chloride sheet 1 (thickness 2 mm, The two non-halogen flame-retardant putty compositions 2 are adhered to each other with a load F of 9.8 N for 1 hour from the upper part.
(B) Pulling the polyvinyl chloride sheet 1 in the shear direction (tensile speed: 10 mm / min), measuring the maximum load A at that time as the adhesive strength between the non-halogen flame retardant putty compositions, the maximum load A being 3N or more, When it was smaller than 3N, it evaluated as x.
[0026]
[Table 2]

[0027]
【Effect of the invention】
According to the non-halogen flame-retardant putty composition of the present invention, the flame retardancy and workability of the conventional conventional flame-retardant putty composition are equivalent or better, and the adhesiveness between putties is high even if a fire occurs. Therefore, it is possible to provide a non-halogen flame-retardant putty composition that is hard to be softened, in particular, is not easily peeled off, and that forms a strong ashed layer even after combustion.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing a procedure for evaluating adhesiveness.
1 Polyvinyl chloride sheet 2 Non-halogen flame-retardant putty composition F Load and direction A for applying the polyvinyl chloride sheet and non-halogen flame-resistant putty composition to stick A Maximum when PVC is pulled in the shear direction load

Claims (9)

The metal hydrate is 200 to 700 parts by weight, the tackifier is 5 to 30 parts by weight, the clay component is 1 to 20 parts by weight, and the heat resistant fiber is 20 to 100 parts by weight per 100 parts by weight of the non-halogen liquid polymer. Non-halogen flame retardant putty composition characterized in that the non-halogen liquid polymer comprises liquid polybutadiene and liquid polybutene, and the liquid polybutene is 0 to 80 parts by weight with respect to 100 to 20 parts by weight of the liquid polybutadiene. object. The non-halogen flame retardant putty composition according to claim 1, wherein the liquid polybutadiene has a viscosity lower than that of the liquid polybutene. The non-halogen flame-retardant putty composition according to claim 1, wherein the tackifier comprises at least one of a hydrogenated terpene resin, a polyterpene resin, and a terpene-phenol resin. 2. The non-halogen flame-retardant putty composition according to claim 1, wherein the clay component comprises at least one of clay, talc, siliceous earth, and bentonite. The non-halogen flame-retardant putty composition according to claim 1, wherein the heat-resistant fiber comprises at least one kind of inorganic fiber, metal fiber, or organic polymer fiber having a heat distortion temperature of 250 ° C or higher. 2. The non-halogen flame-retardant putty composition according to claim 1, wherein the metal hydrate has a mean particle size of greater than 10 μm and less than 100 μm and less than 10 μm. 7. The non-halogen flame retardant according to claim 6, wherein the metal hydrate having an average particle size of 10 μm or more and 100 μm or less is 50 to 200 parts by weight with respect to 100 parts by weight of the metal hydrate. Sex putty composition. Furthermore, the liquid functional silicone oligomer was added, The non-halogen flame-retardant putty composition of Claim 1 characterized by the above-mentioned. 9. The non-halogen flame-retardant putty composition according to claim 8, wherein 1 to 30 parts by weight of the liquid functional silicone oligomer is added to 100 parts by weight of the non-halogen liquid polymer.

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