JPH08155969A - Washing agent for molding machine - Google Patents
Washing agent for molding machineInfo
- Publication number
- JPH08155969A JPH08155969A JP6330370A JP33037094A JPH08155969A JP H08155969 A JPH08155969 A JP H08155969A JP 6330370 A JP6330370 A JP 6330370A JP 33037094 A JP33037094 A JP 33037094A JP H08155969 A JPH08155969 A JP H08155969A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- molding machine
- parts
- polymer
- resin
- 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.)
- Granted
Links
Landscapes
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Detergent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、熱可塑性樹脂（以下単
に「樹脂」という）用成形機による所定作業終了時に、
当該成形機内に残留する樹脂そのもの及び成形材料中に
含まれる染顔料等の添加物を除去するための洗浄剤に関
する。BACKGROUND OF THE INVENTION The present invention relates to a thermoplastic resin (hereinafter simply referred to as "resin") molding machine at the end of a predetermined operation.
The present invention relates to a cleaning agent for removing the resin itself remaining in the molding machine and additives such as dyes and pigments contained in the molding material.
【０００２】[0002]
【従来の技術】一般に、樹脂の着色、混合、成形等を目
的に成形機（押出・射出）が用いられているが、所定の
作業終了時に、当該樹脂そのものや成形材料中に含まれ
ている染顔料等の添加剤が成形機内に残留する。この残
留物は、次に行われる異種樹脂又は異色樹脂による成形
時に成形品中に混入し、製品外観不良の原因となる。2. Description of the Related Art Generally, a molding machine (extrusion / injection) is used for the purpose of coloring, mixing, molding, etc. of a resin, but it is contained in the resin itself or a molding material at the end of a predetermined work. Additives such as dyes and pigments remain in the molding machine. This residue is mixed into the molded product during the subsequent molding with a different resin or a different color resin, which causes a defective product appearance.
【０００３】従来、上記残留物を成形機内から除去する
ため、人手により成形機の分解掃除をする方法、成形機
を停止せずにそのまま次に使用する成形材料を成形機に
充填し、これにより残留物を少しづつ置換して行く方法
の他に洗浄剤を用いる方法が実施されている。Conventionally, in order to remove the above residue from the inside of the molding machine, the molding machine is manually disassembled and cleaned, and the molding material to be used next is directly charged into the molding machine without stopping the molding machine. In addition to the method of gradually replacing the residue, a method of using a cleaning agent is practiced.
【０００４】洗浄剤を用いる場合、洗浄剤で洗浄した
後、次の成形に入る前に、通常、次の成形材料によっ
て、残留する洗浄剤の置換作業を行う。従って、洗浄剤
には、前の成形で使用した成形材料に対する高い洗浄力
と、次の成形に使用する成形材料による易置換性とが要
求される。When a cleaning agent is used, the remaining cleaning agent is usually replaced with the next molding material after cleaning with the cleaning agent and before starting the next molding. Therefore, the cleaning agent is required to have high detergency with respect to the molding material used in the previous molding and easily replaceable with the molding material used in the next molding.
【０００５】本発明者等は既に、洗浄力・易置換性とも
に優れる洗浄剤として、スチレン系樹脂と特定のグラフ
ト重合体よりなる洗浄剤を提案しており、更に該洗浄剤
にガラス繊維又はガラス粒を含有させることにより洗浄
力を向上できることを提案している（特開平４−４２５
４７号）。The present inventors have already proposed a detergent comprising a styrene-based resin and a specific graft polymer as a detergent having excellent detergency and easy-displacement property. Further, the detergent is glass fiber or glass. It has been proposed that the cleaning power can be improved by incorporating particles (Japanese Patent Laid-Open No. 4-425).
47).
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、洗浄剤
にガラス繊維又はガラス粒を含有させた場合、ガラス繊
維又はガラス粒が洗浄に際し成形機内部を傷つける、或
いは使用後の洗浄剤の焼却処理においてガラス繊維又は
ガラス粒が燃え残るという問題があった。However, when the cleaning agent contains glass fibers or glass particles, the glass fibers or glass particles damage the inside of the molding machine during cleaning, or the glass is used in the incineration treatment of the cleaning agent after use. There is a problem that fibers or glass particles remain unburned.
【０００７】本発明は、このような従来未解決の課題に
着目してなされたもので、ガラス繊維又はガラス粒を使
用せずに、これらを使用した場合と同等以上の洗浄力及
び易置換性を得ることができる洗浄剤とすることを目的
とする。The present invention has been made by paying attention to such an unsolved problem in the past, and does not use glass fibers or glass particles, but has the same or higher detergency and ease of replacement as in the case of using them. The purpose of the present invention is to provide a cleaning agent capable of obtaining
【０００８】[0008]
【課題を解決するための手段及び作用】上記課題を解決
するために本発明において講じられた手段を説明する
と、本発明では、熱可塑性樹脂１００重量部に対して熱
可塑性超高分子５〜４０重量部混合するという手段を講
じているものである。Means and Actions for Solving the Problems The means taken in the present invention for solving the above problems will be described. In the present invention, the thermoplastic superpolymer 5 to 40 is added to 100 parts by weight of the thermoplastic resin. The means of mixing parts by weight is taken.
【０００９】本発明で用いられる熱可塑性樹脂として
は、例えばエチレン系樹脂、スチレン−アクリロニトリ
ル系樹脂、プロピレン系樹脂、メチルメタクリレート系
樹脂等が挙げられる。熱可塑性樹脂の分子量は特に限定
されないが、２０万〜３０万が好ましい。また、熱可塑
性樹脂のメルトフローレイトは０．５〜３０ｇ／１０分
であることが好ましい。メルトフローレイトが０．５ｇ
／１０分未満では、標準的な成形条件、例えば成形温度
２００〜２８０℃で使用しにくく、また３０ｇ／１０分
を越えると十分な洗浄効果が得にくくなる。尚、本明細
書におけるメルトフローレイトは、２２０℃、１０ｋｇ
の条件下における値をいう。Examples of the thermoplastic resin used in the present invention include ethylene resin, styrene-acrylonitrile resin, propylene resin, methyl methacrylate resin and the like. The molecular weight of the thermoplastic resin is not particularly limited, but 200,000 to 300,000 is preferable. Further, the melt flow rate of the thermoplastic resin is preferably 0.5 to 30 g / 10 minutes. Melt flow rate is 0.5g
If it is less than / 10 minutes, it is difficult to use it under standard molding conditions, for example, at a molding temperature of 200 to 280 ° C., and if it exceeds 30 g / 10 minutes, it becomes difficult to obtain a sufficient cleaning effect. The melt flow rate in the present specification is 220 ° C. and 10 kg.
