JPS62161843A - Production of colored expandable styrene resin bead - Google Patents

Production of colored expandable styrene resin bead

Info

Publication number
JPS62161843A
JPS62161843A JP388986A JP388986A JPS62161843A JP S62161843 A JPS62161843 A JP S62161843A JP 388986 A JP388986 A JP 388986A JP 388986 A JP388986 A JP 388986A JP S62161843 A JPS62161843 A JP S62161843A
Authority
JP
Japan
Prior art keywords
dye
resin particles
styrenic resin
styrene resin
colored
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
Application number
JP388986A
Other languages
Japanese (ja)
Other versions
JPH0464623B2 (en
Inventor
Tetsuya Kato
哲也 加藤
Hideaki Shibata
英昭 柴田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to JP388986A priority Critical patent/JPS62161843A/en
Publication of JPS62161843A publication Critical patent/JPS62161843A/en
Publication of JPH0464623B2 publication Critical patent/JPH0464623B2/ja
Granted legal-status Critical Current

Links

Landscapes

  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

PURPOSE:To obtain the titled resin particle capable of giving a molded article resistant to the falling off of dye and having freely adjustable color tone and color density, by coating a styrene resin with a dye, dispersing the coated resin in an aqueous medium and impregnating a highly volatile foaming agent in the resin. CONSTITUTION:A styrene resin particle is mixed together with 0.001-0.5(wt)% dye (e.g. monoazo dye). Prior to, during or after the above process, 0.01-1% plasticizer (e.g. dioctyl phthalate) is added to the system and stirred. The styrene resin particle coated with the dye is dispersed in an aqueous medium and added with a highly volatile foaming agent (e.g. propane, butane, etc.) to effect the impregnation of 3-10% foaming agent in the resin particle.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は2着色された発泡性スチレン系樹脂粒子の製造
法に関する。
DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing bi-colored expandable styrenic resin particles.

(従来の技術) 従来9着色された発泡性ポリスチレンビーズを得る方法
としては、1)発泡性ポリスチレンビーズに染料又は顔
料を混合した後、−次発泡及び成形を行う方法、2)ポ
リスチレンビーズを核として。
(Prior Art) Conventionally, the methods for obtaining colored expandable polystyrene beads include 1) mixing dyes or pigments with expandable polystyrene beads, followed by subsequent foaming and molding, and 2) forming polystyrene beads into cores. As.

これに染料を含む有機溶剤を含浸させた後、又は。After impregnating this with an organic solvent containing a dye, or.

これに染料を含む単量体を含浸させて重合途中若しくは
重合後2発泡剤を含浸させて着色発泡性ポリスチレンピ
ーズとする方法等が知られている。
A known method is to impregnate this with a monomer containing a dye and then impregnate it with a blowing agent during or after polymerization to obtain colored expandable polystyrene peas.

(発明が解決しようとする問題点) しかしながら、これらの方法は一長一短を有しておシ、
改善が求められている。
(Problems to be solved by the invention) However, these methods have advantages and disadvantages.
Improvement is required.

例えば、前記の1)の方法では、染料、顔料の発泡性ポ
リスチレンビーズへの付着が弱く、脱離して予備発泡機
を汚染し、iた。染料を高濃度にすると、成形の際の融
着を阻害するという欠点がある。2)の方法では、染料
が重合触媒によって脱色されるため、染料が限定された
り、溶剤に染料を溶解して含浸する場合は、溶解性及び
濃度に制約があり、任意の染料の任意の量を含浸するこ
とが出来ないという欠点がある。このような欠点がある
ため、従来法によって着色された発泡ポリスチレン成形
体においては、商品価値が低下したり。
For example, in method 1), dyes and pigments adhered poorly to expandable polystyrene beads, and were detached, contaminating the pre-foaming machine. A high concentration of dye has the disadvantage of inhibiting fusion during molding. In method 2), the dye is decolorized by a polymerization catalyst, so the number of dyes is limited, and when the dye is dissolved in a solvent and impregnated, there are restrictions on solubility and concentration, and it is possible to use any amount of any dye. The disadvantage is that it cannot be impregnated with. Due to these drawbacks, the commercial value of expanded polystyrene molded articles colored by conventional methods is reduced.

また、自由な展開が出来なかった。Also, it was not possible to develop freely.

そこで1本発明は、成形品にした時の色調の選択、a度
の調整を自在に行うことができ、しかも染料の脱離の起
こらない着色発泡性ポリスチレンビーズを提供すること
を目的とする。
Accordingly, one object of the present invention is to provide colored expandable polystyrene beads that can freely select the color tone and adjust the degree of a when molded into a molded product, and that do not cause detachment of the dye.

