JP3217188B2 - Method for forming fine particles of thermoplastic resin - Google Patents
Method for forming fine particles of thermoplastic resinInfo
- Publication number
- JP3217188B2 JP3217188B2 JP14900493A JP14900493A JP3217188B2 JP 3217188 B2 JP3217188 B2 JP 3217188B2 JP 14900493 A JP14900493 A JP 14900493A JP 14900493 A JP14900493 A JP 14900493A JP 3217188 B2 JP3217188 B2 JP 3217188B2
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- Japan
- Prior art keywords
- thermoplastic resin
- fine particles
- weight
- parts
- copolymer
- 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.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、熱可塑性樹脂の連続的
な微粒子化方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for continuously pulverizing a thermoplastic resin.
【０００２】[0002]
【従来の技術】熱可塑性樹脂の微粒子を連続的に製造す
る方法は、たとえば、熱可塑性樹脂を機械的に粉砕する
方法、溶剤中に熱可塑性樹脂を溶解し、晶析する方法、
乳化を利用する方法などが挙げられる。しかし、従来用
いられていたこれらの方法は、微粒子の形状や大きさが
均一でないとか、有機溶媒を使用するとか、経済的でな
いとかの問題を有していた。2. Description of the Related Art Methods for continuously producing fine particles of a thermoplastic resin include, for example, a method of mechanically pulverizing a thermoplastic resin, a method of dissolving a thermoplastic resin in a solvent and crystallization,
Examples include a method utilizing emulsification. However, these conventional methods have problems that the shape and size of the fine particles are not uniform, that an organic solvent is used, and that the method is not economical.
【０００３】[0003]
【発明が解決しようとする問題点】勿論、これらの問題
を解決するための提案もなされてきた。なかでも、乳化
を利用し有機溶剤を使用しない方法は、環境面や経済的
に有利、かつ、真球状の粉末を得ることができるすぐれ
た提案であって、たとえば、特公昭３９−２３９５号公
報、特公平４−３４１６号公報などに記載されている。
また、連続的に熱可塑性樹脂を乳化、分散する方法につ
いては、特公昭５１−２５３７１号公報に記載されてい
る。その方法は、原料熱可塑性樹脂の溶融指数が２０以
上となるような温度条件を選び、界面活性剤としてエチ
レンオキシド−プロピレンオキシド共重合体を用い、水
中で強撹拌することにより熱可塑性樹脂を連続して微粒
子化しようとするものである。具体的には、高温、高圧
の連続分散槽を用いて熱可塑性樹脂を連続的に分散し、
水分散液を連続的に分散槽より抜き出し熱可塑性樹脂の
融点以下の温度に冷却する。しかし、ここで、冷却後に
生成するエチレンオキシド−プロピレンオキシド共重合
体と熱可塑性樹脂微粒子とがゲル状集合体になって充分
に分散されず、流動性の悪い分散液となって冷却管を閉
塞するという問題に悩まされていた。本発明者は、この
問題を解決するために研究の結果、本発明を完成した。Problems to be Solved by the Invention Of course, proposals have been made to solve these problems. Above all, a method utilizing emulsification and not using an organic solvent is an excellent proposal which is environmentally and economically advantageous and can obtain a spherical powder, for example, Japanese Patent Publication No. 39-2395. And Japanese Patent Publication No. 4-31616.
A method for continuously emulsifying and dispersing a thermoplastic resin is described in JP-B-51-25371. The method is to select a temperature condition such that the melting index of the raw material thermoplastic resin is 20 or more, use ethylene oxide-propylene oxide copolymer as a surfactant, and continuously stir the thermoplastic resin by vigorous stirring in water. And try to make it finer. Specifically, the thermoplastic resin is continuously dispersed using a high-temperature, high-pressure continuous dispersion tank,
The aqueous dispersion is continuously withdrawn from the dispersion tank and cooled to a temperature below the melting point of the thermoplastic resin. However, here, the ethylene oxide-propylene oxide copolymer and the thermoplastic resin fine particles generated after cooling become a gel-like aggregate and are not sufficiently dispersed, and become a dispersion having poor fluidity and block the cooling pipe. I was suffering from the problem. The present inventor has completed the present invention as a result of research for solving this problem.