The value under the conditions of.
【００１０】エチレン系樹脂は、ＬＤＰＥでもＬＬＰＥ
でもよいがＨＤＰＥが最も好ましい。また、プロピレン
その他との共重合体でもよく、ブロック共重合体でもラ
ンダム共重合体でもよいが、エチレンの含有量が５０重
量％以上である必要がある。Ethylene-based resin can be LDPE or LLPE
However, HDPE is most preferred. Further, it may be a copolymer with propylene or the like, and may be a block copolymer or a random copolymer, but the ethylene content must be 50% by weight or more.
【００１１】スチレン−アクリロニトリル系樹脂は、ア
クリロニトリル含有量が５重量％以上５０重量％未満の
ものが、洗浄力及び成形機類内への非残留性に優れるこ
とから好ましい。The styrene-acrylonitrile-based resin having an acrylonitrile content of 5% by weight or more and less than 50% by weight is preferable because it is excellent in detergency and non-residuality in the molding machine.
【００１２】プロピレン系樹脂は、ホモポリプロピレン
でもよいし、エチレンその他との共重合体でもよい。共
重合体はブロック共重合体でもランダム共重合体でもよ
いが、プロピレンの含有量が５０重量％以上である必要
がある。The propylene resin may be homopolypropylene or a copolymer with ethylene or the like. The copolymer may be a block copolymer or a random copolymer, but the content of propylene needs to be 50% by weight or more.
【００１３】メチルメタクリレート系樹脂は、ホモポリ
メチルメタクリレートでもよいしスチレンその他との共
重合体でもよい。共重合体はブロック共重合体でもラン
ダム共重合体でもよいが、メチルメタクリレートの含有
量が５０重量％以上である必要がある。The methyl methacrylate resin may be homopolymethyl methacrylate or a copolymer with styrene or the like. The copolymer may be a block copolymer or a random copolymer, but the content of methyl methacrylate needs to be 50% by weight or more.
【００１４】また、熱可塑性超高分子とは、分子量１０
０万以上の高分子をいい、例えばエチレン系超高分子、
スチレン−アクリロニトリル系超高分子、メチルメタク
リレート系超高分子等が挙げられる。分子量の上限は特
に限定されないが、一般的には１０００万以下であるこ
とが実用上好ましい。また、超高分子はホモポリマーで
もコポリマーでもよく、コポリマーの場合は主成分、例
えばエチレン、スチレン−アクリロニトリル共重合体、
メチルメタクリレート等の含有量が５０重量％以上であ
る必要がある。The thermoplastic ultra-high polymer has a molecular weight of 10
A polymer of more than 0,000, such as an ethylene-based ultra polymer,
Examples thereof include styrene-acrylonitrile superpolymers and methylmethacrylate superpolymers. The upper limit of the molecular weight is not particularly limited, but in general, it is practically preferable to be 10 million or less. Further, the ultrapolymer may be a homopolymer or a copolymer, and in the case of the copolymer, the main component, for example, ethylene, a styrene-acrylonitrile copolymer,
The content of methyl methacrylate or the like needs to be 50% by weight or more.
【００１５】これらのうちで好ましい組み合わせは、エ
チレン系樹脂とエチレン系超高分子、スチレン−アクリ
ロニトリル系樹脂とエチレン系超高分子、スチレン−ア
クリロニトリル系樹脂とスチレン−アクリロニトリル系
超高分子、スチレン−アクリロニトリル系樹脂とメチル
メタクリレート系超高分子、メチルメタクリレート系樹
脂とメチルメタクリレート系超高分子、メチルメタクリ
レート系樹脂とスチレン−アクリロニトリル系超高分子
であり、特に好ましい組み合わせは、エチレン系樹脂と
エチレン系超高分子、スチレン−アクリロニトリル系樹
脂とエチレン系超高分子である。Among these, preferred combinations are ethylene resin and ethylene superpolymer, styrene-acrylonitrile resin and ethylene superpolymer, styrene-acrylonitrile resin and styrene-acrylonitrile superpolymer, styrene-acrylonitrile. -Based resin and methylmethacrylate-based ultrapolymer, methylmethacrylate-based resin and methylmethacrylate-based ultrapolymer, methylmethacrylate-based resin and styrene-acrylonitrile-based ultrapolymer, and particularly preferred combinations are ethylene-based resin and ethylene-based ultrahigh polymer. Molecules, styrene-acrylonitrile-based resin and ethylene-based ultra polymer.
【００１６】本発明では、熱可塑性超高分子をベースと
なる熱可塑性樹脂と混合して洗浄剤としているものであ
る。熱可塑性超高分子は、一般的にベースとなる熱可塑
性樹脂に比べて粘度が高いのであるが、本発明の洗浄剤
により得られる高い洗浄効果は、単に熱可塑性超高分子
混合による増粘効果によって得られるものではないと考
えられる。In the present invention, a thermoplastic superpolymer is mixed with a base thermoplastic resin to form a detergent. The thermoplastic superpolymer generally has a higher viscosity than the base thermoplastic resin, but the high cleaning effect obtained by the cleaning agent of the present invention is simply the thickening effect by the thermoplastic superpolymer mixture. It is not considered to be obtained by
【００１７】熱可塑性樹脂と熱可塑性超高分子の混合比
は、熱可塑性樹脂１００重量部に対して熱可塑性超高分
子２〜５０重量部で、好ましくは熱可塑性樹脂１００重
量部に対して熱可塑性超高分子５〜４０重量部、最も好
ましくは熱可塑性樹脂１００重量部に対して熱可塑性超
高分子１０〜３０重量部である。The mixing ratio of the thermoplastic resin and the thermoplastic superpolymer is 2 to 50 parts by weight of the thermoplastic ultrapolymer with respect to 100 parts by weight of the thermoplastic resin, preferably 100 parts by weight of the thermoplastic resin. The thermoplastic superpolymer is 5 to 40 parts by weight, most preferably 10 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
【００１８】また、例えばスチレン−アクリロニトリル
系樹脂とエチレン系超高分子の組み合わせの如く相溶性
に乏しい組み合わせの場合には、更に相溶化剤として、
主鎖をなすオレフィン系重合体と、側鎖をなすスチレン
系重合体とから構成されるグラフト重合体を混合するの
が易置換性の点で好ましい。Further, in the case of a combination having a poor compatibility such as a combination of a styrene-acrylonitrile resin and an ethylene superpolymer, a compatibilizing agent is further added.
