JP2003041042A - Method for producing foamable colored resin particle - Google Patents
Method for producing foamable colored resin particleInfo
- Publication number
- JP2003041042A JP2003041042A JP2001228106A JP2001228106A JP2003041042A JP 2003041042 A JP2003041042 A JP 2003041042A JP 2001228106 A JP2001228106 A JP 2001228106A JP 2001228106 A JP2001228106 A JP 2001228106A JP 2003041042 A JP2003041042 A JP 2003041042A
- Authority
- JP
- Japan
- Prior art keywords
- colored resin
- resin particles
- weight
- dye
- expandable
- 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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Links
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、発泡性着色樹脂粒子、
着色樹脂発泡体および着色樹脂発泡成形体に関するもの
である。FIELD OF THE INVENTION The present invention relates to expandable colored resin particles,
The present invention relates to a colored resin foam and a colored resin foam molded article.
【０００２】[0002]
【従来の技術】従来、発泡性着色樹脂粒子を得る方法と
して、熱可塑性樹脂粒子を水性媒体中に分散させた後、
易揮発性発泡剤を含浸させる際に、水性媒体中に、最大
長さが３００μｍ以上のものの含有量が４０％以下であ
る染料を分散させる方法が提案されている（特開平６−
１５７８０５号公報）。しかしながら、この方法では、
陰イオン界面活性剤の存在下に染料を分解させてなる染
料分散液をプロペラ翼で撹拌した場合は分散が不充分
で、染料が熱可塑性樹脂粒子の表面に細かく均一に吸着
せず、粗大な状態で吸着するので、成形品の色むらが著
しく発生する。そこで、プロペラ翼よりも攪拌する能力
が高く、染料を破砕する働きのあるホモミキサーにより
１０分以上撹拌し、染料を分散させなければならないと
いう問題がある。また、２種類以上の染料を使用した場
合には、それぞれの染料の吸収速度の違いにより、１種
類の染料を使用した場合よりも色むらが発生し易くな
り、本生産にスケールアップした場合には色むらの発生
がさらに顕著となる。2. Description of the Related Art Conventionally, as a method of obtaining expandable colored resin particles, after dispersing thermoplastic resin particles in an aqueous medium,
A method of dispersing a dye having a maximum length of 300 μm or more and a content of 40% or less in an aqueous medium when impregnating a volatile foaming agent has been proposed (JP-A-6-
157805). However, with this method,
When a dye dispersion prepared by decomposing the dye in the presence of an anionic surfactant is agitated with a propeller blade, the dispersion is insufficient and the dye does not adsorb finely and uniformly on the surface of the thermoplastic resin particles, resulting in coarse particles. Since it is adsorbed in the state, the color unevenness of the molded product remarkably occurs. Therefore, there is a problem that the dye has to be dispersed by stirring with a homomixer having a higher stirring ability than the propeller blade and having a function of crushing the dye for 10 minutes or more. Also, when two or more types of dyes are used, color unevenness is more likely to occur than when one type of dye is used due to the difference in absorption rate of each dye, and when scaled up to the main production The occurrence of color unevenness becomes more remarkable.
【０００３】特開昭５７−１１１３３１号公報では、界
面活性剤としてプロピレンオキシドとエチレンオキシド
とのブロック共重合体で、ＨＬＢ価が８〜１８、平均分
子量が１０００以上である非イオン界面活性剤を約０．
００５〜０．３重量％（水に対し）含む水性懸濁媒質中
で、樹脂粒子に発泡剤を含浸させることにより発泡性ス
チレン系重合体ビーズを製造する方法が提案されてい
る。この方法によれば、予備発泡後のビーズのセルが不
均一になる、すなわち、外側周辺に向かってセルが小さ
くなり、芯に向かってセルが大きくなるようなセル構造
を有する予備発泡重合体ビーズの得られることが記載さ
れている［図２参照］。このような不均一なビーズは、
最終成形処理での冷却時間を短縮するためには、均一な
セル分布を有する場合よりも好ましいことが報告されて
いる。また、このビーズに染料を含ませることができる
と報告されている。In JP-A-57-111331, a nonionic surfactant having a HLB value of 8 to 18 and an average molecular weight of 1,000 or more is used as a surfactant, which is a block copolymer of propylene oxide and ethylene oxide. 0.
It has been proposed to produce expandable styrenic polymer beads by impregnating resin particles with a blowing agent in an aqueous suspension medium containing 005 to 0.3% by weight (based on water). According to this method, the pre-expanded polymer beads have a cell structure in which the cells of the beads after pre-expansion become nonuniform, that is, the cells become smaller toward the outer periphery and become larger toward the core. Is obtained [see FIG. 2]. Such non-uniform beads
It has been reported that it is preferable to have a uniform cell distribution in order to shorten the cooling time in the final molding process. It is also reported that the beads can contain a dye.
【０００４】しかしながら、このような発泡性スチレン
系重合体ビーズに染料を含ませると、外側周辺のセルが
小さくなっていることから色が薄く見えるという問題が
ある。したがって、均一なセル分布を有する着色ビーズ
と同じ色合いにするためには染料の添加量を増やさなけ
ればならず、特に濃厚色に着色するためには、より多量
の染料が必要となる。そして、多量の染料が用いられる
と、染料が樹脂に吸収されないで反応液中に多量に残存
するため、排水処理が繁雑になる。However, when a dye is contained in such expandable styrenic polymer beads, there is a problem that the color appears light because the cells around the outside are small. Therefore, the amount of the dye added must be increased in order to obtain the same shade as that of the colored beads having a uniform cell distribution, and a larger amount of dye is required for coloring in a particularly deep color. When a large amount of dye is used, the dye is not absorbed by the resin and remains in the reaction liquid in a large amount, which makes wastewater treatment complicated.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、以上のよう
な問題を解決するためになされたものであり、均一に着
色でき、発泡体の気泡サイズが外側周辺に向かって小さ
くならない発泡性着色樹脂粒子の製造方法、この製造方
法で得られる発泡性着色樹脂粒子、着色樹脂発泡体およ
び着色樹脂発泡成形体を提供するものである。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and is capable of uniformly coloring, and foaming coloring in which the cell size of the foam does not decrease toward the outer periphery. The present invention provides a method for producing resin particles, an expandable colored resin particle obtained by this method, a colored resin foam and a colored resin foam molded article.
