JP2009073989A - Resin composition containing fly ash - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem that it is generally difficult to use a fly ash raw powder as a filler or a reinforcing agent for a polyvinyl chloride resin, a rubber resin, a polyolefin resin or the like, due to problems, such as deterioration of physical properties of the material, deterioration of physical properties of a molded body and poor appearance after being molded, caused by a large unburned carbon content, a large particle size with a large variation and low sphericity (a ratio of the long axis and the short axis) of 0.8 or less of the fly ash raw powder, and the like. <P>SOLUTION: This resin composition containing fly ash contains fly ash satisfying all the conditions that an average particle size is 5 μm or less, that unburned carbon is 1% or less, that sphericity (a ratio of the long axis and the short axis) is 0.9-1.0, and that a residue on 45 μm sieve is 4% or less, and a polyvinyl chloride resin, a rubber resin, or a polyolefin resin as a resin, and other required additives, the fly ash being blended in a predetermined blending ratio to the resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyvinyl chloride resin composition, a rubber composition (hereinafter referred to as a rubber resin composition for convenience) and a polyolefin resin composition containing fly ash.

Many resin compositions contain calcium carbonate and silicon oxide (silica) for the purpose of reducing material costs, improving mechanical properties such as rigidity and tensile strength, improving dimensional stability, improving flame retardancy, and improving wear resistance. ), Fillers such as aluminum silicate and talc, and reinforcing agents are added.
On the other hand, fly ash generated by thermal power generation or the like is used as an admixture for concrete due to its low cost and its reinforcing effect. However, for the most part, no effective means for use other than landfill has been found, and there are industrial wastes that are difficult to process.
From the above background, attempts have been made to mix and use fly ash in a resin composition. For example, Japanese Laid-Open Patent Publication No. 61-72059 (Patent Document 1) discloses a mixture of fly ash and thermoplastic resin in an amount of 70 parts by weight or less, and Japanese Laid-Open Patent Publication No. 3-146564 (Patent Document). 2) discloses a vibration damping material comprising fly ash and a tackifier of 250 parts by weight or less. However, in any of the above cases, if the amount of fly ash added increases, mechanical properties and molding processability deteriorate, and the amount of fly ash added is limited. From the viewpoint of processing things, the contribution is low.
JP 09-263667 A (Patent Document 3) is a vinyl chloride resin composition comprising a vinyl chloride resin, a lead stabilizer, fly ash, and a white filler. Reference 4) is a polyethylene resin composition containing 100 to 900 parts by weight of fly ash with respect to 100 parts by weight of polyethylene resin having a density of 0.840 to 0.925 g / cm ³ , and the former resin composition. The fly ash used in the above has an average particle size of 0.1 to 30 μm, and the fly ash used in the latter resin composition is coarse with a particle size of 1 to 200 μm and an average particle size of 20 μm, and has a large amount of unburned carbon. Other physical properties are not specified for industrial waste. For this reason, it is very difficult to obtain a polyethylene-based resin composition having various properties such as tension and elongation and molding processability stabilized at a high level. In addition, since many coarse fly ash particles are mixed during molding, there is a problem that the wear damage of the molding equipment is severe and the moldability is greatly affected, and the blending amount is limited.
JP 61-72059 A Japanese Patent Laid-Open No. 3-146564 JP 09-263667 A JP 09-263662 A

<Problems of the above prior art>
As described above, fly ash raw powder generally contains a large amount of unburned carbon, has a large particle size, and has a sphericity (long / short axis ratio) of 0.8 or less. Due to variations in ash components and properties, there are problems such as a decrease in material properties, a decrease in physical properties of molded products, and a poor appearance after molding, making it difficult to use as a filler or reinforcing agent for resin compositions. It was.

The present invention has been made to solve the above problems, and the features thereof are the following (1) to (3).
(1) fly ash satisfying all conditions of an average particle size of 5 μm or less, unburned carbon of 1% or less, sphericity (long / short axis ratio) of 0.9 to 1.0, and 45 μm sieve residue of 4% or less; A fly ash containing a polyvinyl chloride resin, a plasticizer, and a heat stabilizer, wherein the fly ash is blended in an amount of 10 to 150 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. Polyvinyl chloride resin composition.
(2) fly ash satisfying all conditions of an average particle size of 5 μm or less, unburned carbon of 1% or less, sphericity (long / short axis ratio) of 0.9 to 1.0, and 45 μm sieve residue of 4% or less; A rubber resin composition containing fly ash, comprising a rubber resin, a crosslinking agent, and a heat stabilizer, wherein the fly ash is blended in an amount of 100 to 1200 parts by weight with respect to 100 parts by weight of the rubber resin. .
(3) fly ash satisfying all conditions of an average particle size of 5 μm or less, unburned carbon of 1% or less, sphericity (long / short axis ratio) of 0.9 to 1.0, and 45 μm sieve residue of 4% or less; A polyolefin resin composition containing fly ash, wherein the fly ash is blended in an amount of 10 to 150 parts by weight per 100 parts by weight of the polyolefin resin.
In the present invention, the weight part means PHR. In the case of rubber resin, P = per, H = hundred, R = rubber, in the case of polyvinyl chloride resin or polyolefin resin other than rubber resin, P = = Per, H = hundred, R = resin. When the weight of the main rubber or resin is 100, the unit used to display the weight of other blends and added substances numerically.

According to the present invention, the following excellent effects can be obtained by the above configuration.
By specifying the components and properties of fly ash as described above, this fly ash can be advantageously used as a filler and reinforcing agent for polyvinyl chloride resin compositions, rubber resin compositions, and polyolefin resin compositions. I made it.
That is, the fly ash-containing polyvinyl chloride resin composition under specific conditions, as introduced in Example 1, has excellent reinforcing effects such as stably maintaining the physical properties of tensile strength, elongation at break and cold resistance at a high level. In addition, the appearance after molding is very good.
In addition, as described in Example 2, the fly ash-containing rubber resin composition under specific conditions stably keeps various physical property values such as tensile strength, elongation at break, tear strength, cold resistance, and oxygen index at a high level. The reinforcing effect such as that is excellent and the appearance after molding is very good.
Further, the fly ash-containing polyolefin resin composition under specific conditions is excellent in a reinforcing effect such as stably maintaining each physical property value such as tensile strength and tear strength at a high level as introduced in Example 3. At the same time, it is possible to impart flame retardancy, and the appearance after molding is very good.

