JP2004346264A - Methacrylic resin particle composition - Google Patents
Methacrylic resin particle composition Download PDFInfo
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- JP2004346264A JP2004346264A JP2003147390A JP2003147390A JP2004346264A JP 2004346264 A JP2004346264 A JP 2004346264A JP 2003147390 A JP2003147390 A JP 2003147390A JP 2003147390 A JP2003147390 A JP 2003147390A JP 2004346264 A JP2004346264 A JP 2004346264A
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、メタクリル樹脂粒子組成物に関する。
【０００２】
【従来の技術】
メタクリル樹脂粒子は粒子状のメタクリル樹脂であって、成形材料として広く用いられており、成形装置へは通常、ポリエチレン製の袋などからホッパーを通じて供給されている。
【０００３】
一方、メタクリル樹脂粒子の最小着火エネルギーは、容易には着火しない点で、大きい方が好ましい。このため、メタクリル樹脂粒子を成形装置に供給する際には、例えば水を配合して着火しにくくしたメタクリル樹脂粒子組成物としてから供給されていた〔非特許文献１：「防火・防爆対策技術ハンドブック」（フジ・テクノシステム発行、１９９８年発行）第１２２頁〕。
【０００４】
しかし、かかる従来のメタクリル樹脂粒子組成物では、最小着火エネルギーを十分に大きくするに足る量の水を配合するとメタクリル樹脂粒子単独よりも流動性が低下してしまい、ポリエチレン製袋から取り出しにくくなったり、ホッパーなどが詰まり易くなるという問題があった。
【０００５】
【非特許文献１】「防火・防爆対策技術ハンドブック」（フジ・テクノシステム発行、１９９８年発行）第１２２頁
【０００６】
【発明が解決しようとする課題】
そこで本発明者は、メタクリル樹脂粒子単独と同等の流動性で、最小着火エネルギーが十分に大きなメタクリル樹脂粒子組成物を開発するべく鋭意検討した結果、メタクリル樹脂粒子１００質量部あたりリン酸エステルを０．７質量部以上配合すると、流動性を低下させることなく、最小着火エネルギーの大きなメタクリル樹脂粒子組成物となし得ることを見出し、本発明に至った。
【０００７】
【課題を解決するための手段】
すなわち本発明は、メタクリル樹脂粒子１００質量部あたり、０．７質量部以上のリン酸エステルが配合されてなることを特徴とするメタクリル樹脂粒子組成物を提供するものである。
【０００８】
【発明の実施の形態】
本発明の増加方法に適用されるメタクリル樹脂粒子は、粒子状のメタクリル樹脂であって、メタクリル酸メチル単位を５０質量％以上含む重合体からなるものである。メタクリル樹脂は、メタクリル酸メチルの単独重合体であってもよいし、メタクリル酸メチルおよびこれと共重合可能な単量体の共重合体であってもよい。
【０００９】
メタクリル酸メチルと共重合可能な単量体は、分子内にメタクリル酸メチルとラジカル重合可能な二重結合を一つ有する単官能単量体であってもよいし、二つ以上有する多官能単量体であってもよい。単官能単量体としては、例えばアクリル酸メチル、アクリル酸２−エチルヘキシル、アクリル酸シクロヘキシルなどのアクリル酸エステル類、メタクリル酸エチル、メタクリル酸２−エチルヘキシル、メタクリル酸シクロヘキシルなどのメタクリル酸エステル類、アクリル酸、メタクリル酸、スチレンなどが挙げられる。多官能単量体としては、例えばネオペンチルグリコールジメタクリレート、エチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレートなどが挙げられる。かかる単量体は、それぞれ単独で、または２種以上を組み合わせて用いられる。
【００１０】
メタクリル樹脂粒子は、添加剤を含有していてもよい。添加剤としては、例えば可塑剤、染料、顔料、紫外線吸収剤、熱安定剤などが挙げられる。かかる添加剤を含有する場合、その含有量は、メタクリル樹脂粒子を基準として５０質量％以下である。
【００１１】
メタクリル樹脂粒子は、その粒子径が通常１μｍ〜１ｍｍ（１０００μｍ）の範囲であるが、本発明の組成物は、メタクリル樹脂粒子の３０質量％以上が粒子径１００μｍ以下、さらには実質的に全量が粒子径１００μｍ以下の粒子である場合に好ましく適用される。