【０００６】[0006]
【課題を解決するための手段】本発明によれば、熱可塑
性樹脂粒子が分散された水性分散液中で、前記粒子に染
料および易揮発性発泡剤を含浸させることにより発泡性
着色樹脂粒子を製造する方法において、重量平均分子量
が６５００以上である非イオン界面活性剤の存在下に染
料を含浸させることを特徴とする発泡性着色樹脂粒子の
製造方法が提供される。According to the present invention, expandable colored resin particles are prepared by impregnating the particles with a dye and a volatile foaming agent in an aqueous dispersion in which thermoplastic resin particles are dispersed. In the method for producing, there is provided a method for producing expandable colored resin particles, which comprises impregnating a dye in the presence of a nonionic surfactant having a weight average molecular weight of 6500 or more.
【０００７】また、本発明によれば、上記の方法により
得られた発泡性着色樹脂粒子、並びに該発泡性着色樹脂
粒子からなる着色樹脂発泡体および着色樹脂発泡成形体
が提供される。According to the present invention, there is also provided an expandable colored resin particle obtained by the above method, a colored resin foam made of the expandable colored resin particle, and a colored resin foam molded article.
【０００８】[0008]
【発明の実施の形態】本発明における発泡性着色樹脂粒
子の製造方法は、熱可塑性樹脂粒子が分散された水性分
散液中で、前記粒子に染料および易揮発性発泡剤を含浸
させることにより発泡性着色樹脂粒子を製造する方法に
おいて、重量平均分子量が６５００以上である非イオン
界面活性剤の存在下に染料を含浸させることを特徴とす
る。BEST MODE FOR CARRYING OUT THE INVENTION The method for producing expandable colored resin particles according to the present invention comprises foaming by impregnating the particles with a dye and a volatile foaming agent in an aqueous dispersion in which thermoplastic resin particles are dispersed. The method for producing a colored resin particle is characterized in that the dye is impregnated in the presence of a nonionic surfactant having a weight average molecular weight of 6500 or more.
【０００９】水性分散液は、水性媒体中に少なくとも熱
可塑性樹脂粒子を分散させたものである。熱可塑性樹脂
粒子としては、例えば、ポリスチレン樹脂、少なくとも
５０重量％以上のスチレン成分と他の共重合可能な不飽
和化合物との共重合体等からなる粒子が挙げられる。ス
チレンと共重合可能な不飽和化合物としては、例えばα
−メチルスチレン、アクリロニトリル、アクリル酸もし
くはメタクリル酸と１〜８個の炭素原子数を有するアル
コールとのエステル、マレイン酸、フマル酸と１〜８個
の炭素原子数を有するアルコールとのエステル、無水マ
レイン酸が挙げられる。これらの不飽和化合物には、ジ
ビニルベンゼン、ブタジエン、ポリエチレングリコール
ジタクリレート等の架橋剤を少量加えてもよい。The aqueous dispersion is a dispersion of at least thermoplastic resin particles in an aqueous medium. Examples of the thermoplastic resin particles include particles made of polystyrene resin, a copolymer of at least 50% by weight or more of a styrene component and another copolymerizable unsaturated compound, and the like. Examples of unsaturated compounds copolymerizable with styrene include α
-Methylstyrene, acrylonitrile, esters of acrylic acid or methacrylic acid with alcohols having 1 to 8 carbon atoms, maleic acid, fumaric acid and esters of alcohols having 1 to 8 carbon atoms, maleic anhydride. An acid is mentioned. To these unsaturated compounds, a small amount of a cross-linking agent such as divinylbenzene, butadiene, polyethylene glycol ditacrylate may be added.
【００１０】また、熱可塑性樹脂粒子としては、この他
にメタクリル酸エステルのホモポリマー、メタクリル酸
エステルを主成分とするコポリマー、ポリエチレン、ポ
リプロピレン等のポリオレフィン等からなる粒子が挙げ
られる。これらの熱可塑性樹脂は、それぞれ単独で、ま
たは２種以上を組合わせて用いることができる。また、
熱可塑性樹脂は、適量のゴム状物質を添加して強化樹脂
にしたものであってもよい。Other examples of the thermoplastic resin particles include homopolymers of methacrylic acid ester, copolymers containing methacrylic acid ester as a main component, and particles of polyolefin such as polyethylene and polypropylene. These thermoplastic resins can be used alone or in combination of two or more kinds. Also,
The thermoplastic resin may be a reinforced resin obtained by adding an appropriate amount of a rubber-like substance.
【００１１】非イオン界面活性剤の重量平均分子量は６
５００以上であり、好ましくは６５００〜２００００、
さらに好ましくは８０００〜１５０００である。なお、
重量平均分子量はゲルパーミエーションクロマトグラフ
（ＧＰＣ）により測定したものである。非イオン界面活
性剤の重量平均分子量が６５００を下回ると、非イオン
界面活性剤が熱可塑性樹脂粒子内に過剰に吸収されてし
まう。過剰に吸収された非イオン界面活性剤は、気泡核
剤として作用し、得られる発泡体の気泡サイズが外側周
辺に向かって小さくなるため、着色樹脂発泡成形体の色
が薄くなる。また、非イオン界面活性剤の重量平均分子
量が２００００を上回ると、熱可塑性樹脂粒子内への吸
収が低下し、本発明の効果が低下するおそれがある。The weight average molecular weight of the nonionic surfactant is 6
500 or more, preferably 6500 to 20000,
More preferably, it is 8000-15000. In addition,
The weight average molecular weight is measured by gel permeation chromatography (GPC). When the weight average molecular weight of the nonionic surfactant is less than 6500, the nonionic surfactant is excessively absorbed in the thermoplastic resin particles. The excessively absorbed nonionic surfactant acts as a cell nucleating agent, and the cell size of the obtained foam becomes smaller toward the outer periphery, so that the color of the colored resin foam molded article becomes lighter. Further, when the weight average molecular weight of the nonionic surfactant exceeds 20,000, the absorption into the thermoplastic resin particles is reduced, and the effect of the present invention may be reduced.
【００１２】非イオン界面活性剤は、水性分散液に分散
させた染料に対して、染料の周囲を取り囲んで包み込む
保護コロイドとして作用すると考えられ、染料同士が凝
集して粗大粒子となることを防ぎ、染料を微細粒子のま
ま保つ効果がある。染料が微細粒子である場合には、熱
可塑性樹脂粒子の表面に細かく均一に分散し吸着される
が、粗大粒子となってしまった場合には、樹脂粒子の表
面に大きな固まりとして付着し吸着されてしまうので、
その樹脂粒子の表面の色が濃くなってしまい、樹脂発泡
成形体としたときに色むらとなってしまう。The nonionic surfactant is considered to act as a protective colloid for the dye dispersed in the aqueous dispersion so as to surround and surround the dye, and prevent the dyes from aggregating into coarse particles. , Has the effect of keeping the dye as fine particles. When the dye is fine particles, it is finely and uniformly dispersed and adsorbed on the surface of the thermoplastic resin particles, but when it becomes coarse particles, it is adsorbed by adhering as large lumps on the surface of the resin particles. Because it will be
The color of the surface of the resin particles becomes dark, resulting in uneven coloration when the resin foam molding is formed.