【０００４】[0004]
【課題を解決するための手段】上記の課題は、本発明、
すなわち熱可塑性樹脂１００重量部と水３０〜１５００
重量部とエチレンオキシド−プロピレンオキシド共重合
体１〜３００重量部とを、該熱可塑性樹脂の融点よりも
低くない温度で混合した後、冷却して連続的に熱可塑性
樹脂を微粒子化する方法において、ポリエチレングリコ
ールを添加することによって解決された。使用するポリ
エチレングリコールの平均分子量は、１００〜１００，
０００の範囲がとくに好ましく、また、ポリエチレング
リコールの添加量は、エチレンオキシド−プロピレンオ
キシド共重合体１００重量部に対して１〜１００重量部
が好ましい。The above object is achieved by the present invention,
That is, 100 parts by weight of a thermoplastic resin and 30 to 1500 water
Parts by weight and ethylene oxide-1 to 300 parts by weight of propylene oxide copolymer, after mixing at a temperature not lower than the melting point of the thermoplastic resin, and then cooled to continuously fine particles of the thermoplastic resin, The problem was solved by adding polyethylene glycol. The average molecular weight of the polyethylene glycol used is 100-100,
The range of 000 is particularly preferable, and the amount of polyethylene glycol to be added is preferably 1 to 100 parts by weight based on 100 parts by weight of the ethylene oxide-propylene oxide copolymer.
【０００５】熱可塑性樹脂としては、ポリオレフィン、
ハロゲン化ポリオレフィン、ポリビニルエステル、ポリ
ハロゲン化ビニル、ポリアミド、α，β−不飽和カルボ
ン酸またはそのエステルとオレフィンとの共重合体、お
よび前記の重合体成分の共重合体からなる群から選ばれ
た重合体、またはこれら重合体のうちの２種以上の混合
物が好適であり、なかでも、ポリエチレンまたはポリプ
ロピレン、エチレン−酢酸ビニル共重合体、およびエチ
レン−アクリル酸共重合体に好ましく利用できる。As the thermoplastic resin, polyolefin,
Selected from the group consisting of halogenated polyolefins, polyvinyl esters, polyvinyl halides, polyamides, copolymers of α, β-unsaturated carboxylic acids or their esters and olefins, and copolymers of the aforementioned polymer components. Polymers or mixtures of two or more of these polymers are suitable, and among them, polyethylene or polypropylene, ethylene-vinyl acetate copolymers, and ethylene-acrylic acid copolymers can be preferably used.
【０００６】[0006]
【実施態様例と作用】本発明の熱可塑性樹脂の連続微粒
子化方法について、実施態様例をあげながら具体的に説
明する。本発明者は、水を溶媒とし連続的に熱可塑性樹
脂を微粒子化する方法において、前記の目的を達成する
ために、処理条件、濃度、装置の形状、添加剤などを検
討し、試行錯誤を繰り返すうちに、分散を目的とする界
面活性剤であるエチレンオキシド−プロピレンオキシド
共重合体とポリエチレングリコールとを組み合わせて添
加することにより、前記のゲル状集合体の生成を抑制で
きることを見出だしたのである。Embodiments and Functions The method for continuously forming fine particles of a thermoplastic resin of the present invention will be specifically described with reference to embodiments. The present inventor, in a method of continuously forming a fine particle of a thermoplastic resin using water as a solvent, in order to achieve the above-mentioned object, examines processing conditions, concentration, apparatus shape, additives, and the like, and performs trial and error. During repetition, it was found that the formation of the above-mentioned gel-like aggregates could be suppressed by adding a combination of an ethylene oxide-propylene oxide copolymer, which is a surfactant intended for dispersion, and polyethylene glycol. .
【０００７】まず、本発明の熱可塑性樹脂の連続微粒子
化方法に使用する物質と、使用量について説明する。本
発明が適用される熱可塑性樹脂をとくに制限するもので
ないが、本発明を適用するのに好適な熱可塑性樹脂を例
示すると、ポリオレフィン、ハロゲン化ポリオレフィ
ン、ポリビニルエステル、ポリハロゲン化ビニル、ポリ
アミド、α，β−不飽和カルボン酸またはそのエステル
とオレフィンとの共重合体、およびここにあげた重合体
成分の共重合体があげられる。これらの重合体は、単独
であっても、二種以上の混合体であっても差支えない。First, the substances used in the method for continuous fine particle formation of the thermoplastic resin of the present invention and the amounts used will be described. Although the thermoplastic resin to which the present invention is applied is not particularly limited, examples of the thermoplastic resin suitable for applying the present invention include polyolefin, halogenated polyolefin, polyvinyl ester, polyhalogenated vinyl, polyamide, α, and the like. , .Beta.-unsaturated carboxylic acids or their esters and olefins, and copolymers of the above-mentioned polymer components. These polymers may be used alone or as a mixture of two or more.