From the viewpoint of easy substitution, it is preferable to mix a graft polymer composed of an olefin polymer forming the main chain and a styrene polymer forming the side chain.
【００１９】該グラフト重合体において主鎖をなすオレ
フィン系重合体とは、ポリエチレン、ポリプロピレン、
エチレン−プロピレン共重合体又は、エチレン及び／又
はプロピレンの含有量が５０重量％以上の共重合体をい
う。エチレン及び／又はプロピレンと共重合させる他の
単量体としては、例えば酢酸ビニル、アクリロニトリ
ル、グリシジルメタクリレート、エチルアクリレート、
スチレン等が挙げられる。これらのうち、主鎖をなすオ
レフィン系重合体としてはポリエチレン、ポリプロピレ
ン、エチレン−プロピレン共重合体が好ましい。The olefinic polymer forming the main chain in the graft polymer is polyethylene, polypropylene,
An ethylene-propylene copolymer or a copolymer having an ethylene and / or propylene content of 50% by weight or more. As other monomers to be copolymerized with ethylene and / or propylene, for example, vinyl acetate, acrylonitrile, glycidyl methacrylate, ethyl acrylate,
Examples include styrene and the like. Among these, polyethylene, polypropylene, and ethylene-propylene copolymer are preferable as the olefin polymer forming the main chain.
【００２０】また、側鎖をなすスチレン系重合体とは、
ポリスチレン又は、スチレンと１種もしくは２種以上の
他の単量体との共重合体であって、スチレンの含有量が
５０重量％以上の共重合体をいう。スチレンと共重合さ
せる他の単量体としては、例えばアクリロニトリル、メ
チルメタクリレート等が挙げられる。これらのうち、側
鎖をなすスチレン系重合体としては、スチレン−アクリ
ロニトリル共重合体が好ましい。The styrene-based polymer forming the side chain is
Polystyrene or a copolymer of styrene and one or more other monomers, the styrene content of which is 50% by weight or more. Examples of the other monomer copolymerized with styrene include acrylonitrile and methyl methacrylate. Of these, a styrene-acrylonitrile copolymer is preferable as the styrene-based polymer forming the side chain.
【００２１】上記主鎖をなすオレフィン系重合体と、側
鎖をなすスチレン系重合体の構成比は、一般的にはオレ
フィン系重合体が１５〜９０重量％（スチレン系重合体
が８５〜１０重量％）、好ましくは２０〜８０重量％
（スチレン系重合体が８０〜２０重量％）のものが用い
られるが、更に好ましくはオレフィン系重合体が４０〜
６０重量％（スチレン系重合体が６０〜４０重量％）で
ある。The composition ratio of the olefin polymer forming the main chain to the styrene polymer forming the side chain is generally 15 to 90% by weight of the olefin polymer (85 to 10 of the styrene polymer). %), Preferably 20-80% by weight
(Styrene-based polymer is 80 to 20% by weight), and more preferably olefin-based polymer is 40 to 20% by weight.
60% by weight (60 to 40% by weight of styrene polymer).
【００２２】グラフト重合体の混合比は、熱可塑性樹脂
と熱可塑性超高分子の混合物１００重量部に対してグラ
フト重合体２〜１６０重量部で、好ましくは熱可塑性樹
脂と熱可塑性超高分子の混合物１００重量部に対してグ
ラフト重合体２〜１００重量部、最も好ましくは熱可塑
性樹脂と熱可塑性超高分子の混合物１００重量部に対し
てグラフト重合体５〜８０重量部である。The mixing ratio of the graft polymer is 2 to 160 parts by weight of the graft polymer with respect to 100 parts by weight of the mixture of the thermoplastic resin and the thermoplastic superpolymer, preferably the thermoplastic resin and the thermoplastic superpolymer. 2 to 100 parts by weight of the graft polymer per 100 parts by weight of the mixture, and most preferably 5 to 80 parts by weight of the graft polymer per 100 parts by weight of the mixture of the thermoplastic resin and the thermoplastic superpolymer.
【００２３】グラフト重合体は、公知のグラフト重合体
の製造方法にて容易に製造できるもので、いずれの製造
方法で製造されたものでもよく、この製造方法により制
限されるものではない。The graft polymer can be easily produced by a known method for producing a graft polymer, and may be produced by any production method, and is not limited by this production method.
【００２４】ここで、一般的なグラフト重合体の製造方
法について説明すると、次の方法にて製造できることが
知られている。Here, a general method for producing a graft polymer will be described. It is known that the following method can be used for production.
【００２５】まず、主鎖（又は側鎖）となる重合体に、
例えば過酸化物処理、紫外線照射、高エネルギー放射線
照射、ペルオキシドモノマー（重合性二重結合と活性ペ
ルオキシドを１分子中に共有するモノマー）との共重
合、空気中熱処理等の方法にてグラフト活性点を生成せ
しめる。次いで、このグラフト活性点を生成させた主鎖
（又は側鎖）となる重合体を、必要な条件下において、
側鎖（又は主鎖）を構成する重合体、共重合体、モノマ
ー又はモノマー混合液に接触させることにより、グラフ
ト重合体を製造することができる。First, a polymer to be the main chain (or side chain) is
For example, by using a method such as peroxide treatment, ultraviolet irradiation, high-energy irradiation, copolymerization with a peroxide monomer (monomer that shares a polymerizable double bond and active peroxide in one molecule), or heat treatment in air, the grafting active point Is generated. Then, the polymer that becomes the main chain (or side chain) that generated this graft active site is
The graft polymer can be produced by bringing it into contact with a polymer, a copolymer, a monomer or a monomer mixture liquid which constitutes a side chain (or main chain).