【００１３】非イオン界面活性剤としては、得られる発
泡体における気泡サイズに影響を与えず、色むらを発生
させないという点で、プロピレンオキシドとエチレンオ
キシドのブロック共重合体が好ましい。ここで、エチレ
ンオキシドは水になじみやすい親水基の役割をし、プロ
ピレンオキシドは水になじみにくい親油基の役割をす
る。As the nonionic surfactant, a block copolymer of propylene oxide and ethylene oxide is preferable in that it does not affect the cell size in the obtained foam and does not cause color unevenness. Here, ethylene oxide plays a role of a hydrophilic group which is easily adapted to water, and propylene oxide plays a role of a lipophilic group which is not easily adapted to water.
【００１４】ブロック共重合体におけるエチレンオキシ
ドの含有量は、２０〜９５重量％が好ましく、４０〜９
５重量％がさらに好ましく、６０〜９０重量％が特に好
ましい。エチレンオキシドの含有量が２０重量％を下回
ると、非イオン界面活性剤が水性分散液に難溶となり、
活性剤としての役割を果たし難くなるので好ましくな
い。また、エチレンオキシドの含有量が９５重量％を上
回ると水性分散液に溶けやすくなる反面、熱可塑性樹脂
粒子や染料との相溶性が低くなり、保護コロイドとして
作用する効果も低くなることから、染料を樹脂粒子の表
面に細かく均一に分散し吸着させることが困難になるの
で好ましくない。The content of ethylene oxide in the block copolymer is preferably 20 to 95% by weight, and 40 to 9% by weight.
5% by weight is more preferable, and 60 to 90% by weight is particularly preferable. When the content of ethylene oxide is less than 20% by weight, the nonionic surfactant becomes hardly soluble in the aqueous dispersion,
It is not preferable because it becomes difficult to fulfill the role as an activator. Further, when the content of ethylene oxide exceeds 95% by weight, it becomes easy to dissolve in the aqueous dispersion, but on the other hand, the compatibility with the thermoplastic resin particles and the dye becomes low, and the effect of acting as a protective colloid also becomes low. It is not preferable because it becomes difficult to finely and uniformly disperse and adsorb on the surface of the resin particles.
【００１５】非イオン界面活性剤の添加量は、熱可塑性
樹脂粒子に対して０．００１〜１重量％が好ましく、
０．００５〜０．５重量％がさらに好ましい。非イオン
界面活性剤の添加量が０．００１重量％を下回ると均一
な着色効果が発揮され難く、また、１重量％を上回ると
分散系を壊して樹脂粒子同士の合着が発生しやすくなる
ので好ましくない。The amount of the nonionic surfactant added is preferably 0.001 to 1% by weight based on the thermoplastic resin particles,
0.005-0.5% by weight is more preferable. If the addition amount of the nonionic surfactant is less than 0.001% by weight, it is difficult to exert a uniform coloring effect, and if it exceeds 1% by weight, the dispersion system is broken and the resin particles are likely to be fused with each other. It is not preferable.
【００１６】染料としては、例えばモノアゾ系染料、ア
ントラキノン系染料、ジスアゾ系染料、ペリノン系染
料、フタロシアニン系染料等が挙げられる。これらの染
料は、単独で、または２種以上を組合わせて用いること
ができる。なお、染料を２種以上組合わせて用いると、
顧客の好みに対応したさまざまな色を提供できる点で好
ましい。染料の添加量は、熱可塑性樹脂粒子に対して
０．０００５〜２重量％程度が好ましい。染料の添加量
が０．０００５重量％を下回ると、十分な着色効果が得
られ難い。また、２重量％を上回ると、染料が樹脂に吸
収され難くなり、染料が水性分散液中に残存するため、
排水処理が繁雑になるので好ましくない。染料は、直接
水性分散液に添加してもうまく分散しないため、予め適
当な液体に分散させて染料分散液としたものを添加する
のが好ましい。Examples of the dyes include monoazo dyes, anthraquinone dyes, disazo dyes, perinone dyes and phthalocyanine dyes. These dyes can be used alone or in combination of two or more. If two or more dyes are used in combination,
It is preferable in that various colors can be provided according to customer's taste. The addition amount of the dye is preferably about 0.0005 to 2% by weight with respect to the thermoplastic resin particles. When the amount of the dye added is less than 0.0005% by weight, it is difficult to obtain a sufficient coloring effect. If it exceeds 2% by weight, the dye becomes difficult to be absorbed by the resin, and the dye remains in the aqueous dispersion,
It is not preferable because wastewater treatment becomes complicated. Since the dye does not disperse well even if it is added directly to the aqueous dispersion, it is preferable to add a dye dispersed in an appropriate liquid in advance to form a dye dispersion.
【００１７】易揮発性発泡剤（以下、「発泡剤」とい
う）としては、沸点がポリスチレン系樹脂の軟化点以下
であって、２０℃、１気圧でガス状もしくは液状の有機
化合物が適しており、例えばプロパン、ブタン、ペンタ
ン、石油エーテル等の炭化水素、ジメチルエーテル、ジ
プロピルエーテル等の低沸点のエーテル化合物等が挙げ
られる。これらの発泡剤は、それぞれ単独で、または２
種類以上を組合わせて用いてもよい。発泡剤の添加量
は、通常、熱可塑性樹脂粒子に対して３〜１０重量％含
浸されるように適宜調節され、また、要求される発泡倍
数によっても適宜調節される。As the volatile foaming agent (hereinafter referred to as "foaming agent"), an organic compound having a boiling point not higher than the softening point of the polystyrene resin and being gaseous or liquid at 20 ° C. and 1 atmosphere is suitable. Examples thereof include hydrocarbons such as propane, butane, pentane and petroleum ether, and low boiling point ether compounds such as dimethyl ether and dipropyl ether. These foaming agents may be used alone or in combination with each other.
A combination of more than one type may be used. The amount of the foaming agent added is usually appropriately adjusted so that the thermoplastic resin particles are impregnated with 3 to 10% by weight, and is also appropriately adjusted depending on the required expansion ratio.