【０００８】ポリオレフィンとしては、ポリエチレン、
ポリプロピレン、ポリブチレン、ポリペンテン、ポリヘ
キセン、ポリスチレン等があげられ、ハロゲン化ポリオ
レフィンとしては、塩素化ポリエチレン、臭素化ポリエ
チレン、塩素化ポリプロピレン、臭素化ポリプロピレン
等があげられる。また、ポリビニルエステルとしては、
ポリ酢酸ビニル等があげられ、ポリハロゲン化ビニルと
しては、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリフ
ッ化ビニリデン等が挙げられる。ポリアミドとしては、
ナイロン−６、ナイロン６６、ナイロン１１、ナイロン
１２、共重合ナイロン等があげられる。さらに、α，β
−不飽和カルボン酸またはそのエステルとオレフィンの
共重合体としては、エチレン−アクリル酸共重合体、エ
チレン−アクリル酸エステル共重合体、エチレン−メタ
アクリル酸共重合体、エチレン−メタアクリル酸エステ
ル共重合体、エチレン−アクリル酸−無水マレイン酸共
重合体、エチレン−アクリル酸エステル−無水マレイン
酸共重合体、エチレン−メタアクリル酸−無水マレイン
酸共重合体、エチレン−メタアクリル酸エステル−無水
マレイン酸共重合体およびそれらの金属塩等があげられ
る。また、これらの重合体の２種以上の共重合体として
は、エチレン−酢酸ビニル共重合体、エチレン−塩化ビ
ニル共重合体等があげられる。[0008] Polyolefins include polyethylene,
Examples thereof include polypropylene, polybutylene, polypentene, polyhexene, and polystyrene. Examples of the halogenated polyolefin include chlorinated polyethylene, brominated polyethylene, chlorinated polypropylene, and brominated polypropylene. Further, as the polyvinyl ester,
Examples of polyvinyl acetate include polyvinyl chloride, polyvinylidene chloride, and polyvinylidene fluoride. As a polyamide,
Nylon-6, nylon 66, nylon 11, nylon 12, copolymerized nylon, and the like. Furthermore, α, β
The copolymer of unsaturated carboxylic acid or its ester and olefin includes ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer; Polymer, ethylene-acrylic acid-maleic anhydride copolymer, ethylene-acrylic ester-maleic anhydride copolymer, ethylene-methacrylic acid-maleic anhydride copolymer, ethylene-methacrylic ester-maleic anhydride Acid copolymers and metal salts thereof are exemplified. Examples of the copolymer of two or more of these polymers include an ethylene-vinyl acetate copolymer and an ethylene-vinyl chloride copolymer.
【０００９】エチレンオキシド−プロピレンオキシド共
重合体は、主として乳化のための界面活性剤の作用を有
する。本発明においては、（１）式で示されるエチレン
オキシド−プロピレンオキシド共重合体のいずれをも使
用することができる。[0009] The ethylene oxide-propylene oxide copolymer has a surfactant function mainly for emulsification. In the present invention, any of the ethylene oxide-propylene oxide copolymers represented by the formula (1) can be used.
【００１０】[0010]
【化１】 なかでも、ｘ＝６０〜１３０、ｙ＝３０〜７０、ｚ＝６
０〜１３０の範囲のものが好適である。また、エチレン
オキシド−プロピレンオキシド共重合体の使用量は、通
常、熱可塑性樹脂１００重量部に対して１〜３００重量
部であるが、好ましくは３〜１００重量部である。１重
量部未満では、熱可塑性樹脂を充分に分散させることが
難しくなり、３００重量部を超えると熱可塑性樹脂微粒
子中に混入する量が多くなって、いずれにしても好まし
くない場合が多い。Embedded image Among them, x = 60-130, y = 30-70, z = 6
Those having a range of 0 to 130 are preferred. The amount of the ethylene oxide-propylene oxide copolymer is usually 1 to 300 parts by weight, preferably 3 to 100 parts by weight, per 100 parts by weight of the thermoplastic resin. If the amount is less than 1 part by weight, it is difficult to sufficiently disperse the thermoplastic resin. If the amount exceeds 300 parts by weight, the amount of the thermoplastic resin mixed into the fine particles of the thermoplastic resin increases, and in any case, it is not preferable.