(問題点を解決するための手段) 本発明は、染料でコーティングされたスチレン系樹脂粒
子を水性媒体中に分散させ、易揮発性発泡剤を添加し、
含浸させることを特徴とする着色発泡性スチレン系樹脂
粒子の製造法に関する。
(Means for Solving the Problems) The present invention involves dispersing dye-coated styrenic resin particles in an aqueous medium, adding an easily volatile foaming agent,
The present invention relates to a method for producing colored expandable styrenic resin particles characterized by impregnation.

本発明に使用されるスチレン系樹脂粒子とは。What are styrenic resin particles used in the present invention?

ポリスチレン又はスチレンを主成分とする(好ましくは
スチレンが50重量%以上の)共重合体であって2球状
、ペレット状等の粒子状のものであり、特に懸濁重合に
よって得られる真球状粒子が好ましい。スチレンと共重
合させる単量体とじては、アクリロニトリル、ブチルア
クリレート等のアクリル酸エステル、メチルメタクリレ
ート、セチルメタクリレート等のメタクリル酸エステル
Polystyrene or a copolymer whose main component is styrene (preferably styrene is 50% by weight or more), which is in the form of particles such as bispheres or pellets, especially true spherical particles obtained by suspension polymerization. preferable. Examples of monomers to be copolymerized with styrene include acrylic esters such as acrylonitrile and butyl acrylate, and methacrylic esters such as methyl methacrylate and cetyl methacrylate.

α−メチルスチレン、t−ブチルスチレン等のスチレン
誘導体がある。スチレン系樹脂粒子の製造は、公知の方
法により1行えばよい。
There are styrene derivatives such as α-methylstyrene and t-butylstyrene. The styrenic resin particles may be manufactured in one step using a known method.

上記染料としては油性染料であればよく2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ある。染料
の使用量は、スチレン系樹脂粒子に対して0.001〜
0.5重量%が好ましい。
The above-mentioned dyes may be oil-based dyes2. For example, monoazo dyes, anthraquinone dyes, disazo dyes,
There are perinone dyes, phthalocyanine dyes, etc. The amount of dye used is from 0.001 to 0.001 to styrene resin particles.
0.5% by weight is preferred.

染料の使用量が少なすぎると着色の効果が小さくなシ、
多すぎると全量をスチレン系樹脂粒子に固定しづらくな
る。
If the amount of dye used is too small, the coloring effect will be small.
If the amount is too large, it becomes difficult to fix the entire amount to the styrene resin particles.

染料のコーティングは、染料の存在下にスチレン系樹脂
粒子を攪拌することによって行うことができ、特にヘン
シェルミキサーのような高速回転型ミキサーを用いて摩
擦熱の伴う機械力によって攪拌するのが好ましい。
Dye coating can be carried out by stirring the styrenic resin particles in the presence of the dye, and it is particularly preferable to use a high-speed rotary mixer such as a Henschel mixer and stir by mechanical force accompanied by frictional heat.

染料でコーティングされたスチレン系樹脂粒子は、染料
が可塑剤とともにコーティングされてなるスチレン系樹
脂粒子であるのが好ましい。このためには、上記の染料
のコーティングにおける攪拌の前又は途中で可塑剤を添
加するか、上記の染料のコーティングの後に、可塑剤を
添加し、同様に攪拌するのが好ましい。
The dye-coated styrenic resin particles are preferably styrenic resin particles coated with a dye and a plasticizer. For this purpose, it is preferable to add a plasticizer before or during the stirring in coating the dye, or to add the plasticizer after coating the dye and stirring in the same manner.

可塑剤としては、ジオクチルフタレート、ジブチルフタ
レートのようなフタル酸エステル、ジオクチルアジペー
トのようなアジピン酸エステル等の染料及びスチレン系
樹脂粒子の双方に対して貧溶媒となる物質が好ましく、
使用量はスチレン系樹脂粒子に対して0.01〜1重′
Jkチが好ましい。
The plasticizer is preferably a substance that is a poor solvent for both dyes and styrene resin particles, such as phthalate esters such as dioctyl phthalate and dibutyl phthalate, and adipic esters such as dioctyl adipate.
The amount used is 0.01 to 1 weight per styrene resin particle.
Jk chi is preferable.

可塑剤の使用量が少なすぎると染料固定向上の効果が小
さく、多すぎるとビーズ同士が凝集し、取扱いにくくな
る。
If the amount of plasticizer used is too small, the effect of improving dye fixation will be small, and if it is too large, the beads will aggregate and become difficult to handle.