【００１８】本発明の方法で染料および発泡剤を含浸さ
せる際に、染料と発泡剤のどちらを先に水性分散液に添
加してもよいが、発泡剤を添加する前に、または発泡剤
と同時に染料を添加するのが好ましい。染料および発泡
剤の含浸は、４０℃から１３０℃の範囲で行うのが好ま
しく、８０〜１１０℃で行うのがさらに好ましい。含浸
時の温度が４０℃を下回ると、含浸圧力が低くなり、発
泡剤の含浸に長時間を要するので好ましくない。また、
含浸時の温度が１３０℃を上回ると、得られる発泡体の
気泡が密になり、色が薄く見えやすくなるので好ましく
ない。When the dye and the foaming agent are impregnated by the method of the present invention, either the dye or the foaming agent may be added to the aqueous dispersion first, but before the foaming agent is added or the foaming agent is added. It is preferable to add the dye at the same time. The impregnation with the dye and the foaming agent is preferably performed in the range of 40 ° C to 130 ° C, more preferably 80 to 110 ° C. If the temperature during the impregnation is lower than 40 ° C., the impregnation pressure becomes low, and it takes a long time to impregnate the foaming agent, which is not preferable. Also,
When the temperature at the time of impregnation exceeds 130 ° C., the bubbles of the obtained foam become dense and the color tends to appear light, which is not preferable.
【００１９】本発明の方法では、発泡助剤としてシクロ
ヘキサンのような脂環式炭化水素を水性分散液に添加し
てもよい。発泡助剤を用いる場合、その添加量は、熱可
塑性樹脂粒子に対して０．１〜３．０重量％程度が好ま
しい。本発明の方法では、難燃剤、難燃助剤として、ハ
ロゲン系難燃剤、リン系難燃剤、窒素化合物、金属塩、
金属酸化物等を水性媒体に添加してもよい。本発明の方
法では、発泡性着色樹脂粒子の気泡を均一にする目的
で、アマイド系化合物、高級脂肪酸、高級脂肪酸アミ
ド、食用油、高級脂肪酸トリグリセライド、高級脂肪酸
モノグリセライド、パラフィンワックス、ポリエチレン
ワックス等を水性分散液に添加してもよい。In the method of the present invention, an alicyclic hydrocarbon such as cyclohexane may be added to the aqueous dispersion as a foaming aid. When a foaming aid is used, its addition amount is preferably about 0.1 to 3.0% by weight based on the thermoplastic resin particles. In the method of the present invention, a flame retardant, a flame retardant aid, a halogen flame retardant, a phosphorus flame retardant, a nitrogen compound, a metal salt,
You may add a metal oxide etc. to an aqueous medium. In the method of the present invention, an amide compound, a higher fatty acid, a higher fatty acid amide, an edible oil, a higher fatty acid triglyceride, a higher fatty acid monoglyceride, a paraffin wax, a polyethylene wax or the like is used as an aqueous solution for the purpose of making the bubbles of the expandable colored resin particles uniform. It may be added to the dispersion.
【００２０】本発明の方法では、熱可塑性樹脂粒子を水
性分散液中に均一に分散させるために、分散剤として、
有機高分子系分散剤や難水溶性無機塩などを添加しても
よい。有機高分子系分散剤としては、例えばポリビニル
アルコール、アルキルセルロース、ヒドロキシアルキル
セルロース、カルボキシアルキルセルロース等のセルロ
ース誘導体が挙げられる。難水溶性無機塩としては、例
えばリン酸三カルシウム、リン酸マグネシウム、ピロリ
ン酸マグネシウム等が挙げられる。分散剤の添加量は、
熱可塑性樹脂粒子に対して０．１〜１．０重量％程度が
好ましい。In the method of the present invention, in order to uniformly disperse the thermoplastic resin particles in the aqueous dispersion, the dispersant is
An organic polymer-based dispersant or a poorly water-soluble inorganic salt may be added. Examples of the organic polymer dispersant include polyvinyl alcohol, alkyl cellulose, hydroxyalkyl cellulose, carboxyalkyl cellulose, and other cellulose derivatives. Examples of the poorly water-soluble inorganic salt include tricalcium phosphate, magnesium phosphate, magnesium pyrophosphate and the like. The amount of dispersant added is
It is preferably about 0.1 to 1.0% by weight with respect to the thermoplastic resin particles.
【００２１】本発明の方法では、上記の分散剤と共に、
分散助剤として微量の陰イオン界面活性剤を用いてもよ
い。陰イオン界面活性剤はマイナスの電荷を帯びている
ので、電気的な反発によって、熱可塑樹脂粒子または染
料の凝集を防ぐ。陰イオン界面活性剤としては、例えば
ドデシルベンゼンスルホン酸ナトリウムのようなアルキ
ルベンゼンスルホン酸塩、ラウリル硫酸ナトリウムのよ
うなアルキル硫酸エステル塩、アルキルナフタレンスル
ホン酸ナトリウムのようなアルキルナフタレンスルホン
酸塩、アルキルジアリルエーテルスルホン酸ナトリウム
のようなアルキルジアリルエーテルスルホン酸塩等が挙
げられる。これらの陰イオン界面活性剤は、それぞれ単
独で、または２種以上を組合わせて用いることができ
る。In the method of the present invention, together with the above dispersant,
A small amount of anionic surfactant may be used as the dispersion aid. Since the anionic surfactant has a negative charge, it electrically repels to prevent aggregation of the thermoplastic resin particles or dye. Examples of anionic surfactants include alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfate ester salts such as sodium lauryl sulfate, alkylnaphthalene sulfonates such as sodium alkylnaphthalene sulfonate, and alkyl diallyl ethers. Examples thereof include alkyl diallyl ether sulfonates such as sodium sulfonate. These anionic surfactants may be used alone or in combination of two or more.
【００２２】陰イオン界面活性剤の添加量は、熱可塑性
樹脂粒子に対して０．００１〜０．２重量％程度が好ま
しい。陰イオン界面活性剤の添加量が０．００１重量％
を下回ると、分散助剤としての効果、すなわち電気的な
反発によって熱可塑性樹脂粒子または染料の凝集を防ぐ
効果が得られないので好ましくない。また、陰イオン界
面活性剤の添加量が０．２重量％を上回ると発泡性着色
樹脂粒子の製造時に泡立ちが起こりやすくなるので好ま
しくない。The amount of the anionic surfactant added is preferably about 0.001 to 0.2% by weight based on the thermoplastic resin particles. Addition amount of anionic surfactant is 0.001% by weight
When it is below the range, the effect as a dispersion aid, that is, the effect of preventing aggregation of the thermoplastic resin particles or the dye due to electric repulsion cannot be obtained, which is not preferable. If the amount of the anionic surfactant added exceeds 0.2% by weight, foaming tends to occur during the production of the expandable colored resin particles, which is not preferable.