1. In the present invention, a method for producing fly ash under the above-mentioned specific conditions to be used can be obtained, for example, by the production method introduced in Japanese Patent Application No. 2006-31286 developed and filed by the present inventors. That is, the fly ash raw powder shown in Table 1 is fired while flowing, and spheroidized while removing unburned carbon, and then indirectly cooled while flowing to prevent interparticle bonding, and after this indirect cooling step, Classify and collect.
The classification of the modified fly ash by classification recovery is described in Table 1 and introduced. The modified fly ash is divided into the modified fly ash (A) recovered directly after the indirect cooling process, the modified fly ash (B) recovered by sedimentation classification after the air-crushing cyclone treatment, the bag filter, etc. It is a modified fly ash (C) of floating suction classification recovery by.
The fly ash used in specific examples No1 to No6 of the examples to be described later is equivalent to modified fly ash (C), the average particle size is 5 μm or less, and the unburned carbon (ignition loss) 1 % Or less, sphericity (long / short axis ratio) 0.9 to 1.0, 45 μm sieve residue 4% or less.
Further, the fly ash used in the comparative example of the example is equivalent to the modified fly ash (A) (B), and does not satisfy most of the specific conditions.

２．本発明のポリ塩化ビニル樹脂組成物、ゴム樹脂組成物、ポリオレフィン樹脂組成物の各々において、共通するフライアッシュの前記特定条件の技術的意義
(1)、平均粒度を5μm以下等とする理由
図１、図５、図７に示すように、フライアッシュの平均粒径が5μm以下であれば、フライアッシュ含有する樹脂組成物の引張強度や破断伸びは最も大きな値を示し、5μmを超えた10μm以上になるとそれらは20〜30％低下する傾向を示す。また実施例でも紹介のようにフライアッシュ含有する樹脂組成物の成形後の外観は、平均粒度が5μm以下の小さい領域のものほど滑らかさや光沢などが良好で、5μm を超え10μm以上になるとそれらは好ましくない結果がえられている。
図９に示したSEM写真からも分かるように、フライアシュの粒子形状は球状が多い。この写真で不定形であるものが未燃カーボンで、比較的大きな粒子として存在している。又この粒子が小さくなればなるほど、即ち、微粒子であればあるほどその形状は球に近い状態であることがわかる。したがって、フライアシュの粒径はそれに含まれる未燃カーボン量や45μｍ篩残分量に著しく影響を受けることから、フライアッシュの平均粒径を5μm以下にするためには、未燃カーボン量を1％以下にすると共に45μｍ篩残分量を4％以下にすることが重要な条件である。その結果、真球度（長・短軸比）は1.0に近づき、球に近い粒子が高効率で得られことになる。この球状の粒子を当該樹脂組成物の充填材にすることによりその表面は非常に滑らかで光沢も良く外観性状に優れたものとなる。またフライアシュの平均粒径が5μmを超える大きなものとなると成形時の成形機に対して磨耗損傷の問題を惹起させる。
３．本発明のフライアッシュ含有のポリ塩化ビニル樹脂組成物
(1)、本発明の前記ポリ塩化ビニル樹脂組成物において前記フライアッシュをポリ塩化ビニル樹脂100重量部に対し10〜150重量部配合する理由
フライアッシュが5重量部でも特性は良好であるが、充填材としての効果が低く、実用的でない。又フライアッシュが150重量部を越えると破断伸びが落ち、耐寒性が悪くなり、さらに成形性後の外観も悪くなるため実用的でない。
(2)、その他の配合剤の種類と好ましい配合率範囲とその理由等。
ポリ塩化ビニル樹脂としては重合度800〜2500程度まで、任意に選択が可能。
可塑剤としてはフタル酸系可塑剤やアジピン酸系可塑剤、マレイン酸系可塑剤、トリメリット酸系可塑剤、スルホン酸系可塑剤、リン酸系可塑剤、エポキシ系可塑剤、パラフィン系可塑剤、重合型可塑剤等、一般的な可塑剤を使用することができ、使用用途に応じて２種類以上を混用することも可能。配合量としては一般的に10〜100重量部が適当と考えられ、少なすぎると可塑化効率が低くなり逆に多すぎると強度等の特性の低下があるため好ましくない。
熱安定剤は、金属石けんや無機酸塩類、有機スズ化合物等が一般的な熱安定剤を使用することができ、使用用途に応じて２種類以上を混用することも可能。配合量としては1〜5重量部が適当と考えられ、少なすぎると熱安定性効果が低くなり逆に多すぎると強度等の特性の低下やコストアップとなってしまうため好ましくない。
その他、炭酸カルシウムやケイ酸塩、ケイ酸アルミニウム等、一般的にポリ塩化ビニル樹脂に用いられる充填材、補強剤を混用することも可能である。
(3)、フライアッシュ含有のポリ塩化ビニル樹脂組成物の製造方法例の紹介
樹脂組成物を得るための混合方法としては、一般に使用されるヘンシェルミキサー等の混合機を使ってドライブレンドさせたあと押出混合機やニーダー、バンバリーミキサー等の混合機を用いて溶融しながら混合させる方法が代表的である。以上の混合方法のうち、溶融混練する場合や成形する場合、樹脂組成物に高い温度を作用させると熱分解または脱ハロゲン化水素反応を引起すので、150〜200℃の温度において実施することが好ましい。成形方法としては、一般に射出成形法、押出成形法、圧縮成形法及び中空成形法等の成形方法がある。
４．本発明のフライアッシュ含有のゴム樹脂組成物
(1)、本発明の前記ゴム樹脂組成物において前記フライアッシュをゴム樹脂100重量部に対し10〜800重量部配合する理由
5重量部では少なすぎるため強度の向上がほとんど認められない。800重量部を越えるとゴム樹脂組成物の流動性が下がり成形が困難となるため実用的でない。
(2)、その他の配合剤の種類と好ましい特筆条件
ゴム樹脂としてはエチレンプロピレンゴム以外に天然ゴムやクロロプレンゴム、アクリロニトリルブタジエンゴム（ＮＢＲ）等一般的なゴムを使用することができ、使用用途に応じて２種類以上を混用することも可能。
軟化剤としては鉱物油系軟化剤や植物油系軟化剤、ＮＢＲ等には一般的なポリ塩化ビニル用可塑剤等の一般的な軟化剤を使用することができ、使用用途に応じて２種類以上を混用することも可能。配合量としては150重量部以下が適当と考えられ、多すぎると強度の低下やブリードアウト等の不具合を引き起こすことが考えられる。