【００１１】ポリエチレングリコールの構造式は、ＨＯ
（ＣＨ2 −ＣＨ2 −Ｏ）n Ｈであって、エチレンオキシ
ド−プロピレンオキシド共重合体と共に添加して使用す
る。本発明では、通常は、ｎ＝２〜２３００の範囲のも
のを使用すればよい。なかでも、ｎ＝２０〜５００のも
のが好適である。ポリエチレングリコールの添加量は、
エチレンオキシド−プロピレンオキシド共重合体１００
重量部に対して、１〜１００重量部が好ましく、さらに
好ましくは５〜５０重量部である。１〜１００重量部の
範囲外であっても、効果がないわけではないが、添加量
が１重量部に達しないと、十分な添加効果が得られず、
エチレンオキシド−プロピレンオキシド共重合体と球状
熱可塑性樹脂微粒子のゲル状集合体による冷却管の閉塞
が起こることがある。１００重量部を超えて添加して
も、効果の増大は余り期待できない。The structural formula of polyethylene glycol is HO
(CH 2 —CH 2 —O) n H, which is used in addition to the ethylene oxide-propylene oxide copolymer. In the present invention, usually, one having a range of n = 2 to 2300 may be used. Among them, those having n = 20 to 500 are preferable. The amount of polyethylene glycol added is
Ethylene oxide-propylene oxide copolymer 100
The amount is preferably from 1 to 100 parts by weight, more preferably from 5 to 50 parts by weight, based on parts by weight. Even if it is out of the range of 1 to 100 parts by weight, it is not without effect, but if the addition amount does not reach 1 part by weight, a sufficient addition effect cannot be obtained,
The cooling pipe may be blocked by a gel-like aggregate of the ethylene oxide-propylene oxide copolymer and the spherical thermoplastic resin fine particles. Even if it exceeds 100 parts by weight, the effect cannot be expected to increase much.
【００１２】連続分散時に溶媒として使用する水は、原
料熱可塑性樹脂１００重量部に対し３０〜１５００重量
部、好ましくは１００〜５００重量部の範囲である。水
の使用量が３０重量部に達しないと、熱可塑性樹脂がう
まく水中に分散できず、また１５００重量部を超えて使
用しても、生産効率の低下を招くことが多く好ましいと
はいえない。The amount of water used as a solvent during continuous dispersion is in the range of 30 to 1500 parts by weight, preferably 100 to 500 parts by weight, per 100 parts by weight of the starting thermoplastic resin. If the amount of water used does not reach 30 parts by weight, the thermoplastic resin cannot be dispersed well in water, and even if it is used in excess of 1500 parts by weight, the production efficiency is often lowered, which is not preferable. .
【００１３】さて、本発明の熱可塑性樹脂の微粒子化方
法においては、所定の温度に加熱され必要な圧力下にあ
る、たとえば、連続攪拌分散槽中に、溶融された前記の
熱可塑性樹脂１００重量部と、３０〜１５００重量部の
水と、１〜３００重量部のエチレンオキシド−プロピレ
ンオキシド共重合体と、ポリエチレングリコールとを連
続的に供給する。熱可塑性樹脂、水、エチレンオキシド
−プロピレンオキシド共重合体の供給は、従来用いられ
ていた方法を適用すればよい。ポリエチレングリコール
の供給方法にとくに限定はない。たとえば、ポリエチレ
ングリコールの水溶液として、またはエチレンオキシド
−プロピレンオキシド共重合体と混合した混合水溶液と
して供給してもよいし、熱可塑性樹脂と混合しながら、
または予め熱可塑性樹脂と混練しておいて供給してもよ
い。分散槽中で、熱可塑性樹脂は攪拌され、剪断力をう
けて連続的に微粒子化される。分散槽としては、熱可塑
性樹脂の融点よりも低くない温度にまで加熱できる適当
な加熱手段と、内容物に十分な剪断力を与えることので
きる攪拌手段とを備えた耐圧容器であればよく、たとえ
ば、耐圧オートクレーブや耐圧ホモジナイザを使用すれ
ばよい。In the method for forming fine particles of a thermoplastic resin according to the present invention, 100 parts by weight of the molten thermoplastic resin are heated to a predetermined temperature and under a required pressure, for example, in a continuous stirring and dispersion tank. , 30 to 1500 parts by weight of water, 1 to 300 parts by weight of an ethylene oxide-propylene oxide copolymer and polyethylene glycol are continuously supplied. For the supply of the thermoplastic resin, water, and the ethylene oxide-propylene oxide copolymer, a conventionally used method may be applied. There is no particular limitation on the method of supplying polyethylene glycol. For example, it may be supplied as an aqueous solution of polyethylene glycol or as a mixed aqueous solution mixed with an ethylene oxide-propylene oxide copolymer, or while being mixed with a thermoplastic resin,
Alternatively, it may be supplied after being kneaded with a thermoplastic resin in advance. In the dispersion tank, the thermoplastic resin is agitated and subjected to shearing force to be continuously atomized. The dispersion tank may be any pressure-resistant container provided with a suitable heating means capable of heating to a temperature not lower than the melting point of the thermoplastic resin, and a stirring means capable of providing a sufficient shearing force to the contents, For example, a pressure-resistant autoclave or a pressure-resistant homogenizer may be used.