本発明においては9表面が染料でコーティングされたス
チレン系樹脂粒子を水性媒体中に分散させて発泡剤の含
浸を行うが、その際分散剤として。
In the present invention, styrenic resin particles whose surfaces are coated with a dye are dispersed in an aqueous medium and impregnated with a blowing agent.

水溶性の高分子コロイド、1a溶性リン酸塩等を水性媒
体に存在させる。水溶性高分子コロイドとしてハウポリ
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
セルロース誘導体等が挙げられる。また、難溶性リン酸
塩としては、リン酸三カルシウム、リン酸マグネシウム
等が挙げられる。
A water-soluble polymer colloid, a 1a-soluble phosphate, etc. are present in an aqueous medium. Examples of water-soluble polymer colloids include cellulose derivatives such as polyvinyl alcohol, alkyl cellulose, hydroxyalkyl cellulose, and carboxyalkyl cellulose. In addition, examples of poorly soluble phosphates include tricalcium phosphate, magnesium phosphate, and the like.

分散剤は、スチレン系樹脂粒子に対して0.1〜1重量
%使用するのが好ましく1分散剤として難に対してo、
 o o s〜0.5重量%使用するのが好ましい。
The dispersant is preferably used in an amount of 0.1 to 1% by weight based on the styrene resin particles.
It is preferable to use os to 0.5% by weight.

上記の表面が染料でコーティングされたスチレン系樹脂
粒子を水性媒体中に分散させ1発泡剤を含浸させる前に
、該水性媒体中に、トルエン、エチルベンゼン、キシレ
ン、スチレン等のスチレン系樹脂の溶剤を添加し、攪拌
するのが好ましい。
Before dispersing the above-mentioned styrene-based resin particles whose surfaces are coated with a dye in an aqueous medium and impregnating them with a blowing agent, a styrene-based resin solvent such as toluene, ethylbenzene, xylene, or styrene is added to the aqueous medium. Preferably, the mixture is added and stirred.

これにより、染料のスチレン系樹脂粒子への吸着又は吸
収を促進することができる。溶剤はスチレン系樹脂粒子
に対して0.1〜2.0重量%使用するのが好ましい。
This can promote adsorption or absorption of the dye onto the styrene resin particles. The solvent is preferably used in an amount of 0.1 to 2.0% by weight based on the styrene resin particles.

溶剤が少なすぎると上記効果がなく、多すぎると発泡特
性を阻外しやすくなる。また、このとき、70〜130
℃に加熱して行うのが、上記効果を確実にする上で好ま
しい。
If the amount of the solvent is too small, the above effects will not be obtained, and if the amount is too large, the foaming properties will be likely to be impaired. Also, at this time, 70 to 130
It is preferable to carry out heating to ℃ in order to ensure the above-mentioned effect.

易揮発性の発泡剤としては、スチレン系樹脂粒子の軟化
点より低い沸点を有する脂肪族炭化水素。
Easily volatile blowing agents include aliphatic hydrocarbons having a boiling point lower than the softening point of styrene resin particles.

例えばプロパン、ブタン、ペンタン、ヘキサン等を使用
することができる。更に2発泡助剤として。
For example, propane, butane, pentane, hexane, etc. can be used. In addition, 2 as a foaming aid.

シクロヘキサンのような脂環式炭化水素、トルエン、エ
チルベンゼン、キシレン、スチレンのヨウな芳香族炭化
水素等、スチレン系樹脂粒子に対する溶剤を用いること
もできる。発泡助剤としては。
Solvents for styrenic resin particles can also be used, such as alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene, ethylbenzene, xylene, and styrene. As a foaming aid.

染料の吸着又は吸収するための溶剤を2発泡剤の含浸工
程において、ひきつづき使用することができる。
A solvent for dye adsorption or absorption can be used subsequently in the two-blowing agent impregnation step.

易揮発性発泡剤の含浸け2表面が染料でコーティングさ
れたスチレン系樹脂粒子を分散させた水性媒体に易揮発
性発泡剤を添加、好ましくは圧入して行なうことができ
る。該発泡剤の含浸け。
Impregnation with a readily volatile foaming agent 2 An easily volatile foaming agent can be added to an aqueous medium in which styrene resin particles whose surfaces are coated with a dye are dispersed, preferably by being press-injected. Impregnation with the blowing agent.

65〜110℃で行うのが好ましい。Preferably, the temperature is 65 to 110°C.

易揮発性発泡剤は、スチレン系樹脂粒子に対し3〜10
3ii%含浸されるようにされるのが好ましい。また1
発泡助剤は使用するときは、スチレン系樹脂粒子に対し
て0.1〜3]ii%を水性媒体に添加するのが好まし
い。
The easily volatile blowing agent is 3 to 10% of the styrene resin particles.
Preferably it is impregnated with 3ii%. Also 1
When the foaming aid is used, it is preferably added to the aqueous medium in an amount of 0.1 to 3]ii% based on the styrene resin particles.