熱安定剤としてはナフチルアミン系、ジフェニルアミン系、p-フェニレンジアミン系、キノリン系、ヒドロキノン誘導体、モノフェノール系、ビス、トリス、ポリフェノール系、チオビスフェノール系、ヒンダート・フェノール系、フェノール系、亜リン酸エステル系、硫黄系等、一般的にゴムに使用される老化防止剤や酸化防止剤を使用することが可能。配合量は0.1〜10重量部が適当と考えられ、少なすぎると熱安定性効果が低くなり逆に多すぎると強度等の特性の低下やコストアップ、ブルームアウトとなってしまうため好ましくない。
滑剤は成形性改良のために用いられ、パラフィンおよび炭化水素樹脂、脂肪酸、脂肪酸アミド、脂肪酸エステル等一般的にゴムに使用される滑剤を使用することが可能。配合量は0.1〜10重量部が適当と考えられ、少なすぎると成形性改良効果が低くなり逆に多すぎると強度等の特性の低下やコストアップ、ブリードアウトとなってしまうため好ましくない。
加硫促進剤としてはグアニジン系、アルデヒド−アミン系、アルデヒド−アンモニア系、チアゾール系、スルフェンアミド系、チオ尿酸系、チウラム系、ジチオカルバミン酸塩系、キサントゲン酸塩系、金属酸化物や金属炭酸塩、脂肪酸やその誘導体、アミン類等一般的にゴムに使用される加硫促進剤を使用することが可能。配合量は15重量部以下が適当と考えられ、多すぎると強度等の特性の低下や成形加工時の不具合、コストアップ、ブルームアウトとなってしまうため好ましくない。
架橋材としては有機過酸化物、硫黄、硫黄化合物、オキシム類、ニトロソ化合物、ポリアミン等一般的にゴムに使用される架橋材を使用することが可能。配合量は0.1〜15重量部以下が適当と考えられ、少なすぎると架橋効果が得られず、逆に多すぎると伸び等の特性の低下や成形加工時の不具合、コストアップとなってしまうため好ましくない。
その他、炭酸カルシウムやケイ酸塩、ケイ酸アルミニウム、カーボンブラック、等、一般的にゴムに用いられる充填材、補強剤を混用することも可能。
(3)、フライアッシュ含有のゴム樹脂組成物の製造方法例の紹介
樹脂組成物を得るための混合方法としては、押出混合機やニーダー、バンバリーミキサー等の混合機を用いて溶融しながら混合させる方法が代表的である。以上の混合方法のうち、溶融混練する場合や成形する場合、樹脂組成物に高い温度を作用させると熱分解や架橋反応を引起すので、30〜200℃の温度において実施することが好ましい。成形方法としては、一般に射出成形法、押出成形法、圧縮成形法及び中空成形法等の成形方法がある。
５．本発明のフライアッシュ含有のポリオレフィン樹脂組成物
(1)、本発明の前記ポリオレフィン樹脂組成物において前記フライアッシュをポリオレフィン樹脂100重量部に対し10〜1200重量部配合する理由
フライアッシュが5重量部でも特性は良好であるが、充填材としての効果が低く、難燃性も向上せず、実用的でない。フライアッシュが1200重量部を越えると樹脂組成物の流動性が下がり成形が困難となるため実用的でない。
(2)、その他の配合剤の種類
その他配合剤として、熱安定剤や軟化剤、充填材、加工助剤、架橋材を混用することも可能である。
(3)、フライアッシュ含有のポリオレフィン樹脂組成物の製造方法例の紹介
樹脂組成物を得るための混合方法としては、一般に使用されるヘンシェルミキサー等の混合機を使ってドライブレンドさせたあと押出混合機やニーダー、バンバリーミキサー等の混合機を用いる、もしくはドライブレンドを行わずにニーダー、バンバリーミキサー等の混合機を用いて溶融しながら混合させる方法が代表的である。以上の混合方法のうち、溶融混練する場合や成形する場合、樹脂組成物に高い温度を作用させると熱分解を引起すので、50〜250℃の温度において実施することが好ましい。成形方法としては、一般に射出成形法、押出成形法、圧縮成形法及び中空成形法等の成形方法がある。
６、本発明におけるフライアッシュ含有のポリ塩化ビニル樹脂組成物に関するデーターの照会
図１−１〜図１−６はフライアッシュの平均粒径（横軸）がポリ塩化ビニル樹脂組成物の各種特性に及ぼす影響を示した図で、図１−１は引張強度、図１−２は破断伸び、図１−３は耐寒性、図１−４は加熱変形率、図１−５は体積抵抗率、図１−６は酸素指数との関係で示すグラフである。図２−１〜図２−６は平均粒子径が3μmの改質フライアッシュを用いた場合、その配合割合がポリ塩化ビニル樹脂組成物の各種特性に及ぼす影響を示した図で、図２−１は引張強度、図２−２は破断伸び、図２−３は耐寒性、図２−４は加熱変形率、図２−５は体積抵抗率、図２−６は酸素指数との関係で示すグラフである。
図２−１〜図２−６には、改質フライアッシュ配合割合が500重量部では成形不能であったことから、改質フライアッシュ配合割合が各種特性に及ぼす影響を総合的に判断して、これ以上の配合割合では成形不能となることが予想される限界線も示されている。
ポリ塩化ビニル樹脂組成物の引張試験における「引張強度と破断伸びの関係」について、図３はフライアッシュの平均粒径の影響を示しており、図４は平均粒径3μmの改質フライアッシュの配合割合の影響を示している。図中には、JIS K 6723 軟質ポリ塩化ビニルコンパウンド1種3号（一般シース用ビニル）に相当する規格値（破断伸び200%以上、引張強さ11.8Mpa以上）を破線で示しており、ハッチの部分が規格値を満足するゾーンである。粒径については20μm以下であれば、また、配合割合については200重量部以下であれば、JIS規格値を満足していることがわかる。
これらの図より、成形性（加工性）や成形後の外観状態を考慮すれば、ポリ塩化ビニル樹脂組成物の製造では、改質フライアッシュの平均粒径は5μm以下が望ましく、好ましくは1〜3μmである。また、改質フライアッシュの配合割合は150重量部以下好ましくは100重量部以下である。
7、本発明におけるフライアッシュ含有のゴム樹脂組成物に関するデーターの紹介。
図５−１〜図５−６はフライアッシュの平均粒径がゴム樹脂組成物として用いたエチレンプロピレンゴム樹脂組成物の各種特性に及ぼす影響を示した図で、図５−１は引張強度、図５−２は破断伸び、図５−３は引裂強さ、図５−４は酸素指数との関係を示すグラフである。
図６−１〜図６−４は、粒子径が3μmの改質フライアッシュを用いた場合、その配合割合がエチレンプロピレンゴム樹脂組成物の各種特性に及ぼす影響を示した図で、図６−１は引張強度、図６−２破断伸び、図６−３は引裂強さ、図６−４は酸素指数との関係を示すグラフである。
図６−１〜図６−４には、改質フライアッシュの配合割合が1000重量部では成形不能であったことから、改質フライアッシュ配合割合が各種特性に及ぼす影響を総合的に判断して、これ以上の配合割合では成形不能となることが予想される限界線も示されている。
これらの図より、成形性（加工性）や成形後の外観状態を考慮すれば、エチレンプロピレンゴム樹脂組成物の製造では、改質フライアッシュの平均粒径は5μm以下好ましくは1〜3μmである。また、この改質フライアッシュの配合割合は800重量部以下好ましくは400重量部以下である。
8、本発明におけるフライアッシュ含有のポリオレフィン樹脂組成物に関するデーターの照会。
図７−１〜図７−４はフライアッシュの粒径がポリオレフィン樹脂組成物の各種特性に及ぼす影響を示した図で、図７−１は引張強度、図７−２は破断伸び、図７−３は引裂強さ、図７−４は酸素指数との関係を示すグラフである。
図８−１〜図８−４は平均粒径が3μmの改質フライアッシュを用いた場合、その配合割合がポリオレフィン樹脂組成物の各種特性に及ぼす影響を示した図で、図８−１は引張強度、図８−２は破断伸び、図８−３は引裂強さ、図８−４は酸素指数、である。
図８−１〜図８−４には、改質フライアッシュの配合割合が1500重量部では成形不能であったことから、改質フライアッシュの配合割合が各種特性に及ぼす影響を総合的に判断して、これ以上の配合割合では成形不能となることが予想される限界線も示されている。
これらの図より、成形性（加工性）や成形後の外観状態を考慮すれば、ポリオレフィン樹脂組成物の製造では、改質フライアッシュの粒径は5μm以下好ましくは1〜3μmである。また、改質フライアッシュの配合割合は1000重量部以下好ましくは600重量部以下である。