【００１２】
本発明のメタクリル樹脂粒子組成物は、かかるメタクリル樹脂粒子にリン酸エステルが配合されてなるものである。リン酸エステルとしては、例えばトリメチルホスフェート、トリエチルホスフェート、２−アクリロイルオキシエチルアシッドホスフェートなどが挙げられ、好ましくはトリメチルホスフェートである。
【００１３】
リン酸エステルの配合量は、メタクリル樹脂粒子１００質量部あたり０．７質量部以上である。また、過剰に配合しても、それに見合った効果が得られないため、通常は５質量部以下、好ましくは３質量部以下である。
【００１４】
リン酸エステルをメタクリル樹脂粒子に配合するには、例えばリン酸エステルを水に溶解または分散させたのち、メタクリル樹脂粒子と混合し、水を揮発させればよい。また、リン酸エステルがメタクリル樹脂と親和性のものでメタクリル樹脂粒子の表面に容易に分散して付着し得るものである場合には、水を用いることなく、メタクリル樹脂粒子とリン酸エステルとを混合してもよい。
【００１５】
本発明のメタクリル樹脂粒子組成物は、例えば成形材料のほか、樹脂改質剤、光拡散剤などとして使用することができる。成形材料などとして用いる場合には、通常のメタクリル樹脂粒子と同様に、そのまま単独で、あるいは他の成形材料や添加剤と共に、あるいは予め他の成形材料や添加剤と混合されて、ホッパーなどを通じて成形装置に供給される。また、成形装置によってペレット状に成形されたのち、熱プレスによりプレス成形されてもよい。樹脂改質剤、光拡散剤などとして用いられる場合には、成形材料および他の添加剤と共に、あるいは予め成形材料および他の添加剤と混合されて、ホッパーなどを通じて成形装置に供給される。成形装置としては、例えば押出成形装置、射出成形装置などが挙げられる。
【００１６】
【発明の効果】
本発明のメタクリル樹脂粒子組成物は、最小着火エネルギーが大きいばかりでなく、流動性が低下していないので、例えば成形材料、樹脂改質材、光拡散剤などとして用いる場合には、ホッパーを詰まらせたりすることなく、成形装置へ容易に供給することができる。
【００１７】
【実施例】
以下、実施例によって本発明をより詳細に説明するが、本発明はこれら実施例によって限定されるものではない。
【００１８】
なお、以下の各実施例において、最小着火エネルギーは、吹上げ式粉じん爆発試験装置〔アマノ（株）製〕を用い、温度２３℃〜２４℃、湿度５６℃〜５８℃、放電エネルギー０．１６０７μＦにて測定した。
流動性は、試料６００ｇを、長辺４０ｃｍ、短辺３５ｃｍの長方形で短辺のうちの一つが開口部となっているポリエチレン製袋に入れて開口部を密封し、袋内で試料を十分にほぐしてから開口部を開封し、袋を傾けてこの開口部から別の容器に試料を空けるときの試料の流れ易さと、空けた後にポリエチレン製袋の内部に付着した試料の量で評価した。袋内に試料が付着せずに、留まることなく全量が流れ出たときには、流動性が良好と判定し、試料が付着するか、あるいは途中で留まったときには、不良と判定した。
【００１９】
実施例１
トリメチルホスフェート（ＴＭＰ）５．４ｇを水１００ｇに溶解させ、この溶液をメタクリル酸メチル単独重合体粒子（粒子径は約１４μｍ〜約１０５μｍの範囲、１００μｍ以下の粒子の割合は９９質量％以上、中心粒子径は２８μｍ）６００ｇと室温（約２５℃）で混合したのち、８０℃で真空乾燥して、メタクリル樹脂粒子組成物を得た。このメタクリル樹脂粒子組成物には、メタクリル酸メチル単独重合体粒子１００ｇあたり０．９ｇのＴＭＰが配合されている。この組成物の評価結果を表１に示す。
【００２０】
比較例１
実施例１で用いたと同じメタクリル酸メチル単独重合体粒子について、ＴＭＰを添加することなく最小着火エネルギーを求め、流動性を評価した。結果を表１に示す。
【００２１】
比較例２
実施例１で用いたと同じメタクリル樹脂粒子６００ｇに純水１３．８ｇを添加して撹拌し、メタクリル樹脂粒子組成物を得た。この組成物には、メタクリル樹脂粒子１００ｇあたり２．３ｇの水が配合されている。この組成物の評価結果を表１に示す。
【００２２】
比較例３
ＴＭＰの使用量を３．０ｇとした以外は実施例１と同様に操作して、メタクリル樹脂粒子組成物を得た。このメタクリル樹脂粒子組成物には、メタクリル酸メチル単独重合体粒子１００ｇあたり０．５ｇのＴＭＰが配合されている。この組成物の評価結果を表１に示す。
【００２３】
【表１】
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a methacrylic resin particle composition.