【００１４】次に、分散槽から熱可塑性樹脂微粒子を含
む分散液を連続的に分散槽から取り出し、冷却管で熱可
塑性樹脂の融点以下の温度に冷却する。本発明の熱可塑
性樹脂の微粒子化方法においては、冷却の際、エチレン
オキシド−プロピレンオキシド共重合体と球状熱可塑性
樹脂微粒子とのゲル状集合体を生成することなく、冷却
管内にて良好な流動性を示した状態で、連続的に球状熱
可塑性樹脂微粒子を含む常温の分散液を得ることができ
る。冷却の際、ポリエチレングリコールが、エチレンオ
キシド−プロピレンオキシド共重合体と熱可塑性樹脂微
粒子とのゲル状集合体のゲル強度を極度に低下させ、流
動性を失わないよう作用するものと考えられる。得られ
た熱可塑性樹脂微粒子が分散した分散液を、ろ過、洗
浄、乾燥することにより真球状熱可塑性樹脂微粒子を得
ることができる。用途によっては、水分散液のままで使
用することもできる。Next, the dispersion liquid containing the fine particles of the thermoplastic resin is continuously taken out of the dispersion tank and cooled to a temperature lower than the melting point of the thermoplastic resin by a cooling pipe. In the method for forming fine particles of a thermoplastic resin of the present invention, upon cooling, without forming a gel-like aggregate of ethylene oxide-propylene oxide copolymer and spherical thermoplastic resin particles, good fluidity in the cooling pipe In this state, a dispersion at room temperature containing spherical thermoplastic resin fine particles can be continuously obtained. It is considered that upon cooling, polyethylene glycol extremely lowers the gel strength of the gel-like aggregate of the ethylene oxide-propylene oxide copolymer and the fine particles of the thermoplastic resin, and acts so as not to lose fluidity. By filtering, washing and drying the dispersion liquid in which the obtained thermoplastic resin fine particles are dispersed, spherical thermoplastic resin fine particles can be obtained. Depending on the application, it can be used as an aqueous dispersion.
【００１５】[0015]
【実施例】以下に本発明の実施例および比較例を挙げ、
本発明を具体的に説明する。 実施例 １ 主軸３０ｍｍの押出成形機により溶融した毎時３６ｋｇ
のポリエチレン（スミカセンＧ−８０１：１９０℃での
溶融指数２０：住友化学（株）製）と、熱交換器で１９
５℃に昇温した毎時８４ｋｇの界面活性剤水溶液とを、
加熱用電気炉により２００℃に加熱された内径３４０ｍ
ｍ、高さ９００ｍｍ、内容積８０リットルのオートクレ
ーブに底部より連続的に圧入した。界面活性剤水溶液
は、７．７重量部のエチレンオキシド−プロピレンオキ
シド共重合体（ユニルーブ７０ＤＰ９５０Ｂ：日本油脂
（株）製）と０．９重量部（添加比率１０重量部）のポ
リエチレングリコール（ＨＯ（ＣＨ2 −ＣＨ2 −Ｏ）n
Ｈにおいて、ｎは約４５０：ＰＥＧ−２００００：日本
油脂（株）製）とを１００重量部の水に溶解して調合し
た。オートクレーブは、プロペラ型撹拌羽根を備え、こ
の撹拌羽根により撹拌を行ないポリエチレンの連続分散
を行った。EXAMPLES Examples and comparative examples of the present invention will be described below.