2. Technical significance of the specific conditions of fly ash common to each of the polyvinyl chloride resin composition, rubber resin composition, and polyolefin resin composition of the present invention
(1) Reason why the average particle size is 5 μm or less, etc. As shown in FIGS. 1, 5, and 7, if the average particle size of fly ash is 5 μm or less, the tensile strength of the resin composition containing fly ash The elongation at break shows the largest value, and when it exceeds 10 μm exceeding 5 μm, they tend to decrease by 20 to 30%. In addition, as introduced in the examples, the appearance after molding of the resin composition containing fly ash is better in smoothness and gloss, etc. in the smaller region where the average particle size is 5 μm or less, and when it exceeds 5 μm and becomes 10 μm or more, Unfavorable results have been obtained.
As can be seen from the SEM photograph shown in FIG. 9, the fly ash has many spherical particles. In this photograph, the amorphous particles are unburned carbon and exist as relatively large particles. It can also be seen that the smaller the particle, that is, the finer the particle, the closer the shape is to a sphere. Therefore, the particle size of fly ash is significantly affected by the amount of unburned carbon contained in it and the residual amount of the 45 μm sieve residue. To reduce the average particle size of fly ash to 5 μm or less, the amount of unburned carbon is 1%. It is an important condition that the remaining amount of the 45 μm sieve is 4% or less. As a result, the sphericity (long / short axis ratio) approaches 1.0, and particles close to a sphere can be obtained with high efficiency. By using these spherical particles as a filler for the resin composition, the surface becomes very smooth, glossy and has excellent appearance. Further, if the average particle size of fly ash exceeds 5 μm, it causes a problem of wear damage to the molding machine at the time of molding.
3. The polyvinyl chloride resin composition containing fly ash of the present invention
(1) The reason why the fly ash is blended in the polyvinyl chloride resin composition of the present invention is 10 to 150 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. The effect as a filler is low and not practical. On the other hand, if fly ash exceeds 150 parts by weight, elongation at break falls, cold resistance deteriorates, and appearance after moldability also deteriorates, which is not practical.
(2) Types of other compounding agents, preferable ranges of mixing ratios, and reasons thereof.
Polyvinyl chloride resin can be arbitrarily selected from a degree of polymerization of about 800-2500.
Plasticizers include phthalic acid plasticizer, adipic acid plasticizer, maleic acid plasticizer, trimellitic acid plasticizer, sulfonic acid plasticizer, phosphoric acid plasticizer, epoxy plasticizer, paraffin plasticizer General plasticizers such as polymerization type plasticizers can be used, and two or more types can be mixed depending on the intended use. In general, 10 to 100 parts by weight is considered to be appropriate as the blending amount. If the amount is too small, the plasticizing efficiency is lowered.
As the heat stabilizer, metal soap, inorganic acid salts, organic tin compounds, etc. can use general heat stabilizers, and two or more kinds can be mixed depending on the intended use. The blending amount is considered to be 1 to 5 parts by weight. If the amount is too small, the thermal stability effect is lowered. On the other hand, if the amount is too large, properties such as strength are reduced and the cost is increased.
In addition, fillers and reinforcing agents generally used for polyvinyl chloride resins, such as calcium carbonate, silicate, and aluminum silicate, can be mixed.
(3) Introduction of the production method of the fly ash-containing polyvinyl chloride resin composition As a mixing method for obtaining the resin composition, after dry blending using a mixer such as a commonly used Henschel mixer A typical method is mixing while melting using a mixer such as an extrusion mixer, a kneader, or a Banbury mixer. Among the above mixing methods, in the case of melt kneading or molding, if a high temperature is applied to the resin composition, it causes a thermal decomposition or dehydrohalogenation reaction, so it may be carried out at a temperature of 150 to 200 ° C. preferable. As the molding method, there are generally molding methods such as an injection molding method, an extrusion molding method, a compression molding method and a hollow molding method.
4). Rubber resin composition containing fly ash of the present invention
(1) Reason for blending 10 to 800 parts by weight of the fly ash with respect to 100 parts by weight of the rubber resin in the rubber resin composition of the present invention
At 5 parts by weight, there is too little to improve the strength. If it exceeds 800 parts by weight, the fluidity of the rubber resin composition is lowered and it becomes difficult to mold, so it is not practical.
(2) Types of other compounding agents and preferred special conditions As rubber resins, natural rubber, chloroprene rubber, acrylonitrile butadiene rubber (NBR), etc. can be used in addition to ethylene propylene rubber. It is possible to mix two or more types.
As softeners, mineral oil softeners, vegetable oil softeners, and general softeners such as general plasticizers for polyvinyl chloride can be used for NBR. Can be used together. The blending amount is considered to be 150 parts by weight or less, and if it is too much, it may cause problems such as a decrease in strength and bleed out.
Thermal stabilizers include naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivatives, monophenol, bis, tris, polyphenol, thiobisphenol, hindered phenol, phenol, phosphite It is possible to use antioxidants and antioxidants commonly used for rubber, such as sulfur and sulfur. The blending amount is considered to be 0.1 to 10 parts by weight. If the amount is too small, the thermal stability effect is lowered, and on the contrary, if the amount is too large, the properties such as strength are lowered, the cost is increased, and blooming is not preferred.
Lubricants are used to improve moldability, and it is possible to use lubricants commonly used in rubber such as paraffin and hydrocarbon resins, fatty acids, fatty acid amides, fatty acid esters. The blending amount is considered to be 0.1 to 10 parts by weight. If the amount is too small, the effect of improving the moldability is lowered. On the other hand, if the amount is too large, the strength and other properties are lowered, the cost is increased, and bleed out.
Vulcanization accelerators include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiouric acid, thiuram, dithiocarbamate, xanthate, metal oxide and metal carbonate. It is possible to use vulcanization accelerators commonly used in rubber, such as salts, fatty acids and their derivatives, and amines. It is considered that the blending amount is 15 parts by weight or less, and if it is too large, the properties such as strength are deteriorated, defects at the time of molding, cost increase, and bloom out are not preferable.
As the crosslinking material, it is possible to use crosslinking materials generally used for rubber, such as organic peroxides, sulfur, sulfur compounds, oximes, nitroso compounds, and polyamines. It is considered that the blending amount is 0.1 to 15 parts by weight or less, and if it is too small, a crosslinking effect cannot be obtained. It is not preferable.
In addition, fillers and reinforcing agents that are generally used for rubber, such as calcium carbonate, silicate, aluminum silicate, and carbon black, can be mixed.