[0002]
[Prior art]
The methacrylic resin particles are particulate methacrylic resin and are widely used as a molding material, and are usually supplied to a molding apparatus from a polyethylene bag or the like through a hopper.
[0003]
On the other hand, it is preferable that the minimum ignition energy of the methacrylic resin particles is large in that ignition is not easily performed. For this reason, when supplying methacrylic resin particles to a molding apparatus, they have been supplied as a methacrylic resin particle composition which is made difficult to ignite by, for example, mixing water [Non-Patent Document 1: "Fire and Explosion Proof Measures Handbook" (Published by Fuji Technosystem, 1998), p. 122].
[0004]
However, in such a conventional methacrylic resin particle composition, if water is added in an amount sufficient to sufficiently increase the minimum ignition energy, the fluidity is lower than that of the methacrylic resin particles alone, and it is difficult to remove the particles from the polyethylene bag. However, there is a problem that the hopper and the like are easily clogged.
[0005]
[Non-Patent Document 1] "Fire and Explosion Prevention Technology Handbook" (published by Fuji Techno System, published in 1998), page 122 [0006]
[Problems to be solved by the invention]
Therefore, the present inventor has conducted intensive studies to develop a methacrylic resin particle composition having a fluidity equivalent to that of methacrylic resin particles alone and a sufficiently large minimum ignition energy. As a result, the phosphoric acid ester was reduced to 0 per 100 parts by mass of methacrylic resin particles. The present inventors have found that, when the content is 0.7 parts by mass or more, a methacrylic resin particle composition having a large minimum ignition energy can be obtained without lowering fluidity, and the present invention has been achieved.
[0007]
[Means for Solving the Problems]
That is, the present invention provides a methacrylic resin particle composition characterized in that 0.7 parts by mass or more of a phosphoric ester is blended with respect to 100 parts by mass of methacrylic resin particles.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The methacrylic resin particles applied to the increasing method of the present invention are particulate methacrylic resins and are made of a polymer containing 50% by mass or more of methyl methacrylate units. The methacrylic resin may be a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and a monomer copolymerizable therewith.
[0009]
The monomer copolymerizable with methyl methacrylate may be a monofunctional monomer having one double bond capable of radical polymerization with methyl methacrylate in the molecule, or a polyfunctional monomer having two or more monomers. It may be a monomer. Monofunctional monomers include, for example, acrylates such as methyl acrylate, 2-ethylhexyl acrylate and cyclohexyl acrylate, methacrylates such as ethyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and acrylic Acids, methacrylic acid, styrene and the like. Examples of the polyfunctional monomer include neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate. Such monomers are used alone or in combination of two or more.
[0010]
The methacrylic resin particles may contain an additive. Examples of the additive include a plasticizer, a dye, a pigment, an ultraviolet absorber, and a heat stabilizer. When such an additive is contained, its content is 50% by mass or less based on the methacrylic resin particles.
[0011]
The methacrylic resin particles generally have a particle diameter in the range of 1 μm to 1 mm (1000 μm). However, in the composition of the present invention, 30% by mass or more of the methacrylic resin particles have a particle diameter of 100 μm or less, and substantially the entire amount is less than 100%. It is preferably applied when the particles have a particle diameter of 100 μm or less.
[0012]
The methacrylic resin particle composition of the present invention is obtained by mixing a phosphoric ester with such methacrylic resin particles. Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, 2-acryloyloxyethyl acid phosphate, and the like, and preferably trimethyl phosphate.
[0013]
The compounding amount of the phosphate is 0.7 parts by mass or more per 100 parts by mass of the methacrylic resin particles. Further, even if it is excessively mixed, the effect corresponding thereto is not obtained, so that the amount is usually 5 parts by mass or less, preferably 3 parts by mass or less.
[0014]
In order to mix the phosphate with the methacrylic resin particles, for example, the phosphate may be dissolved or dispersed in water, and then mixed with the methacrylic resin particles to evaporate the water. In addition, when the phosphate ester has an affinity for the methacrylic resin and can be easily dispersed and adhered to the surface of the methacrylic resin particles, the methacrylic resin particles and the phosphate ester are used without using water. You may mix.