The present invention will be specifically described. Example 1 36 kg / hour melted by a 30 mm spindle extruder
Polyethylene (Sumikacene G-801: melting point at 190 ° C: 20: manufactured by Sumitomo Chemical Co., Ltd.) and 19 with a heat exchanger.
84 kg of an aqueous surfactant solution per hour heated to 5 ° C.
340m inner diameter heated to 200 ° C by electric heating furnace
m, a height of 900 mm and an internal volume of 80 liters were continuously press-fitted from the bottom into an autoclave. The aqueous surfactant solution is composed of 7.7 parts by weight of an ethylene oxide-propylene oxide copolymer (Unilube 70DP950B: manufactured by NOF Corporation) and 0.9 parts by weight (addition ratio: 10 parts by weight) of polyethylene glycol (HO (CH) 2 -CH 2 -O) n
In H, n was prepared by dissolving about 450: PEG-20000: manufactured by NOF Corporation in 100 parts by weight of water. The autoclave was equipped with a propeller-type stirring blade, and stirring was performed by the stirring blade to continuously disperse polyethylene.
【００１６】オートクレーブの上部に設けた取出口から
分散液を取り出し、取り出した分散液を内径８ｍｍの多
管式冷却器を通して５０℃に冷却し、ポリエチレン樹脂
微粒子分散液を連続的に得た。冷却管内を流れる分散液
の流れは極めて良好であった。１００時間運転した後、
装置内を検査したところ、冷却管内の閉塞はまったく見
られなかった。得られた分散液をろ過、洗浄、乾燥し、
得られたポリエチレン微粒子の平均粒子径は１８ミクロ
ンで真球状であった。The dispersion was taken out from the outlet provided at the top of the autoclave, and the taken out dispersion was cooled to 50 ° C. through a multitubular cooler having an inner diameter of 8 mm to continuously obtain a dispersion of fine particles of polyethylene resin. The flow of the dispersion flowing through the cooling pipe was extremely good. After driving for 100 hours,
Inspection of the inside of the apparatus revealed no blockage in the cooling pipe. The obtained dispersion is filtered, washed and dried,
The average particle diameter of the obtained polyethylene fine particles was 18 μm and was truly spherical.
【００１７】実施例 ２ 使用したポリエチレングリコールの分子量を変えたほか
は、実施例１と同じ条件でポリエチレン樹脂微粒子を製
造した。用いたポリエチレングリコール（ＨＯ（ＣＨ2
−ＣＨ2 −Ｏ）n Ｈ：ＰＥＧ−４０００：日本油脂
（株）製）のｎは、約９０であった。冷却管内を流れる
分散液の流れは、実施例１と同様、極めて良好であり、
１００時間運転を行なった後、装置内を検査したが、冷
却管内に閉塞は全く見られなかった。得られたポリエチ
レン微粒子の平均粒子径は１７ミクロンで真球状であっ
た。Example 2 Polyethylene resin fine particles were produced under the same conditions as in Example 1 except that the molecular weight of the polyethylene glycol used was changed. The polyethylene glycol used (HO (CH 2
—CH 2 —O) n H: PEG-4000: manufactured by NOF CORPORATION) had an n of about 90. The flow of the dispersion flowing through the cooling pipe was extremely good, as in Example 1.
After 100 hours of operation, the inside of the apparatus was inspected, but no blockage was found in the cooling pipe. The average particle diameter of the obtained polyethylene microparticles was 17 microns and was truly spherical.
【００１８】比較例 １ ポリエチレングリコールを全く添加しない他は、実施例
１と全く同様の条件でポリエチレン樹脂微粒子を製造し
たところ、冷却管が徐々に閉塞し、運転開始２時間後に
冷却管が完全に閉塞した。運転を中止し、内部を点検し
たところ、界面活性剤と微粒子ポリエチレンのゲル状集
合体が原因であることが判った。Comparative Example 1 Polyethylene resin fine particles were produced under the same conditions as in Example 1 except that polyethylene glycol was not added at all. As a result, the cooling pipe was gradually closed, and the cooling pipe was completely closed two hours after the start of operation. Closed. When the operation was stopped and the inside was inspected, it was found that the cause was a gel-like aggregate of a surfactant and fine particle polyethylene.