(3) Introduction of a method for producing a fly ash-containing rubber resin composition As a mixing method for obtaining a resin composition, mixing is carried out using a mixer such as an extrusion mixer, a kneader, or a Banbury mixer. The method is representative. Among the above mixing methods, when melt-kneading or molding, if a high temperature is applied to the resin composition, a thermal decomposition or a crosslinking reaction is caused. Therefore, the mixing is preferably performed at a temperature of 30 to 200 ° C. As the molding method, there are generally molding methods such as an injection molding method, an extrusion molding method, a compression molding method and a hollow molding method.
5). Polyolefin resin composition containing fly ash according to the present invention
(1) The reason why the fly ash is blended in the polyolefin resin composition of the present invention is 10 to 1200 parts by weight with respect to 100 parts by weight of the polyolefin resin. The effect is low, the flame retardancy is not improved, and it is not practical. If fly ash exceeds 1200 parts by weight, the fluidity of the resin composition decreases and molding becomes difficult, which is not practical.
(2) Types of other compounding agents As other compounding agents, heat stabilizers, softeners, fillers, processing aids, and crosslinking materials can be mixed.
(3) Introduction of production method example of fly ash-containing polyolefin resin composition The mixing method for obtaining the resin composition is dry blending using a mixer such as a commonly used Henschel mixer and then extrusion mixing. Typically, a mixing method using a mixer, a kneader, a Banbury mixer, or the like, or a mixer such as a kneader, a Banbury mixer, etc., without performing dry blending, is used for mixing. Among the above mixing methods, when melt-kneading or molding, it is preferable to carry out at a temperature of 50 to 250 ° C., since thermal decomposition is caused when a high temperature is applied to the resin composition. As the molding method, there are generally molding methods such as an injection molding method, an extrusion molding method, a compression molding method and a hollow molding method.
6. Inquiry of data regarding the fly ash-containing polyvinyl chloride resin composition in the present invention FIGS. 1-1 to 1-6 show that the average particle diameter (horizontal axis) of fly ash is various characteristics of the polyvinyl chloride resin composition. FIG. 1-1 is the tensile strength, FIG. 1-2 is the elongation at break, FIG. 1-3 is the cold resistance, FIG. 1-4 is the heat deformation rate, FIG. 1-5 is the volume resistivity, FIG. 1-6 is a graph showing the relationship with the oxygen index. FIGS. 2-1 to 2-6 are diagrams showing the influence of the blending ratio on various properties of the polyvinyl chloride resin composition when a modified fly ash having an average particle diameter of 3 μm is used. 1 is tensile strength, FIG. 2-2 is elongation at break, FIG. 2-3 is cold resistance, FIG. 2-4 is heat deformation rate, FIG. 2-5 is volume resistivity, and FIG. 2-6 is relationship with oxygen index. It is a graph to show.
In Fig. 2-1 to Fig. 2-6, since the reformed fly ash blending ratio was impossible at 500 parts by weight, the influence of the modified fly ash blending ratio on various characteristics was judged comprehensively. Further, there is also shown a limit line that is expected to be impossible to mold at a blending ratio higher than this.
FIG. 3 shows the effect of the average particle size of fly ash on the “relation between tensile strength and elongation at break” in the tensile test of the polyvinyl chloride resin composition, and FIG. 4 shows the effect of the modified fly ash having an average particle size of 3 μm. The influence of the blending ratio is shown. In the figure, the standard values (breaking elongation of 200% or more, tensile strength of 11.8 Mpa or more) equivalent to JIS K 6723 soft polyvinyl chloride compound type 1 No. 3 (vinyl for general sheath) are shown by broken lines. This zone is a zone that satisfies the standard value. If the particle size is 20 μm or less, and the blending ratio is 200 parts by weight or less, it is understood that the JIS standard value is satisfied.
From these figures, in consideration of moldability (workability) and appearance after molding, in the production of the polyvinyl chloride resin composition, the average particle size of the modified fly ash is desirably 5 μm or less, preferably 1 to 3 μm. The blending ratio of the modified fly ash is 150 parts by weight or less, preferably 100 parts by weight or less.
7. Introduction of data on the rubber resin composition containing fly ash in the present invention.
FIGS. 5-1 to 5-6 are views showing the influence of the average particle diameter of fly ash on various properties of the ethylene propylene rubber resin composition used as the rubber resin composition, and FIG. FIG. 5-2 is an elongation at break, FIG. 5-3 is a tear strength, and FIG. 5-4 is a graph showing a relationship with an oxygen index.
FIGS. 6-1 to 6-4 are diagrams showing the influence of the blending ratio on various properties of the ethylene propylene rubber resin composition when a modified fly ash having a particle size of 3 μm is used. 1 is tensile strength, FIG. 6-2 elongation at break, FIG. 6-3 is tear strength, and FIG. 6-4 is a graph showing the relationship with oxygen index.
In FIGS. 6-1 to 6-4, since the blending ratio of the modified fly ash cannot be molded at 1000 parts by weight, the influence of the blending ratio of the modified fly ash on various characteristics is comprehensively determined. Further, there is also shown a limit line that is expected to be impossible to mold at a blending ratio higher than this.
From these figures, in consideration of moldability (workability) and appearance after molding, in the production of ethylene propylene rubber resin composition, the average particle size of the modified fly ash is 5 μm or less, preferably 1 to 3 μm. . The blending ratio of the modified fly ash is 800 parts by weight or less, preferably 400 parts by weight or less.
8. Inquiry of data on polyolefin resin composition containing fly ash in the present invention.
FIGS. 7-1 to 7-4 are views showing the influence of the particle size of fly ash on various properties of the polyolefin resin composition, FIG. 7-1 is the tensile strength, FIG. 7-2 is the elongation at break, FIG. -3 is the tear strength, and FIG. 7-4 is a graph showing the relationship with the oxygen index.
FIGS. 8-1 to 8-4 are diagrams showing the influence of the blending ratio on various properties of the polyolefin resin composition when a modified fly ash having an average particle size of 3 μm is used. FIG. The tensile strength, FIG. 8-2 is the elongation at break, FIG. 8-3 is the tear strength, and FIG. 8-4 is the oxygen index.
In FIGS. 8-1 to 8-4, since the blending ratio of the modified fly ash cannot be molded at 1500 parts by weight, the influence of the blending ratio of the modified fly ash on various characteristics is comprehensively determined. Further, there is also shown a limit line that is expected to be impossible to mold at a blending ratio higher than this.
From these figures, considering the moldability (workability) and the appearance after molding, in the production of the polyolefin resin composition, the particle size of the modified fly ash is 5 μm or less, preferably 1 to 3 μm. The blending ratio of the modified fly ash is 1000 parts by weight or less, preferably 600 parts by weight or less.