【００２６】具体的には、例えば、空気中にてγ線を照
射したポリプロピレン粉末に、スチレン及びアクリロニ
トリルの混合モノマーを加え、加熱重合した後、メタノ
ール抽出を行って未重合モノマーを除去することで製造
することができる。また、例えば、ポリプロピレン粉末
に、スチレン、アクリロニトリル、ｔ−ブチルペルオキ
シメタクリロイロキシエチルカーボネイト（ペルオキシ
ドモノマー）、エチルカーボネイト及びベンゾイルパー
オキサイド（重合触媒）よりなる混合モノマー溶液を含
浸させ、５０℃〜１００℃で１０時間程度含浸重合させ
た後、未重合モノマーを除去し、プラストミルにて溶融
混練グラフトすることによっても製造することができ
る。Specifically, for example, by adding a mixed monomer of styrene and acrylonitrile to polypropylene powder irradiated with γ-rays in the air and polymerizing by heating, methanol extraction is performed to remove unpolymerized monomer. It can be manufactured. Further, for example, polypropylene powder is impregnated with a mixed monomer solution composed of styrene, acrylonitrile, t-butylperoxymethacryloyloxyethyl carbonate (peroxide monomer), ethyl carbonate and benzoyl peroxide (polymerization catalyst), and the temperature is 50 ° C to 100 ° C. It can also be produced by carrying out impregnation polymerization for about 10 hours, removing unpolymerized monomers, and melt-kneading and grafting with a plastomill.
【００２７】熱可塑性樹脂と熱可塑性超高分子、必要で
あればグラフト重合体との混合は、各々のペレットを粒
状のままブレンダー等で混合したものでもよいが、より
高い洗浄効果が得やすい点から、両者又は三者を押出機
等で溶融混練混合してペレット状にしたものが好まし
い。The thermoplastic resin and the thermoplastic superpolymer, and if necessary, the graft polymer may be mixed by mixing the pellets in a granular form with a blender or the like, but a higher cleaning effect is easily obtained. Therefore, it is preferable to melt-knead and mix both or three of them with an extruder or the like to form pellets.
【００２８】本洗浄剤は、これを成形機に投入して、成
形機を通常通り作動させることで洗浄効果を奏するもの
である。The present cleaning agent exhibits a cleaning effect by charging it into a molding machine and operating the molding machine as usual.
【００２９】本洗浄剤は、滑剤として、アルカリ金属
塩、特にステアリン酸マグネシウム等のステアリン酸金
属塩を添加して使用することが好ましい。このアルカリ
金属塩を添加すると、本洗浄剤を一層残留しにくくで
き、また残留しても除去しやすくなる。アルカリ金属塩
の添加量は、本洗浄剤１００重量部に対して０．１〜１
０重量部が好ましい。The detergent is preferably used by adding an alkali metal salt, especially a metal stearate such as magnesium stearate, as a lubricant. When the alkali metal salt is added, the cleaning agent can be made less likely to remain, and even if it remains, it can be easily removed. The amount of alkali metal salt added is 0.1 to 1 with respect to 100 parts by weight of the detergent.
0 parts by weight is preferred.
【００３０】上記アルカリ金属塩は、あらかじめ本洗浄
剤を構成する樹脂に添加混合しておいたり、本洗浄剤の
使用時に別途添加してもよいが、熱可塑性樹脂と熱可塑
性超高分子、必要な場合にはグラフト重合体とを混練し
た本洗浄剤に練り込んでおくと、その添加効果が大きい
ので好ましい。The above-mentioned alkali metal salt may be added to and mixed with the resin constituting the present cleaning agent in advance, or may be added separately when the present cleaning agent is used, but a thermoplastic resin and a thermoplastic ultrapolymer are required. In such a case, it is preferable to knead the same into the present cleaning agent in which the graft polymer is kneaded, because the addition effect is great.
【００３１】上記本洗浄剤を構成する樹脂へのアルカリ
金属塩の練り込みは、例えば、アルカリ金属塩と、熱可
塑性樹脂と熱可塑性超高分子とグラフト重合体のいずれ
か又は全部と予備ブレンドし、その後押出機のホッパー
口からこの予備ブレンド物を所定量押出機内に投入し
て、熱可塑性樹脂と熱可塑性超高分子とグラフト重合体
のいずれか又は全部と更に混練することで行うことがで
きる。The kneading of the alkali metal salt into the resin constituting the present cleaning agent is carried out, for example, by pre-blending with the alkali metal salt and any or all of the thermoplastic resin, the thermoplastic ultrapolymer and the graft polymer. After that, a predetermined amount of this pre-blended product is put into the extruder through the hopper port of the extruder, and further kneading can be performed with any or all of the thermoplastic resin, the thermoplastic ultrapolymer and the graft polymer. .
【００３２】本洗浄剤は、発泡剤を添加して使用すると
洗浄効果が向上するので好ましい。この発泡剤として
は、例えば重炭酸ナトリウム、炭酸アンモニウム等の無
機発泡剤であっても、例えばアゾジカルボナミド、アゾ
ビスイソブチロニトリル等の有機発泡剤でもよい。発泡
剤の添加量は、本洗浄剤１００重量部に対して０．１〜
４重量部が好ましく、特に前記アルカリ金属塩と併せて
添加することが好ましい。The present cleaning agent is preferably used by adding a foaming agent because the cleaning effect is improved. The foaming agent may be an inorganic foaming agent such as sodium bicarbonate or ammonium carbonate, or an organic foaming agent such as azodicarbonamide or azobisisobutyronitrile. The amount of the foaming agent added is 0.1 to 100 parts by weight of the detergent.
It is preferably 4 parts by weight, and particularly preferably added together with the alkali metal salt.
【００３３】発泡剤は、あらかじめ本洗浄剤を構成する
樹脂に練り込んでおいたり、本洗浄剤の使用時に別途添
加してもよいが、熱可塑性樹脂と熱可塑性超高分子、必
要な場合にはグラフト重合体とを混練した本洗浄剤に練
り込んでおくと、その添加効果が大きいので好ましい。The foaming agent may be kneaded in advance with the resin constituting the cleaning agent, or may be added separately when the cleaning agent is used, but the thermoplastic resin and the thermoplastic ultrapolymer, if necessary, may be added. Is preferably kneaded with the graft polymer and kneaded with the present cleaning agent because the effect of addition is great.