【００１９】実施例 ３〜６ 実施例１に用いたのと同じ装置を使用し、表１に示した
条件以外は実施例１と同じにして、各種の熱可塑性樹脂
微粒子を製造した。製造条件および得られた熱可塑性樹
脂微粒子の平均粒子径を表１に示す。Examples 3 to 6 The same apparatus as used in Example 1 was used, and various kinds of thermoplastic resin fine particles were produced in the same manner as in Example 1 except for the conditions shown in Table 1. Table 1 shows the production conditions and the average particle diameter of the obtained thermoplastic resin fine particles.
【００２０】[0020]
【表１】 いずれの場合も、運転停止後冷却管内を確かめたが、冷
却管内での閉塞はみられず内部の分散液の流動性は極め
て良好であった。[Table 1] In each case, the inside of the cooling pipe was checked after the operation was stopped, but no blockage was observed in the cooling pipe, and the fluidity of the dispersion liquid inside was extremely good.
【００２１】比較例 ２〜３ ポリエチレングリコールを全く添加しない他は、比較例
２は実施例４と、比較例３は実施例５と全く同様の条件
で熱可塑性樹脂の微粒子を製造した。いずれの場合もエ
チレンオキシド−プロピレンオキシド共重合体と微粒子
熱可塑性のゲル状集合体により、冷却管が運転開始後２
時間以内に閉塞し、連続運転を中止せざるをえなかっ
た。Comparative Examples 2 and 3 Fine particles of a thermoplastic resin were produced under exactly the same conditions as in Example 4 and Comparative Example 3 except that no polyethylene glycol was added. In each case, the cooling pipe was operated after the start of operation by the ethylene oxide-propylene oxide copolymer and the fine particle thermoplastic gel aggregate.
Blockage occurred within hours and continuous operation had to be stopped.
【００２２】[0022]
【発明の効果】本発明の熱可塑性樹脂の微粒子化方法を
用い、熱可塑性樹脂微粒子を連続的に製造する際に、界
面活性剤として用いるエチレンオキシド−プロピレンオ
キシド共重合体の他にポリエチレングリコールを添加す
ることにより、熱可塑性樹脂を加熱、溶融、混合、分散
する工程を経て製造した熱可塑性樹脂微粒子の分散液を
冷却する過程において、従来、頻発していた冷却管内で
の閉塞を防止することができる。従って、長時間、連続
して効率的に熱可塑性樹脂の連続微粒子化を行うことが
可能となった。製造した熱可塑性樹脂微粒子は、流動
性、分散性などの粉末特性にすぐれ、多方面に利用する
ことができる。例えば、化粧品、セラミック用バイン
ダ、印刷用インキ、塗料添加剤、顔料、接着加工剤、高
分子製品の改質材、金属被覆剤、紙、繊維の被覆剤、高
分子製品の粉末成形体などに広く使用することができ
る。According to the method of the present invention for producing fine particles of a thermoplastic resin, polyethylene glycol is added in addition to the ethylene oxide-propylene oxide copolymer used as a surfactant when continuously producing thermoplastic resin fine particles. By heating, melting, mixing and dispersing the thermoplastic resin, in the process of cooling the dispersion of the thermoplastic resin fine particles produced through the process, conventionally, it is possible to prevent the frequently occurring blockage in the cooling pipe. it can. Therefore, it has become possible to continuously and efficiently make the thermoplastic resin fine particles continuously for a long time. The produced thermoplastic resin fine particles have excellent powder properties such as fluidity and dispersibility, and can be used in various fields. For example, cosmetics, binders for ceramics, printing inks, paint additives, pigments, adhesives, modifiers for polymer products, metal coating agents, paper and fiber coating agents, powder compacts for polymer products, etc. Can be widely used.
フロントページの続き (72)発明者 内海 正人 兵庫県姫路市飾磨区入船町１番地 住友 精化株式会社第２研究所内 (72)発明者 船引 裕平 兵庫県姫路市飾磨区入船町１番地 住友 精化株式会社第２研究所内 (56)参考文献 特開 平１−261425（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 3/12 Continuing from the front page (72) Inventor Masato Utsumi 1st Irifunecho, Shimama-ku, Himeji-shi, Hyogo Sumitomo Seika Co., Ltd. (72) Inventor Yuhei Funabiki 1st Irifunecho, Shikarima-ku, Himeji-shi, Hyogo Sumitomo Refinement (56) References JP-A-1-261425 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08J 3/12
Claims (7)
００重量部とエチレンオキシド−プロピレンオキシド共
重合体１〜３００重量部とを、該熱可塑性樹脂の融点よ
りも低くない温度で混合した後、冷却して連続的に熱可
塑性樹脂を微粒子化する方法において、ポリエチレング
リコールを添加することを特徴とする、熱可塑性樹脂の
微粒子化方法。1. 100 parts by weight of a thermoplastic resin and 30 to 15 water.