【００２３】本発明の方法では、熱可塑性樹脂粒子に染
料および発泡剤を含浸させた後、発泡性着色樹脂粒子を
水性分散液から分離することにより、発泡性着色樹脂粒
子が得られる。上記のようにして得られる発泡性着色樹
脂粒子は、所望により水洗し、乾燥した後、使用に供さ
れる。また、使用前に、ブロッキング防止剤（例えば、
金属石けん等）で表面をコーティングしてもよい。In the method of the present invention, the expandable colored resin particles are obtained by impregnating the thermoplastic resin particles with the dye and the foaming agent and then separating the expandable colored resin particles from the aqueous dispersion. The expandable colored resin particles obtained as described above are washed with water if desired, dried and then used. In addition, before use, an antiblocking agent (for example,
The surface may be coated with metal soap).
【００２４】上記の発泡性着色樹脂粒子を、例えば、予
備発泡装置内で、水蒸気圧０．１〜５．０ｋｇ／ｃｍ2
Ｇ程度の雰囲気下で加熱することによって、着色樹脂発
泡体を得ることができる。The expandable colored resin particles described above are added, for example, in a pre-expanding device to a water vapor pressure of 0.1 to 5.0 kg / cm 2.
A colored resin foam can be obtained by heating in an atmosphere of about G.
【００２５】上記の着色樹脂発泡体を、例えば、所望の
形状を有する型内に発泡体を充填し、水蒸気圧０．１〜
５．０ｋｇ／ｃｍ2 Ｇ程度の雰囲気下で成形し、水冷あ
るいは空冷後、型内から取り出すことにより、着色樹脂
発泡成形体が得られる。The above colored resin foam is filled in a mold having a desired shape, for example, and the water vapor pressure is 0.1 to 10.
A colored resin foam molded product is obtained by molding in an atmosphere of about 5.0 kg / cm 2 G, cooling with water or air, and then taking out from the mold.
【００２６】[0026]
【実施例】以下、本発明を実施例により説明するが、本
発明はこれらの実施例により限定されるものではない。
なお、ここで表わされる「重量％」は、いずれも実施例
で使用される熱可塑性樹脂粒子に対する量である。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
The "% by weight" shown here is the amount based on the thermoplastic resin particles used in the examples.
【００２７】［染料分散液の調整］染料としてオイルブ
ルー６３０Ｓ［オリエント化学工業（株）製］１．４ｇ
（０．０７重量％）、プラストレッド８３０５［有本化
学工業（株）製］０．４ｇ（０．０２重量％）およびパ
ピリオンレッドＳ‐ＥＰＳ［（株）京仁洋行製］１．４
ｇ（０．０７重量％）を、ドデシルベンゼンスルホン酸
ナトリウム０．２ｇ（０．０１重量％）とともに水１０
０ｇに添加して、分散させ、プロペラ翼にて１０分間撹
拌することにより、染料分散液１）１０３．４ｇを調整
する。[Preparation of Dye Dispersion] 1.4 g of Oil Blue 630S [manufactured by Orient Chemical Industry Co., Ltd.] as a dye
(0.07% by weight), Plastread 8305 [manufactured by Arimoto Chemical Industry Co., Ltd.] 0.4 g (0.02% by weight) and Papillion Red S-EPS [manufactured by Keihin Yoko Co., Ltd.] 1.4
g (0.07% by weight) together with 0.2 g (0.01% by weight) of sodium dodecylbenzenesulfonate and water 10
103.4 g of Dye Dispersion Solution 1) is prepared by adding 0 g to disperse the mixture and stirring with a propeller blade for 10 minutes.
【００２８】ドデシルベンゼンスルホン酸ナトリウムの
代わりに、プロノン２０８［日本油脂（株）製］０．８
ｇ（０．０４重量％）を用いた以外は、染料分散液１）
と同様にして染料分散液２）１０４．０ｇを調整する。
ドデシルベンゼンスルホン酸ナトリウムを使用しない以
外は、染料分散液１）と同様にして染料分散液３）１０
３．２ｇを調製する。Instead of sodium dodecylbenzene sulfonate, Pronone 208 [manufactured by NOF CORPORATION] 0.8
Dye dispersion 1) except that g (0.04% by weight) was used
In the same manner as above, 104.0 g of Dye Dispersion Liquid 2) is prepared.
Dye Dispersion Liquid 3) 10 as in Dye Dispersion Liquid 1), except that sodium dodecylbenzene sulfonate is not used.
Prepare 3.2 g.
【００２９】［非イオン界面活性剤の重量平均分子量の
測定条件］ゲルパーミエーションクロマトグラフ（以
下、「ＧＰＣ」という）による重量平均分子量の測定条
件は次のとおり。[Conditions for Measuring Weight Average Molecular Weight of Nonionic Surfactant] The conditions for measuring the weight average molecular weight by gel permeation chromatograph (hereinafter referred to as "GPC") are as follows.
【００３０】＜ＧＰＣの測定条件＞ 機種：Shodex GPC SYSTEM-11（昭和電工株式会社製） カラム：Shodex KF-804L×３（昭和電工株式会社製） カラム温度：４０℃ 検出器：ＲＩ 溶媒：テトラヒドロフラン（ＴＨＦ） 流速：１．０ｍｌ／分 試料濃度：０．１０％ 注入量：１００μｌ 標準サンプル：ポリオキシエチレングリコール<GPC measurement conditions> Model: Shodex GPC SYSTEM-11 (Showa Denko KK) Column: Shodex KF-804L × 3 (Showa Denko KK) Column temperature: 40 ° C Detector: RI Solvent: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Sample concentration: 0.10% Injection volume: 100 μl Standard sample: Polyoxyethylene glycol
【００３１】実施例１
内容積５Ｌの撹拌羽付きオートクレーブに、水１６５０
ｇを入れ、分散剤としてピロリン酸マグネシウム４ｇ
（０．２重量％）、分散助剤としてドデシルベンゼンス
ルホン酸ナトリウム（陰イオン系界面活性剤）１．６ｇ
（０．０８重量％）、プロノン２０８［日本油脂（株）
製］（非イオン界面活性剤）２ｇ（０．１重量％）を添
加し、さらに粒径０．７〜１．０ｍｍのスチレン系樹脂
粒子（熱可塑性樹脂粒子）２０００ｇを入れ、これらを
撹拌しながら染料分散液１）１０３．４ｇを添加した。Example 1 Water 1650 was added to an autoclave with an internal volume of 5 L and equipped with stirring blades.
g, 4g magnesium pyrophosphate as a dispersant
(0.2% by weight), 1.6 g of sodium dodecylbenzenesulfonate (anionic surfactant) as a dispersion aid
(0.08% by weight), Pronon 208 [NOF CORPORATION]
(Production) (nonionic surfactant) 2 g (0.1% by weight) is added, and 2000 g of styrene-based resin particles (thermoplastic resin particles) having a particle size of 0.7 to 1.0 mm are added and stirred. While adding 103.4 g of Dye Dispersion Liquid 1).