[0015]
The methacrylic resin particle composition of the present invention can be used, for example, as a resin modifier, a light diffusing agent, and the like, in addition to a molding material. When used as a molding material, as in the case of ordinary methacrylic resin particles, they can be used alone or with other molding materials or additives, or can be mixed with other molding materials or additives in advance and molded through a hopper or the like. Supplied to the device. Alternatively, after being formed into a pellet by a molding device, the pellet may be press-formed by hot pressing. When used as a resin modifier, light diffusing agent, or the like, it is supplied to a molding device through a hopper or the like, together with a molding material and other additives, or mixed in advance with a molding material and other additives. Examples of the molding device include an extrusion molding device and an injection molding device.
[0016]
【The invention's effect】
The methacrylic resin particle composition of the present invention not only has a high minimum ignition energy, but also has a low fluidity.For example, when used as a molding material, a resin modifier, a light diffusing agent, etc., the hopper is clogged. It can be easily supplied to the molding device without being hampered.
[0017]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[0018]
In each of the following examples, the minimum ignition energy was measured using a blow-up type dust explosion test apparatus (manufactured by Amano Corporation) at a temperature of 23 ° C. to 24 ° C., a humidity of 56 ° C. to 58 ° C., and a discharge energy of 0.1607 μF. Was measured.
The fluidity is as follows. 600 g of the sample is placed in a polyethylene bag having a long side of 40 cm and a short side of 35 cm, and one of the short sides is an opening. The opening is sealed, and the sample is sufficiently filled in the bag. After loosening, the opening was opened, and the bag was tilted to evaluate the ease of flow of the sample when the sample was emptied from the opening into another container, and the amount of the sample adhered to the inside of the polyethylene bag after the emptiness. When the entire amount of the sample flowed out without remaining in the bag without sticking, it was judged that the fluidity was good, and when the sample adhered or stayed halfway, it was judged as poor.
[0019]
Example 1
5.4 g of trimethyl phosphate (TMP) is dissolved in 100 g of water, and this solution is mixed with methyl methacrylate homopolymer particles (particle diameter is in the range of about 14 μm to about 105 μm, the proportion of particles of 100 μm or less is 99% by mass or more, and After mixing 600 g with a particle size of 28 μm at room temperature (about 25 ° C.), the mixture was vacuum-dried at 80 ° C. to obtain a methacrylic resin particle composition. The methacrylic resin particle composition contains 0.9 g of TMP per 100 g of methyl methacrylate homopolymer particles. Table 1 shows the evaluation results of the composition.
[0020]
Comparative Example 1
For the same methyl methacrylate homopolymer particles used in Example 1, the minimum ignition energy was determined without adding TMP, and the fluidity was evaluated. Table 1 shows the results.
[0021]
Comparative Example 2
13.8 g of pure water was added to 600 g of the same methacrylic resin particles as used in Example 1 and stirred to obtain a methacrylic resin particle composition. This composition contains 2.3 g of water per 100 g of methacrylic resin particles. Table 1 shows the evaluation results of the composition.
[0022]
Comparative Example 3
A methacrylic resin particle composition was obtained in the same manner as in Example 1, except that the amount of TMP used was 3.0 g. This methacrylic resin particle composition contains 0.5 g of TMP per 100 g of methyl methacrylate homopolymer particles. Table 1 shows the evaluation results of the composition.
[0023]
[Table 1]
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003147390A JP4251017B2 (en) | 2003-05-26 | 2003-05-26 | Method for producing methacrylic resin particle composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003147390A JP4251017B2 (en) | 2003-05-26 | 2003-05-26 | Method for producing methacrylic resin particle composition |
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| Publication Number | Publication Date |
|---|---|
| JP2004346264A true JP2004346264A (en) | 2004-12-09 |
| JP4251017B2 JP4251017B2 (en) | 2009-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010113796A1 (en) * | 2009-03-31 | 2010-10-07 | 昭和高分子株式会社 | Resin composition and processed paper or fiber product treated therewith |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010113796A1 (en) * | 2009-03-31 | 2010-10-07 | 昭和高分子株式会社 | Resin composition and processed paper or fiber product treated therewith |
| CN102369224A (en) * | 2009-03-31 | 2012-03-07 | 昭和电工株式会社 | Resin composition and processed paper or fiber product treated therewith |
| CN102369224B (en) * | 2009-03-31 | 2015-11-25 | 昭和电工株式会社 | Resin combination and with its paper processed or fiber process product |
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| Publication number | Publication date |
|---|---|
| JP4251017B2 (en) | 2009-04-08 |
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