Example 1 introduces a polyvinyl chloride resin composition containing fly ash under the above specific conditions.
Table 2 shows a specific example of a polyvinyl chloride resin (PVC resin) + plasticizer + heat stabilizer + a fly ash-containing polyvinyl chloride resin composition under the above-mentioned specific conditions, and a polymer containing fly ash outside the specific conditions. Comparative examples of vinyl chloride resin compositions are described.
As the fly ash under specific conditions, the fly ash equivalent to the modified fly ash (3) described in Table 1 is used, and as the fly ash of the comparative example, the modified fly ash (1) described in Table 1 is used. Or (2) equivalent fly ash was used.

表３には、表２に記載の前記特定条件範囲のフライアッシュ含有のポリ塩化ビニル樹脂組成物の具体例と特定条件外のフライアッシュ含有のポリ塩化ビニル樹脂組成物との比較例の各種物性値と最適用途例を記載してある。
表２に示すとおり、前記特定条件範囲のフライアッシュ含有のポリ塩化ビニル樹脂組成物と特定条件外のフライアッシュ含有のポリ塩化ビニル樹脂組成物とを比較すると、特定条件のフライアッシュ含有のポリ塩化ビニル樹脂組成物では引張強さ、破断伸び、耐寒性、加熱変形率、体積抵抗率、酸素指数、引裂き強さが向上していることがわかる。また成形後の外観は、特定条件のフライアッシュ含有のポリ塩化ビニル樹脂組成物が特定条件外のフライアッシュ含有のポリ塩化ビニル樹脂組成物より向上していることを確認した。成形後の外観は実製品の見栄えの他に、強度、磨耗性、耐劣化性、成形性等に影響を与えるものと考えられ、外観が良いものはいずれの特性も良くなるものと考えられる。
さらに例記していないが炭酸カルシウムと比較し特定条件のフライアッシュを充填材として使用することで、耐摩耗性や熱伝導性、難燃性が向上するものと思われる。