【００３２】そしてブタン（易揮発性発泡剤）１４０ｇ
（７重量％）、シクロヘキサン（発泡助剤）４０ｇ（２
重量％）を圧入した後、４０分間で９０℃まで昇温し、
５時間保温した後、３０℃まで冷却した。３０℃でオー
トクレーブより取出した後、脱水、洗浄、乾燥を行い、
グレー色に着色された発泡性スチレン系樹脂粒子（発泡
性着色樹脂粒子）を得た。140 g of butane (easily volatile foaming agent)
(7 wt%), cyclohexane (foaming aid) 40 g (2
(% By weight), and then heated to 90 ° C. in 40 minutes,
After keeping the temperature for 5 hours, it was cooled to 30 ° C. After taking out from the autoclave at 30 ° C, dehydration, washing and drying are performed.
Expandable styrenic resin particles (expandable colored resin particles) colored in gray were obtained.
【００３３】この発泡性着色樹脂粒子にブロッキング防
止剤、帯電防止剤を被覆し、３日間放置（熟成）させた
後、バッチ式発泡機によって、蒸気で加熱し、約６０倍
のかさ倍率に予備発泡させ、着色スチレン系樹脂発泡体
（着色樹脂発泡体）を得た。次いで、この着色樹脂発泡
体を１日放置（熟成）した後、型内成形を行い、放冷し
て成形体の内部発泡圧が減少した後、取出すことによ
り、着色スチレン系樹脂発泡成形体（着色樹脂発泡成形
体）を得た（寸法：４００×３００×２５ｍｍ）。成形
条件は、蒸気調圧を０．８ｋｇ／ｃｍ2、１次加熱時間
を８秒、２次加熱時間を２秒、３次加熱時間を８秒、水
冷を１５秒とした。得られた発泡性着色樹脂粒子および
着色樹脂発泡成形体の特性を表３に示す。The expandable colored resin particles were coated with an antiblocking agent and an antistatic agent, left for 3 days (aging), and then heated with steam by a batch type foaming machine to prepare a bulk ratio of about 60 times. By foaming, a colored styrene resin foam (colored resin foam) was obtained. Next, after leaving the colored resin foam for 1 day (aging), it is subjected to in-mold molding, and after being left to cool to reduce the internal foaming pressure of the molded body, it is taken out to give a colored styrene resin foam molded body ( A colored resin foam molding was obtained (dimensions: 400 × 300 × 25 mm). The molding conditions were steam pressure adjustment of 0.8 kg / cm 2 , primary heating time of 8 seconds, secondary heating time of 2 seconds, tertiary heating time of 8 seconds, and water cooling of 15 seconds. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００３４】実施例２
分散剤としてピロリン酸マグネシウムの代わりにポリビ
ニルアルコール８ｇ（０．４重量％）を使用し、分散助
剤のドデシルベンゼンスルホン酸ナトリウムは使用せ
ず、プロノン２０８を２ｇ（０．１重量％）の代わりに
１．２ｇ（０．０６重量％）を使用し、染料分散液１）
の代わりに染料分散液２）１０４．０ｇを使用した以外
は、実施例１と同様にして発泡性着色樹脂粒子、着色樹
脂発泡体、着色発泡成形体を得た。ここで、添加された
プロノン２０８の熱可塑性樹脂粒子に対する重量％の総
量は、直接添加した０．０６重量％と染料分散液２）に
含まれていた０．０４重量％との合計量であり、０．１
重量％である。得られた発泡性着色樹脂粒子および着色
樹脂発泡成形体の特性を表３に示す。Example 2 As a dispersant, 8 g (0.4% by weight) of polyvinyl alcohol was used instead of magnesium pyrophosphate, 2 g of pronone 208 (0.1% by weight) was used without using sodium dodecylbenzenesulfonate as a dispersion aid. 1.2 g (0.06% by weight) is used instead of 1% by weight, and the dye dispersion 1)
In the same manner as in Example 1 except that 104.0 g of the Dye Dispersion Liquid 2) was used instead, the expandable colored resin particles, the colored resin foam, and the colored foam molded product were obtained. Here, the total amount by weight of the added pronone 208 with respect to the thermoplastic resin particles is the total amount of 0.06% by weight directly added and 0.04% by weight contained in the dye dispersion liquid 2). , 0.1
% By weight. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００３５】実施例３
プロノン２０８を１ｇ（０．０５重量％）とした以外
は、実施例１と同様にして発泡性着色樹脂粒子、着色樹
脂発泡体、着色発泡成形体を得た。得られた発泡性着色
樹脂粒子および着色樹脂発泡成形体の特性を表３に示
し、発泡体の断面写真を図１に示す。Example 3 Expandable colored resin particles, a colored resin foam and a colored foam molded product were obtained in the same manner as in Example 1 except that 1 g (0.05% by weight) of pronone 208 was used. The properties of the expandable colored resin particles and the colored resin foam-molded product obtained are shown in Table 3, and a cross-sectional photograph of the foamed product is shown in FIG.
【００３６】実施例４
プロノン２０８を０．５ｇ（０．０２５重量％）とした
以外は、実施例１と同様にして発泡性着色樹脂粒子、着
色樹脂発泡体、着色発泡成形体を得た。得られた発泡性
着色樹脂粒子および着色樹脂発泡成形体の特性を表３に
示す。Example 4 Expandable colored resin particles, a colored resin foam and a colored foam molded product were obtained in the same manner as in Example 1 except that 0.5 g (0.025% by weight) of pronone 208 was used. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００３７】実施例５
プロノン２０８を０．２ｇ（０．０１重量％）とした以
外は、実施例１と同様にして発泡性着色樹脂粒子、着色
樹脂発泡体、着色発泡成形体を得た。得られた発泡性着
色樹脂粒子および着色樹脂発泡成形体の特性を表３に示
す。Example 5 Expandable colored resin particles, a colored resin foam and a colored foam molded product were obtained in the same manner as in Example 1 except that 0.2 g (0.01% by weight) of pronone 208 was used. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００３８】実施例６
プロノン２０８を０．５ｇ（０．０２５重量％）とし、
直接オートクレーブに添加するのではなく、染料分散液
１）に添加した以外は、実施例１と同様にして発泡性着
色樹脂粒子、着色樹脂発泡体、着色発泡成形体を得た。
得られた発泡性着色樹脂粒子および着色樹脂発泡成形体
の特性を表３に示す。Example 6 0.5 g (0.025% by weight) of pronone 208,
Expandable colored resin particles, a colored resin foam, and a colored foam molded product were obtained in the same manner as in Example 1 except that the dye dispersion 1) was not directly added to the autoclave.
Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００３９】実施例７
プロノン２０８の代わりにプロノン２０７［日本油脂
（株）製］０．５ｇ（０．０２５重量％）を用いた以外
は、実施例１と同様にして発泡性着色樹脂粒子、着色樹
脂発泡体、着色発泡成形体を得た。得られた発泡性着色
樹脂粒子および着色樹脂発泡成形体の特性を表３に示
す。Example 7 Foamable colored resin particles were prepared in the same manner as in Example 1 except that 0.5 g (0.025% by weight) of Pronone 207 [Nippon Oil & Fats Co., Ltd.] was used instead of Pronone 208. A colored resin foam and a colored foam molding were obtained. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００４０】比較例１
プロノン２０８を使用しない以外は、実施例１と同様に
して発泡性着色樹脂粒子、着色樹脂発泡体、着色発泡成
形体を得た。得られた発泡性着色樹脂粒子および着色樹
脂発泡成形体の特性を表３に示す。Comparative Example 1 Expandable colored resin particles, a colored resin foam and a colored foam molded product were obtained in the same manner as in Example 1 except that Pronone 208 was not used. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００４１】比較例２
プロノン２０８の直接添加を行わず、また染料分散液
２）の代わりに染料分散液３）１０３．２ｇを使用した
以外は、実施例２と同様にして発泡性着色樹脂粒子、着
色樹脂発泡体、着色発泡成形体を得た。得られた発泡性
着色樹脂粒子および着色樹脂発泡成形体の特性を表３に
示す。Comparative Example 2 Expandable colored resin particles were prepared in the same manner as in Example 2 except that Pronone 208 was not directly added and that 103.2 g of Dye Dispersion Solution 3) was used instead of Dye Dispersion Solution 2). A colored resin foam and a colored foam molded product were obtained. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００４２】比較例３
プロノン２０８の代わりに、ＬＴ‐２２１［日本油脂
（株）製］３ｇ（０．１５重量％）を使用した以外は、
実施例１と同様にして発泡性着色樹脂粒子、着色樹脂発
泡体、着色発泡成形体を得た。得られた発泡性着色樹脂
粒子および着色樹脂発泡成形体の特性を表３に示す。Comparative Example 3 Protonone 208 was replaced by LT-221 (manufactured by NOF CORPORATION) 3 g (0.15% by weight), except that
In the same manner as in Example 1, expandable colored resin particles, a colored resin foam, and a colored foam molded product were obtained. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００４３】比較例４
プロノン２０８の代わりに、ＬＴ‐２２１ ２ｇ（０．
１重量％）を使用した以外は、実施例１と同様にして発
泡性着色樹脂粒子、着色樹脂発泡体、着色発泡成形体を
得た。得られた発泡性着色樹脂粒子および着色樹脂発泡
成形体の特性を表３に示す。Comparative Example 4 Instead of Pronone 208, 2 g of LT-221 (0.
1% by weight), but in the same manner as in Example 1 to obtain expandable colored resin particles, a colored resin foam, and a colored foam molded article. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００４４】比較例５
プロノン２０８の代わりに、ＬＴ‐２２１ １ｇ（０．
０５重量％）を使用した以外は、実施例１と同様にして
発泡性着色樹脂粒子、着色樹脂発泡体、着色発泡成形体
を得た。得られた発泡性着色樹脂粒子および着色樹脂発
泡成形体の特性を表３に示す。Comparative Example 5 1 g of LT-221 (0.
The expandable colored resin particles, the colored resin foam, and the colored foamed molded product were obtained in the same manner as in Example 1 except that (05 wt%) was used. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００４５】比較例６
プロノン２０８の代わりに、ＬＴ‐２２１ ０．５ｇ
（０．０２５重量％）を使用した以外は、実施例１と同
様にして発泡性着色樹脂粒子、着色樹脂発泡体、着色発
泡成形体を得た。この発泡体の断面写真を図２に示す。
得られた発泡性着色樹脂粒子および着色樹脂発泡成形体
の特性を表３に示す。Comparative Example 6 Instead of Pronone 208, 0.5 g of LT-221
Expandable colored resin particles, a colored resin foam, and a colored foam molded product were obtained in the same manner as in Example 1 except that (0.025% by weight) was used. A cross-sectional photograph of this foam is shown in FIG.
Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００４６】比較例７
プロノン２０８の代わりに、プロノン２０１［日本油脂
（株）製］０．５ｇ（０．０２５重量％）を使用した以
外は、実施例１と同様にして発泡性着色樹脂粒子、着色
樹脂発泡体、着色発泡成形体を得た。得られた発泡性着
色樹脂粒子および着色樹脂発泡成形体の特性を表３に示
す。Comparative Example 7 Foamable colored resin particles were prepared in the same manner as in Example 1 except that 0.5 g (0.025% by weight) of Pronone 201 (manufactured by NOF CORPORATION) was used instead of Pronone 208. A colored resin foam and a colored foam molded product were obtained. Table 3 shows the characteristics of the expandable colored resin particles and the colored resin foam-molded product obtained.
【００４７】［色むらの評価方法］色むらは、得られた
着色樹脂発泡成形体の表面（４００ｍｍ×３００ｍｍ×
２５ｍｍ）における色むら部分の数を求め、以下の基準
により評価した。色むら部分とそうでない部分を示す概
念図を図３に示す。
○・・・なし
△・・・２個
×・・・３個以上[Evaluation Method of Color Unevenness] Color unevenness is the surface (400 mm × 300 mm ×) of the obtained colored resin foam molded article.
The number of uneven color portions in 25 mm) was obtained and evaluated according to the following criteria. FIG. 3 is a conceptual diagram showing the non-uniform color portion and the non-uniform color portion. ○ ・ ・ ・ None △ ・ ・ ・ 2 × × 3 or more
【００４８】［着色樹脂発泡成形体の色合いの濃さ］着
色樹脂発泡成形体の色合いの濃さは、次式によって定め
られ、従来の方法である比較例1の発泡成形体の色合い
の濃さを１００として比較している。そして得られる濃
さ（％）から以下の基準により評価する。
濃さ ＝[（１００−Ｌ）2＋ａ2＋ｂ2]0.5
濃さ（％）＝（比較するものの濃さ）／（比較例１の濃
さ）[Darkness of tint of colored resin foam-molded article] The tint strength of the colored resin foam-molded article is determined by the following equation, and the tint strength of the foamed article of Comparative Example 1 which is a conventional method. Is compared as 100. Then, based on the obtained density (%), evaluation is made according to the following criteria. Darkness = [(100-L) 2 + a 2 + b 2 ] 0.5 Darkness (%) = (darkness of comparison) / (darkness of Comparative Example 1)
【００４９】なお、このときのＬ値、ａ値、ｂ値は色差
計により計測された数値である。色差計は、ミノルタ
（株）製の色彩色差計（商品名：ＣＲ‐３００）を用い
た。
○・・・９５〜１０５％
×・・・９５％未満または１０５％を超える
目視判定を行う場合、９５％未満であると色差があると
認識され、染料の調整（増量）が必要となる。１０５％
を超える場合についても色差があると認識され、染料の
調整（減量）が必要となる。The L value, the a value, and the b value at this time are numerical values measured by a color difference meter. As the color difference meter, a color difference meter (trade name: CR-300) manufactured by Minolta Co., Ltd. was used. ∘: 95 to 105% x: When performing visual determination of less than 95% or more than 105%, it is recognized that a color difference of less than 95% requires dye adjustment (increase). 105%
Even when the value exceeds, it is recognized that there is a color difference, and it is necessary to adjust (reduce) the dye.