In a method of mixing 00 parts by weight and 1 to 300 parts by weight of an ethylene oxide-propylene oxide copolymer at a temperature not lower than the melting point of the thermoplastic resin, and then cooling and continuously forming the thermoplastic resin into fine particles. A method of forming fine particles of a thermoplastic resin, comprising adding polyethylene glycol.
１００〜１００，０００であることを特徴とする、請求
項１に記載の熱可塑性樹脂の微粒子化方法。2. The polyethylene glycol having an average molecular weight of:
The method for pulverizing a thermoplastic resin according to claim 1, wherein the number is from 100 to 100,000.
レンオキシド−プロピレンオキシド共重合体１００重量
部に対して１〜１００重量部であることを特徴とする、
請求項１または２に記載の熱可塑性樹脂の微粒子化方
法。3. The method according to claim 1, wherein the amount of the polyethylene glycol is 1 to 100 parts by weight based on 100 parts by weight of the ethylene oxide-propylene oxide copolymer.
The method for forming fine particles of a thermoplastic resin according to claim 1 or 2.
ルエステル、ポリハロゲン化ビニル、ポリアミド、α，
β−不飽和カルボン酸またはそのエステルとオレフィン
との共重合体、および前記の重合体成分の共重合体、か
らなる群から選ばれた重合体、または２種以上の前記重
合体の混合物であることを特徴とする、請求項１、２ま
たは３に記載の熱可塑性樹脂の微粒子化方法。4. The thermoplastic resin comprises polyolefin, halogenated polyolefin, polyvinyl ester, polyvinyl halide, polyamide, α,
a polymer selected from the group consisting of a copolymer of β-unsaturated carboxylic acid or an ester thereof and an olefin, and a copolymer of the above polymer components, or a mixture of two or more kinds of the above polymers. The method according to claim 1, 2 or 3, wherein the thermoplastic resin is finely divided.
プロピレンであることを特徴とする、請求項１、２また
は３に記載の熱可塑性樹脂の微粒子化方法。5. The method for producing fine particles of a thermoplastic resin according to claim 1, wherein the thermoplastic resin is polyethylene or polypropylene.
重合体であることを特徴とする、請求項１、２または３
に記載の熱可塑性樹脂の微粒子化方法。6. The thermoplastic resin according to claim 1, wherein the thermoplastic resin is an ethylene-vinyl acetate copolymer.
The method for forming fine particles of a thermoplastic resin according to the above.
重合体であることを特徴とする、請求項１、２または３
に記載の熱可塑性樹脂の微粒子化方法。7. The method according to claim 1, wherein the thermoplastic resin is an ethylene-acrylic acid copolymer.
The method for forming fine particles of a thermoplastic resin according to the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14900493A JP3217188B2 (en) | 1993-06-21 | 1993-06-21 | Method for forming fine particles of thermoplastic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14900493A JP3217188B2 (en) | 1993-06-21 | 1993-06-21 | Method for forming fine particles of thermoplastic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH073032A JPH073032A (en) | 1995-01-06 |
| JP3217188B2 true JP3217188B2 (en) | 2001-10-09 |
Family
ID=15465563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14900493A Expired - Fee Related JP3217188B2 (en) | 1993-06-21 | 1993-06-21 | Method for forming fine particles of thermoplastic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3217188B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006016414A (en) * | 2004-06-30 | 2006-01-19 | Sumitomo Seika Chem Co Ltd | Method for producing ethylene/(meth)acrylic ester copolymer particle |
| JP4606806B2 (en) * | 2004-08-03 | 2011-01-05 | 住友精化株式会社 | Method for producing polyolefin resin particles |
| JP4907939B2 (en) * | 2005-09-28 | 2012-04-04 | 住友精化株式会社 | Flat granular resin powder and cosmetics using the same |
| KR101734599B1 (en) * | 2009-09-04 | 2017-05-11 | 스미또모 세이까 가부시키가이샤 | Polyolefin-based composite resin spherical particles, coating composition and coated object |
-
1993
- 1993-06-21 JP JP14900493A patent/JP3217188B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH073032A (en) | 1995-01-06 |
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