Table 3 shows various physical properties of specific examples of the fly ash-containing polyvinyl chloride resin composition in the specific condition range described in Table 2 and comparative examples of the fly ash-containing polyvinyl chloride resin composition outside the specific conditions. Values and examples of optimum use are described.
As shown in Table 2, when the fly ash-containing polyvinyl chloride resin composition in the specific condition range was compared with the fly ash-containing polyvinyl chloride resin composition outside the specific conditions, the fly ash-containing polyvinyl chloride in the specific conditions was compared. It can be seen that the vinyl resin composition has improved tensile strength, elongation at break, cold resistance, heat deformation rate, volume resistivity, oxygen index, and tear strength. Moreover, the external appearance after shaping | molding confirmed that the fly ash containing polyvinyl chloride resin composition of specific conditions was improving rather than the polyvinyl ash resin composition containing fly ash outside specific conditions. The appearance after molding is considered to affect the strength, wear resistance, deterioration resistance, moldability, etc. in addition to the appearance of the actual product, and those with good appearance are considered to improve all the characteristics.
Although not specifically described, it is considered that wear resistance, thermal conductivity, and flame retardancy are improved by using fly ash under specific conditions as a filler as compared with calcium carbonate.

Example 2 introduces an ethylene propylene rubber resin composition as a rubber resin composition containing fly ash under the above specific conditions.
Table 4 shows specific examples of ethylene propylene rubber resin + softener + heat stabilizer + lubricant + crosslinking agent + vulcanization accelerator + sulfur + fly ash-containing ethylene propylene rubber resin composition under the above specific conditions and out of specific conditions The comparative example of the ethylene propylene rubber resin composition containing the fly ash is fried.
As the fly ash under specific conditions, the fly ash equivalent to the modified fly ash (3) described in Table 1 is used, and as the fly ash of the comparative example, the modified fly ash (1) described in Table 1 is used. Or (2) equivalent fly ash was used.

表５には、表４に記載の前記特定条件範囲のフライアッシュ含有組成物の具体例と特定条件外のフライアッシュ含有組成物の比較例の各種物性値と最適用途例を記載してある。
表５に示すとおり、特定条件のフライアッシュ含有のエチレンプロピレンゴム樹脂組成物による効果としては、特定条件外のフライアッシュ含有のエチレンプロピレンゴム樹脂組成物よりも引張強さ、破断伸び、引裂強さ、耐寒性、酸素指数が高く、補強効果に優れており、成形後の外観も良好である。
また前記軟質ＰＶＣ場合と同様に、難燃性や耐摩耗性、熱伝導性といった特性も付与できる可能性があり、これまで使用していた難燃剤を減量することや補強剤の変更によるコストダウンも可能となるものと思われる。

Table 5 shows various physical property values and optimum application examples of specific examples of the fly ash-containing composition in the specific condition range described in Table 4 and comparative examples of the fly ash-containing composition outside the specific conditions.
As shown in Table 5, the effects of the fly ash-containing ethylene propylene rubber resin composition under specific conditions include tensile strength, breaking elongation, and tear strength as compared with the fly ash-containing ethylene propylene rubber resin composition outside the specific conditions. Cold resistance, high oxygen index, excellent reinforcing effect, and good appearance after molding.
In addition, as in the case of the soft PVC, there is a possibility that properties such as flame retardancy, wear resistance, and thermal conductivity can be imparted, and it is possible to reduce the cost by reducing the amount of flame retardant used so far and changing the reinforcing agent. Seems to be possible.

Example 3 introduces a polyolefin resin composition containing fly ash under the specific conditions.
Table 6 lists specific examples of polyolefin resin compositions in which fly ash under specific conditions is contained in a polyolefin resin and comparative examples of polyolefin resin compositions containing fly ash outside specific conditions. As the fly ash under specific conditions, the fly ash equivalent to the modified fly ash (3) described in Table 1 is used, and as the fly ash of the comparative example, the modified fly ash (1) described in Table 1 is used. Or (2) equivalent fly ash was used.