【００３４】また、本洗浄剤には、水分を含有させてお
くことが好ましい。この水分は、成形機内で蒸気とな
り、残留物の引き剥しに有効に作用する。Further, it is preferable that the cleaning agent contains water. This moisture turns into steam in the molding machine and effectively acts to strip off the residue.
【００３５】水分を含有させる場合、例えば本洗浄剤を
構成する樹脂の吸湿性を利用して吸着させたり、本洗浄
剤を構成する樹脂を多孔質として内部に水を封じ込める
ことで、本洗浄剤の投入時に水が外部に離脱しないよう
にしておくことが好ましい。例えば本洗浄剤の周囲に水
をまぶして付着させただけの場合、本洗浄剤の成形機へ
の投入時に、成形機のホッパーやホッパー直下に離脱し
た水が付着したり溜ってしまい、このままでは次に投入
される成形材料を濡らして次の成形に悪影響を及ぼすの
で、これを乾燥除去又はふき取ることが必要となる。In the case of containing water, for example, the hygroscopicity of the resin constituting the present cleaning agent is used for adsorption, or the resin constituting the present cleaning agent is made porous to confine water therein, whereby the present cleaning agent is contained. It is preferable to prevent water from being released to the outside at the time of charging. For example, in the case where the cleaning agent is simply sprinkled with water and adhered to the periphery of the cleaning agent, when the cleaning agent is put into the molding machine, the separated water adheres to or accumulates in the hopper of the molding machine or directly below the hopper. Since the molding material to be charged next has a bad influence on the next molding by being wetted, it is necessary to dry and remove it.
【００３６】水分は、本洗浄剤と共に他の樹脂を混合し
て用いる場合、この他の樹脂に含有させておくこともで
きる。When other resin is mixed with the present detergent and used, the water content can be contained in the other resin.
【００３７】含有させる水分量は、本洗浄剤１００重量
部に対して０．２〜１０重量部が好ましい。水分量が
０．２重量部未満では水分を含有させた効果が十分得に
くく、１０重量部を越えると洗浄操作が機械的に困難と
なる。The amount of water contained is preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the present detergent. If the water content is less than 0.2 parts by weight, the effect of containing water is difficult to obtain sufficiently, and if it exceeds 10 parts by weight, the washing operation becomes mechanically difficult.
【００３８】本洗浄剤は、これを成形機に投入して、成
形機をほぼ通常通り作動させることで洗浄効果を奏する
もので、射出成形機、押出成形機に対して特に有益であ
るが、これらと同様に樹脂を加熱溶融させて混練するシ
リンダー部を有する装置であれば広く適用することがで
きる。The present cleaning agent has a cleaning effect by putting it into a molding machine and operating the molding machine almost normally, and is particularly useful for injection molding machines and extrusion molding machines. Similar to these, any device having a cylinder part for melting and kneading a resin by heating can be widely applied.
【００３９】本洗浄剤をベント付成形機に使用する場合
は、使用する本洗浄剤の一部をベント口からも添加する
と好ましい結果が得られる。When the present cleaning agent is used in a molding machine with a vent, it is possible to obtain preferable results by adding a part of the present cleaning agent to be used also from the vent port.
【００４０】本洗浄剤を用いる場合の成形機の運転条件
は、シリンダーの内圧が上昇するような条件に設定する
と、効果がより顕著になるので好ましい。即ち、シリン
ダー温度を吐出可能な範囲で下げる、背圧を掛ける、高
速で射出させる、等の操作を行うことが好ましい。When the present cleaning agent is used, the operating conditions of the molding machine are preferably set so that the internal pressure of the cylinder rises, because the effect becomes more remarkable. That is, it is preferable to perform operations such as lowering the cylinder temperature within a dischargeable range, applying back pressure, and injecting at high speed.
【００４１】[0041]
【実施例】次に、本発明を実施例及び比較例によって説
明する。EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.
【００４２】実施例及び比較例における使用成形機、成
形温度及び測定条件を以下に示す。The molding machine used, the molding temperature and the measurement conditions in the examples and comparative examples are shown below.
【００４３】（１）成形機 インラインスクリュー型の射出成形機（型締力１２５ト
ン・容量１０オンス）を用いた。(1) Molding Machine An in-line screw type injection molding machine (mold clamping force 125 tons, capacity 10 ounces) was used.
【００４４】（２）成形温度 各実施例及び比較例毎に表１に示す。(2) Molding temperature Table 1 shows each example and comparative example.
【００４５】（３）メルトフローレイト ＪＩＳ−Ｋ７２１０によって測定した。(3) Melt flow rate Measured according to JIS-K7210.
【００４６】（４）アクリロニトリル含有量（ＡＮ％） 赤外線分光光度計により測定した。(4) Acrylonitrile content (AN%) It was measured by an infrared spectrophotometer.
【００４７】実施例１ スチレン−ブタジエン−アクリロニトリル共重合体（Ａ
ＢＳ）の黒色着色成形材料を成形機内に充填後、射出操
作によりに排出して成形機内を空にした。Example 1 Styrene-butadiene-acrylonitrile copolymer (A
After the black colored molding material (BS) was filled in the molding machine, it was discharged by an injection operation to empty the molding machine.
【００４８】次に、メルトフローレイトが３ｇ／１０
分、ＡＮ％が２０重量％のスチレン−アクリロニトリル
共重合体（ＡＳ）１００重量部と、分子量４５０万のポ
リエチレン（ＰＥ）系超高分子（ａ1）１０重量部とを
混練混合した本発明の洗浄剤１００重量部に対して、４
重量部の主鎖がポリプロピレン（ＰＰ）で側鎖がＡＳの
グラフト重合体（ＰＰ：５０重量％、ＡＳ：５０重量
％）を混練混合したものを成形機に０．５ｋｇ投入して
１回目の射出操作（洗浄射出操作）を行い、排出し終る
までの時間を測定した。また、洗浄剤の排出後に一般成
形用のＰＰの無色成形材料で２回目の射出操作（置換射
出操作）を行って、残留物の影響（黒色の汚班）が無い
ことが確認されるまでの時間と使用したＰＰの無色成形
材料の量を測定した。その結果を表１に示す。Next, the melt flow rate was 3 g / 10.