【００５０】［粒子合着の評価方法］発泡性着色樹脂粒
子を目開き１．４ｍｍの篩にかけ、篩上に残留した合着
粒子の重量を測定して粒子合着量(発泡性着色樹脂粒子
の全量に対する重量％)を求める。合着量０．１重量％
未満を合格水準○とし、それ以外を×とする。[Evaluation Method of Particle Cohesion] The expandable colored resin particles are sieved with a sieve having an opening of 1.4 mm, and the weight of the coalesced particles remaining on the sieve is measured to determine the particle coalescence amount (expandable colored resin particles (% By weight based on the total amount of). Coalescing amount 0.1% by weight
The less than is the pass level, and the others are x.
【００５１】［実施例および比較例で用いられる非イオ
ン界面活性剤の物性表］[Physical Properties Table of Nonionic Surfactants Used in Examples and Comparative Examples]
【表１】 [Table 1]
【００５２】［実施例および比較例で用いられる材料を
示す一覧表］[List showing materials used in Examples and Comparative Examples]
【表２】 [Table 2]
【００５３】［実施例および比較例で得られたものの特
性を示す一覧表］[List showing characteristics of those obtained in Examples and Comparative Examples]
【表３】
以上の結果より、本発明の方法により得られる着色樹脂
発泡成形体（実施例１〜７）は、色むらがなく、しかも
充分な濃さを示すことが分かる。[Table 3] From the above results, it is understood that the colored resin foam-molded articles (Examples 1 to 7) obtained by the method of the present invention have no color unevenness and exhibit sufficient darkness.
【００５４】[0054]
【発明の効果】本発明の方法によれば、色むらがなく、
しかも充分な濃さを示す着色樹脂発泡成形体を得ること
ができる。According to the method of the present invention, there is no uneven color,
Moreover, it is possible to obtain a colored resin foam molded article having a sufficient density.
【図１】実施例３で得られた発泡体の断面写真である。FIG. 1 is a photograph of a cross section of a foam obtained in Example 3.
【図２】比較例６で得られた発泡体の断面写真である。FIG. 2 is a photograph of a cross section of the foam obtained in Comparative Example 6.
【図３】色むら部分とそうでない部分を示す概念図であ
る。FIG. 3 is a conceptual diagram showing an uneven color part and a non-uniform color part.
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Claims (8)
液中で、前記粒子に染料および易揮発性発泡剤を含浸さ
せることにより発泡性着色樹脂粒子を製造する方法にお
いて、 重量平均分子量が６５００以上である非イオン界面活性
剤の存在下に染料を含浸させることを特徴とする発泡性
着色樹脂粒子の製造方法。1. A method for producing expandable colored resin particles by impregnating the particles with a dye and a volatile foaming agent in an aqueous dispersion in which thermoplastic resin particles are dispersed, wherein the weight average molecular weight is 6500. A method for producing expandable colored resin particles, which comprises impregnating a dye in the presence of a nonionic surfactant as described above.
シドとエチレンオキシドのブロック共重合体であり、該
ブロック共重合体におけるプロピレンオキシドの含有量
が５〜８０重量％であり、エチレンオキシドの含有量が
９５〜２０重量％である請求項１に記載の製造方法。2. The nonionic surfactant is a block copolymer of propylene oxide and ethylene oxide, the content of propylene oxide in the block copolymer is 5 to 80% by weight, and the content of ethylene oxide is 95. The manufacturing method according to claim 1, wherein the amount is -20% by weight.
性樹脂粒子に対して０．００１〜１重量％である請求項
1または２に記載の製造方法。3. The amount of nonionic surfactant used is 0.001 to 1% by weight based on the thermoplastic resin particles.
The manufacturing method according to 1 or 2.
して０．０００５〜２重量％である請求項１〜３のいず
れかに記載の製造方法。4. The manufacturing method according to claim 1, wherein the amount of the dye used is 0.0005 to 2% by weight based on the thermoplastic resin particles.
のいずれかに記載の製造方法。5. The method according to claim 1, wherein two or more kinds of dyes are used.
The manufacturing method according to any one of 1.
法により得られた発泡性着色樹脂粒子。6. Expandable colored resin particles obtained by the method according to any one of claims 1 to 5.
発泡させることにより得られた着色樹脂発泡体。7. A colored resin foam obtained by foaming the expandable colored resin particles according to claim 6.
することにより得られた着色樹脂発泡成形体。8. A colored resin foam molded article obtained by molding the colored resin foam according to claim 7.
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|---|---|---|---|
| JP2001228106A JP3756430B2 (en) | 2001-07-27 | 2001-07-27 | Method for producing expandable colored resin particles |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001228106A JP3756430B2 (en) | 2001-07-27 | 2001-07-27 | Method for producing expandable colored resin particles |
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| JP3756430B2 JP3756430B2 (en) | 2006-03-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007099790A (en) * | 2005-09-30 | 2007-04-19 | Jsp Corp | Method for producing colored expandable styrene-based resin particle |
| CN107043513A (en) * | 2016-02-05 | 2017-08-15 | 株式会社Jsp | The manufacture method of compound resin expanded beads, compound resin expanded beads formed body and compound resin expanded beads |
-
2001
- 2001-07-27 JP JP2001228106A patent/JP3756430B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007099790A (en) * | 2005-09-30 | 2007-04-19 | Jsp Corp | Method for producing colored expandable styrene-based resin particle |
| CN107043513A (en) * | 2016-02-05 | 2017-08-15 | 株式会社Jsp | The manufacture method of compound resin expanded beads, compound resin expanded beads formed body and compound resin expanded beads |
| CN107043513B (en) * | 2016-02-05 | 2021-01-01 | 株式会社Jsp | Composite resin expanded particle, composite resin expanded particle molded body, and method for producing composite resin expanded particle |
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