表７には、表６に記載の前記特定条件範囲のフライアッシュ含有のポリオレフィン樹脂組成物の具体例と特定条件外のフライアッシュ含有のポリオレフィン樹脂組成物の比較例の各種物性値と最適用途例を記載してある。
表７に示すとおり、特定条件のフライアッシュ含有のポリオレフィン樹脂組成物による効果としては、特定条件外のフライアッシュ含有のポリオレフィン樹脂組成物よりも引張強さ、破断伸び、引裂強さ、耐寒性、酸素指数が高く、補強効果に優れており、成形後の外観も良好である。
また軟質ＰＶＣ場合と同様に、難燃性や耐摩耗性、熱伝導性といった特性も付与できる可能性があり、これまで使用していた難燃剤を減量することや補強剤の変更によるコストダウンも可能となるものと思われる。

Table 7 shows various physical property values and optimum application examples of specific examples of the fly ash-containing polyolefin resin composition in the specific condition range described in Table 6 and comparative examples of the fly ash-containing polyolefin resin composition outside the specific conditions. Is described.
As shown in Table 7, as an effect of the fly ash-containing polyolefin resin composition under specific conditions, the tensile strength, elongation at break, tear strength, cold resistance, than the fly ash-containing polyolefin resin composition outside the specific conditions, The oxygen index is high, the reinforcing effect is excellent, and the appearance after molding is also good.
In addition, as in the case of soft PVC, there is a possibility that properties such as flame retardancy, wear resistance, and thermal conductivity can be imparted, reducing the amount of flame retardant used so far and reducing costs by changing the reinforcing agent. It seems to be possible.

  Since the present invention has the above-described excellent effects, it is a molded article of a polyvinyl chloride resin composition, such as a member of various electronic devices, a covering material for electric wires, furniture furnishings, automobile-related parts, toys, and household goods, and a rubber resin composition. It can be applied to molded articles and polyolefin resin composition molded articles and contributes greatly to this kind of industry.

FIGS. 1-1 to 1-6 are views showing the influence of the average particle size (horizontal axis) of fly ash on various properties of the polyvinyl chloride resin composition, and FIG. 1-1 shows the relationship with the tensile strength. It is a graph which shows. It is a graph which shows the relationship between an average particle diameter and breaking elongation. It is a graph which shows the relationship between an average particle diameter and cold resistance. It is a graph which shows the relationship between an average particle diameter and a heating deformation rate. It is a graph which shows the relationship between an average particle diameter and volume resistivity. It is a graph which shows the relationship between an average particle diameter and an oxygen index. FIGS. 2-1 to 2-6 are diagrams showing the influence of the blending ratio on various properties of the polyvinyl chloride resin composition when a modified fly ash having an average particle diameter of 3 μm is used. -1 is a graph showing the relationship between the blending ratio (indicated in the figure as the mixing ratio; the same applies hereinafter) and the tensile strength. It is a graph which shows the relationship between a mixture ratio and breaking elongation. It is a graph which shows the relationship between a mixture ratio and cold resistance. It is a graph which shows the relationship between a mixture ratio and a heat deformation rate. It is a graph which shows the relationship between a mixture ratio and volume resistivity. It is a graph which shows the relationship between a mixture ratio and an oxygen index. It is a graph which shows the influence of the average particle diameter of fly ash about "the relationship between the tensile strength and breaking elongation" in the tensile test of a polyvinyl chloride resin composition. 4 is a graph showing the influence of the blending ratio of modified fly ash having an average particle size of 3 μm on the “relation between tensile strength and breaking elongation” in a tensile test of a polyvinyl chloride resin composition. FIGS. 5-1 to 5-6 are views showing the influence of the average particle size of fly ash on various properties of the ethylene propylene rubber resin composition used as the rubber resin composition, and FIG. It is a graph which shows the relationship between a diameter and tensile strength. It is a graph which shows the relationship between an average particle diameter and breaking elongation. It is a graph which shows the relationship between an average particle diameter and tear strength. It is a graph which shows the relationship between an average particle diameter and an oxygen index. FIGS. 6-1 to 6-4 show the effect of the blending ratio on various properties of the ethylene propylene rubber resin composition when a modified fly ash having a particle size of 3 μm is used. FIG. It is a graph which shows the relationship between a mixture ratio and tensile strength. It is a graph which shows the relationship between a mixture ratio and breaking elongation. It is a graph which shows the relationship between a mixture ratio and tear strength. It is a graph which shows the relationship between a mixture ratio and an oxygen index. FIGS. 7-1 to 7-4 are diagrams showing the influence of the average particle size of fly ash on various properties of the polyolefin resin composition, and are graphs showing the relationship between the average particle size of FIG. 7-1 and the tensile strength. . It is a graph which shows the relationship between an average particle diameter and breaking elongation. It is a graph which shows the relationship between an average particle diameter and tear strength. It is a graph which shows the relationship between an average particle diameter and an oxygen index. FIGS. 8-1 to 8-4 are diagrams showing the effect of the blending ratio on various properties of the polyolefin resin composition when a modified fly ash having an average fly ash particle size of 3 μm is used. -1 is a graph showing the relationship between the average particle size and the tensile strength. It is a graph which shows the relationship between a mixture ratio and breaking elongation. It is a graph which shows the relationship between a mixture ratio and tear strength. It is a graph which shows the relationship between a mixture ratio and an oxygen index. The SEM photograph of the particle shape of fly ash is shown.

Claims (3)

  Fly ash satisfying all conditions of average particle size of 5 μm or less, unburned carbon of 1% or less, sphericity (long / short axis ratio) of 0.9 to 1.0, and 45 μm sieve residue of 4% or less, and polyvinyl chloride resin A polyvinyl chloride resin containing fly ash, wherein the fly ash is blended in an amount of 10 to 150 parts by weight per 100 parts by weight of the polyvinyl chloride resin. Composition.   Fly ash satisfying all conditions of average particle size 5 μm or less, unburned carbon 1% or less, sphericity (long / short axis ratio) 0.9-1.0, 45 μm sieve residue 4% or less, rubber resin, A rubber resin composition containing fly ash, comprising a crosslinking agent and a heat stabilizer, wherein the fly ash is blended in an amount of 10 to 800 parts by weight per 100 parts by weight of the rubber resin.   A fly ash that satisfies all conditions of an average particle size of 5 μm or less, unburned carbon of 1% or less, sphericity (long / short axis ratio) of 0.9 to 1.0, and 45 μm sieve residue of 4% or less, and polyolefin resin A polyolefin resin composition containing fly ash, comprising 10 to 1200 parts by weight of the fly ash based on 100 parts by weight of polyolefin resin.

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