Of 100% by weight of a styrene-acrylonitrile copolymer (AS) having an AN% of 20% by weight and 10 parts by weight of a polyethylene (PE) -based ultrapolymer (a 1 ) having a molecular weight of 4.5 million are kneaded and mixed. 4 for 100 parts by weight of detergent
0.5 kg of a mixture obtained by kneading and mixing a graft polymer (PP: 50% by weight, AS: 50% by weight) in which a main chain of polypropylene (PP) is a side chain and a side chain is AS is charged into a molding machine for the first time. The injection operation (cleaning injection operation) was performed, and the time until the end of discharging was measured. Further, after the cleaning agent is discharged, the second injection operation (replacement injection operation) is performed with the PP colorless molding material for general molding until it is confirmed that there is no influence of the residue (black stains). The time and the amount of PP colorless molding material used were measured. Table 1 shows the results.
【００４９】比較例１ ＡＢＳの黒色着色成形材料の排出後直ちに、一般成形用
のＰＰの無色成形材料で、残留物の影響が無いことが確
認されるまで、置換射出操作を兼ねた洗浄射出操作を行
った以外は、実施例１と同様にして測定を行った。その
結果を表１に示す。COMPARATIVE EXAMPLE 1 Immediately after the black colored molding material of ABS was discharged, a colorless molding material of PP for general molding was used, and until it was confirmed that there was no influence of the residue, a washing injection operation that also served as a substitution injection operation was performed. The measurement was performed in the same manner as in Example 1 except that the above was performed. Table 1 shows the results.
【００５０】実施例２ 洗浄対象をポリフェニレンオキサイド（ＰＰＯ）の黒色
着色成形材料とし、実施例１と同じ洗浄剤１００重量部
に対し、実施例１と同じグラフト重合体４重量部を混練
混合したものを１．０ｋｇ成形機に投入した以外は、実
施例１と同様にして測定を行った。その結果を表１に示
す。Example 2 Polyphenylene oxide (PPO) was used as a black colored molding material for cleaning, and 100 parts by weight of the same cleaning agent as in Example 1 was kneaded and mixed with 4 parts by weight of the same graft polymer as in Example 1. Was measured in the same manner as in Example 1 except that was charged into a molding machine of 1.0 kg. Table 1 shows the results.
【００５１】比較例２ ＰＰＯの黒色着色成形材料を成形機内に充填後、射出操
作によりに排出して成形機内を空にした。Comparative Example 2 After the PPO black colored molding material was filled in the molding machine, it was discharged by an injection operation to empty the molding machine.
【００５２】次に、実施例１と同じＡＳ１００重量部に
対し、実施例１と同じグラフト重合体４重量部及びガラ
ス繊維２０重量部を混練混合したものを成形機に１．５
ｋｇ投入して、洗浄射出操作により排出し終るまでの時
間を測定した。また、洗浄剤の排出後に一般成形用のＰ
Ｐの無色成形材料で置換射出操作を行って、残留物の影
響が無いことが確認されるまでの時間と使用したＰＰの
無色成形材料の量を測定した。その結果を表１に示す。Next, 100 parts by weight of the same AS as in Example 1 was kneaded and mixed with 4 parts by weight of the same graft polymer as in Example 1 and 20 parts by weight of glass fiber, and the mixture was mixed in a molding machine at 1.5.
The time until the end of discharging by the injection of washing was measured by charging kg. Also, after discharging the cleaning agent, P for general molding is used.
The displacement injection operation was performed using the colorless molding material of P, and the time until it was confirmed that there was no influence of the residue and the amount of the colorless molding material of PP used were measured. Table 1 shows the results.
【００５３】実施例３ ポリエーテルイミド（ＰＥＩ）の黒色着色成形材料を成
形機内に充填後、射出操作によりに排出して成形機内を
空にした。Example 3 A black colored molding material of polyetherimide (PEI) was filled in the molding machine and then discharged by an injection operation to empty the molding machine.
【００５４】次に、メルトフローレイトが１０ｇ／１０
分のＰＥ１００重量部と、実施例１と同じＰＥ系超高分
子（ａ1）３０重量部とを混練混合した本発明の洗浄剤
を成形機に０．５ｋｇ投入して、洗浄射出操作により排
出し終るまでの時間を測定した。また、洗浄剤の排出後
に一般成形用のポリフェニレンサルファイド（ＰＰＳ）
の無色成形材料で置換射出操作を行って、残留物の影響
が無いことが確認されるまでの時間と使用したＰＰＳの
無色成形材料の量を測定した。その結果を表１に示す。Next, the melt flow rate was 10 g / 10.
Of 100 parts by weight of PE and 30 parts by weight of the same PE-based ultra-polymer (a 1 ) as in Example 1 were kneaded and mixed, and 0.5 kg of the cleaning agent of the present invention was charged into a molding machine and discharged by a cleaning injection operation. The time until the end was measured. Also, after discharging the cleaning agent, polyphenylene sulfide (PPS) for general molding is used.
Substitution injection operation was performed with the colorless molding material of No. 3, and the time until it was confirmed that there was no influence of the residue and the amount of the colorless molding material of PPS used were measured. Table 1 shows the results.
【００５５】比較例３ ＰＥＩの黒色着色成形材料の排出後直ちに、一般成形用
のＰＰＳの無色成形材料で、残留物の影響が無いことが
確認されるまで、置換射出操作を兼ねた洗浄射出操作を
行った以外は、実施例３と同様にして測定を行った。そ
の結果を表１に示す。Comparative Example 3 Immediately after the PEI black colored molding material was discharged, a PPS colorless molding material for general molding was used, and a washing and injection operation which was also performed as a replacement injection operation was performed until it was confirmed that there was no influence of the residue. The measurement was performed in the same manner as in Example 3 except that the above was performed. Table 1 shows the results.
【００５６】実施例４ メルトフローレイトが３０ｇ／１０分のＰＰ１００重量
部と実施例１と同じＰＥ系超高分子（ａ1）１０重量部
とを混練混合した本発明の洗浄剤１００重量部に対し、
実施例１と同じグラフト重合体４重量部を混練混合した
ものを成形機に１．０ｋｇ投入して洗浄射出操作を行っ
た以外は、実施例１と同様にして測定を行った。その結
果を表１に示す。Example 4 100 parts by weight of the detergent of the present invention prepared by kneading and mixing 100 parts by weight of PP having a melt flow rate of 30 g / 10 min and 10 parts by weight of the same PE-based ultrapolymer (a 1 ) as in Example 1 In contrast,
The measurement was performed in the same manner as in Example 1 except that 1.0 kg of a mixture obtained by kneading and mixing 4 parts by weight of the same graft polymer as in Example 1 was charged into the molding machine and the washing injection operation was performed. Table 1 shows the results.
【００５７】実施例５ 実施例１と同じＡＳ１００重量部と分子量２００万のＰ
Ｅ系超高分子（ａ2）１０重量部とを混練混合した本発
明の洗浄剤１００重量部に対し、実施例１と同じグラフ
ト重合体４重量部を混練混合したものを成形機に１．０
ｋｇ投入して洗浄射出操作を行った以外は、実施例１と
同様にして測定を行った。その結果を表１に示す。Example 5 The same AS 100 parts by weight as in Example 1 and P having a molecular weight of 2,000,000 were used.
1. A molding machine was prepared by kneading and mixing 4 parts by weight of the same graft polymer as in Example 1 with 100 parts by weight of the cleaning agent of the present invention obtained by kneading and mixing 10 parts by weight of E-type ultra-high polymer (a 2 ). 0
The measurement was performed in the same manner as in Example 1 except that the washing injection operation was performed by introducing kg. Table 1 shows the results.
【００５８】比較例４ 実施例１と同じＡＳ１００重量部と分子量８０万のＰＥ
系超高分子（ａ3）１０重量部とを混練混合した洗浄剤
１００重量部に対し、実施例１と同じグラフト重合体４
重量部を混練混合したものを成形機に３．０ｋｇ投入し
て洗浄射出操作を行った以外は、実施例１と同様にして
測定を行った。その結果を表１に示す。Comparative Example 4 100 parts by weight of AS same as in Example 1 and PE having a molecular weight of 800,000
The same graft polymer 4 as in Example 1 was added to 100 parts by weight of the cleaning agent obtained by kneading and mixing 10 parts by weight of the ultra-high polymer (a 3 ).
The measurement was performed in the same manner as in Example 1 except that 3.0 kg of a mixture obtained by kneading and mixing parts by weight was put into a molding machine and a washing injection operation was performed. Table 1 shows the results.
【００５９】実施例６ 実施例１と同じＡＳ１００重量部と分子量４５０万のポ
リメチルメタクリレート（ＰＭＭＡ）系超高分子
（ｂ1）１０重量部とを混練混合した本発明の洗浄剤１
００重量部に対し、実施例１と同じグラフト重合体４重
量部を混練混合したものを成形機に０．５ｋｇ投入して
洗浄射出操作を行った以外は、実施例１と同様にして測
定を行った。その結果を表１に示す。Example 6 The cleaning agent 1 of the present invention prepared by kneading and mixing 100 parts by weight of the same AS as in Example 1 and 10 parts by weight of a polymethylmethacrylate (PMMA) type ultra polymer (b 1 ) having a molecular weight of 4.5 million.
Measurement was carried out in the same manner as in Example 1 except that 0.5 part of the same graft polymer as in Example 1 was kneaded and mixed with 0.5 part by weight, and 0.5 kg was put into a molding machine to perform a washing injection operation. went. Table 1 shows the results.
【００６０】実施例７ 実施例１と同じＡＳ１００重量部と分子量４００万のＡ
Ｓ系超高分子（ｂ2）１０重量部とを混練混合した本発
明の洗浄剤１００重量部に対し、実施例１と同じグラフ
ト重合体４重量部を混練混合したものを成形機に０．５
ｋｇ投入して洗浄射出操作を行った以外は、実施例１と
同様にして測定を行った。その結果を表１に示す。Example 7 100 parts by weight of AS same as in Example 1 and A having a molecular weight of 4,000,000
100 parts by weight of the cleaning agent of the present invention obtained by kneading and mixing 10 parts by weight of S-based ultra-polymer (b 2 ) with 4 parts by weight of the same graft polymer as in Example 1 were mixed and mixed in a molding machine. 5
The measurement was performed in the same manner as in Example 1 except that the washing injection operation was performed by introducing kg. Table 1 shows the results.
【００６１】実施例８ 実施例１と同じＡＳ１００重量部と実施例１と同じＰＥ
系超高分子（ａ1）５重量部とを混練混合した本発明の
洗浄剤１００重量部に対し、実施例１と同じグラフト重
合体４重量を部混練混合したものを成形機に１．５ｋｇ
投入して洗浄射出操作を行った以外は、実施例１と同様
にして測定を行った。その結果を表１に示す。Example 8 100 parts by weight of AS same as in Example 1 and PE same as in Example 1
1.5 kg of a mixture obtained by kneading and mixing 4 parts of the same graft polymer as in Example 1 with 100 parts by weight of the cleaning agent of the present invention obtained by kneading and mixing 5 parts by weight of the system ultrapolymer (a 1 ) was used in a molding machine.
The measurement was performed in the same manner as in Example 1 except that the cleaning and injection operation was performed after charging. Table 1 shows the results.
【００６２】比較例５ 実施例１と同じＡＳ１００重量部と実施例１と同じＰＥ
系超高分子（ａ1）６０重量部とを混練混合した洗浄剤
１００重量部に対し、実施例１と同じグラフト重合体４
重量部を混練混合したものを成形機に０．５ｋｇ投入し
て洗浄射出操作を行った以外は、実施例１と同様にして
測定を行った。その結果を表１に示す。Comparative Example 5 AS 100 parts by weight same as in Example 1 and PE same as in Example 1
System ultrahigh molecular (a 1) to a 60 parts by weight of kneaded mixture was cleaner 100 parts by weight, the same graft polymer 4 of Example 1
The measurement was performed in the same manner as in Example 1 except that 0.5 kg of a mixture obtained by kneading and mixing parts by weight was put into a molding machine and a washing injection operation was performed. Table 1 shows the results.
【００６３】[0063]
【表１】 [Table 1]
【００６４】[0064]
【発明の効果】本発明は、以上説明した通りのものであ
り、高い洗浄効果が得られるのみでなく、ガラス繊維又
はガラス粒を混入する必要がないため、洗浄時に成形機
内部を傷つけることなく、しかも洗浄剤廃棄時には完全
焼却が可能である。EFFECTS OF THE INVENTION The present invention is as described above, and not only a high cleaning effect is obtained, but it is not necessary to mix glass fibers or glass particles, so that the inside of the molding machine is not damaged during cleaning. Moreover, it is possible to completely incinerate the cleaning agent when it is discarded.
Claims (3)
塑性超高分子２〜５０重量部混合されていることを特徴
とする成形機用洗浄剤。1. A detergent for a molding machine, wherein 2 to 50 parts by weight of a thermoplastic ultrapolymer are mixed with 100 parts by weight of a thermoplastic resin.
可塑性超高分子がポリエチレン系超高分子であることを
特徴とする請求項１記載の成形機用洗浄剤。2. The cleaning agent for a molding machine according to claim 1, wherein the thermoplastic resin is a polyethylene resin and the thermoplastic ultra-polymer is a polyethylene ultra-polymer.
をなすスチレン系重合体とから構成されるグラフト重合
体が、スチレン−アクリロニトリル系樹脂とポリエチレ
ン系超高分子よりなる請求項１記載の成形機用洗浄剤１
００重量部に対して２〜１６０重量部混合されているこ
とを特徴とする成形機用洗浄剤。3. The graft polymer composed of an olefin polymer forming a main chain and a styrene polymer forming a side chain is composed of a styrene-acrylonitrile resin and a polyethylene ultrapolymer. Molding machine cleaner 1
A cleaning agent for a molding machine, which is mixed in an amount of 2 to 160 parts by weight with respect to 00 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33037094A JP3218422B2 (en) | 1994-12-07 | 1994-12-07 | Cleaning agent for molding machines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33037094A JP3218422B2 (en) | 1994-12-07 | 1994-12-07 | Cleaning agent for molding machines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08155969A true JPH08155969A (en) | 1996-06-18 |
| JP3218422B2 JP3218422B2 (en) | 2001-10-15 |
Family
ID=18231851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33037094A Expired - Lifetime JP3218422B2 (en) | 1994-12-07 | 1994-12-07 | Cleaning agent for molding machines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3218422B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001138339A (en) * | 1999-11-16 | 2001-05-22 | Nitto Kako Kk | Resin composition for cleaning plastic molding machine/ extruder |
| JP2001348600A (en) * | 2000-06-06 | 2001-12-18 | Asahi Kasei Corp | Detergent for molding machine |
| US6551411B1 (en) | 1999-03-24 | 2003-04-22 | Asahi Kasei Kabushiki Kaisha | Detergent composition |
| JP2005231108A (en) * | 2004-02-18 | 2005-09-02 | Asahi Kasei Chemicals Corp | Washing agent for molding machine |
| JPWO2007116920A1 (en) * | 2006-04-05 | 2009-08-20 | 脩 井澤 | Resin switching detergent for injection molding machines |
| JP2010125663A (en) * | 2008-11-26 | 2010-06-10 | Asahi Kasei Chemicals Corp | Detergent |
| WO2011024828A1 (en) | 2009-08-26 | 2011-03-03 | ダイセルポリマー株式会社 | Thermoplastic resin composition for cleaning |
| US20160101553A1 (en) * | 2014-10-10 | 2016-04-14 | Ticona Llc | Processes for cleaning melt processing equipment |
| WO2019039542A1 (en) * | 2017-08-25 | 2019-02-28 | 長瀬産業株式会社 | Molding machine cleaning agent |
-
1994
- 1994-12-07 JP JP33037094A patent/JP3218422B2/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6551411B1 (en) | 1999-03-24 | 2003-04-22 | Asahi Kasei Kabushiki Kaisha | Detergent composition |
| JP2001138339A (en) * | 1999-11-16 | 2001-05-22 | Nitto Kako Kk | Resin composition for cleaning plastic molding machine/ extruder |
| JP4670110B2 (en) * | 1999-11-16 | 2011-04-13 | 日東化工株式会社 | Cleaning resin composition for plastic molding machines and extruders |
| JP2001348600A (en) * | 2000-06-06 | 2001-12-18 | Asahi Kasei Corp | Detergent for molding machine |
| JP4564133B2 (en) * | 2000-06-06 | 2010-10-20 | 旭化成ケミカルズ株式会社 | Cleaning agent for molding machine and cleaning method of molding machine |
| JP4504699B2 (en) * | 2004-02-18 | 2010-07-14 | 旭化成ケミカルズ株式会社 | Cleaning agent for molding machine |
| JP2005231108A (en) * | 2004-02-18 | 2005-09-02 | Asahi Kasei Chemicals Corp | Washing agent for molding machine |
| JPWO2007116920A1 (en) * | 2006-04-05 | 2009-08-20 | 脩 井澤 | Resin switching detergent for injection molding machines |
| JP2010125663A (en) * | 2008-11-26 | 2010-06-10 | Asahi Kasei Chemicals Corp | Detergent |
| WO2011024828A1 (en) | 2009-08-26 | 2011-03-03 | ダイセルポリマー株式会社 | Thermoplastic resin composition for cleaning |
| JP2011046808A (en) * | 2009-08-26 | 2011-03-10 | Daicel Polymer Ltd | Thermoplastic resin composition for cleaning |
| US20160101553A1 (en) * | 2014-10-10 | 2016-04-14 | Ticona Llc | Processes for cleaning melt processing equipment |
| WO2019039542A1 (en) * | 2017-08-25 | 2019-02-28 | 長瀬産業株式会社 | Molding machine cleaning agent |
| JPWO2019039542A1 (en) * | 2017-08-25 | 2019-11-07 | 長瀬産業株式会社 | Molding machine cleaner |
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|---|---|
| JP3218422B2 (en) | 2001-10-15 |
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