易揮発性発泡剤の含浸が終了したのち、水性媒体から目
的の着色された発泡性スチレン系樹脂粒子を分離し、場
合により水洗して、乾燥し、使用に供される。
After the impregnation with the easily volatile blowing agent is completed, the desired colored expandable styrenic resin particles are separated from the aqueous medium, optionally washed with water, dried, and used.

使用前に、ブロッキング防止剤(例えば、金属石けん等
)で2着色された発泡性スチレン系樹脂粒子をコーティ
ングしてもよい。
The bi-colored expandable styrenic resin particles may be coated with an antiblocking agent (eg, metallic soap, etc.) before use.

(作用) 本発明において9発泡剤の含浸時に、スチレン系樹脂粒
子表面付近に存在する染料が発泡剤に同伴されて該粒子
の内部に浸透する。この結果、染料の粒子白濃度は1表
面で濃く、中心部で薄くなるような濃度勾配を有する。
(Function) In the present invention, at the time of impregnation with the blowing agent 9, the dye present near the surface of the styrenic resin particles is accompanied by the blowing agent and penetrates into the inside of the particles. As a result, the white density of the dye particle has a concentration gradient such that it is high on one surface and becomes thin at the center.

以上のように、染料は表面付近で濃度が大きくしかも内
部に浸透しているので、よシ少ない染料でより濃い色に
着色することかできる。
As mentioned above, the dye has a high concentration near the surface and also penetrates into the interior, so it is possible to color the material in a deeper color with a smaller amount of dye.

また2種々の染料を組み合わせることにより色調の選択
が容易にできる。
Furthermore, by combining two various dyes, color tone can be easily selected.

(実施例) 次に、実施例に基づいて本発明を詳述するが。(Example) Next, the present invention will be explained in detail based on examples.

本発明はこれに限定されるものではない。The present invention is not limited to this.

実施例1 内容積101!のヘンシェルミキサーに粒子径が0.7
〜1.2胴であり2分子量が約3.0X10 の懸濁重
合で得られたポリスチレンビーズ50009及び染料と
してダイヤレジンブルーP(商標、三菱化成社製)20
9を入れ、1分間2000fpmで混合した後、ジオク
チルアジペート5gを入れ。
Example 1 Internal volume 101! Henschel mixer with a particle size of 0.7
Polystyrene beads 50009 obtained by suspension polymerization with ~1.2 cylinders and a molecular weight of about 3.0 x 10 and Diamond Resin Blue P (trademark, manufactured by Mitsubishi Kasei Corporation) 20 as a dye.
9 and mixed at 2000 fpm for 1 minute, then 5 g of dioctyl adipate was added.

再度2分間混合し、青色に着色されたポリスチレンビー
ズを作った。
Mix again for 2 minutes to produce blue colored polystyrene beads.

次に、内容積12Jの攪拌翼付きオートクレーブに、0
.3%ポリビニルアルコールsooog及び前記のポリ
スチレンビーズ50009を入れ。
Next, in an autoclave with an internal volume of 12 J and equipped with stirring blades,
.. Add 3% polyvinyl alcohol sooog and the polystyrene beads 50009 mentioned above.

攪拌を行った。室温で、トルエン30gを入れ。Stirring was performed. At room temperature, add 30g of toluene.

120℃まで120分で昇温した。昇温後、その温度に
120分保持して、染料をポリスチレンビーズ表面へ吸
着させた。その後、100℃まで冷却し、W−ゴシクロ
ヘキサン100g及びブタンガス600m/を圧入し、
4時間保温後、40℃まで冷却した。
The temperature was raised to 120°C in 120 minutes. After raising the temperature, the temperature was maintained for 120 minutes to allow the dye to be adsorbed onto the surface of the polystyrene beads. After that, it was cooled to 100°C, and 100 g of W-gocyclohexane and 600 m of butane gas were introduced under pressure.
After keeping the temperature for 4 hours, it was cooled to 40°C.

40℃でオートクレーブから取シ出した後、脱7.5重
量%)を得た。これにステアリン酸亜鉛0.1重量%及
びステアリン酸トリグリセリド0.1重量%をプレンダ
ー内で混合し、ビーズ表面に付着させ9着色された発泡
性ポリスチレンビーズを得た。
After removal from the autoclave at 40° C., 7.5% by weight of dehydration was obtained. To this, 0.1% by weight of zinc stearate and 0.1% by weight of stearic acid triglyceride were mixed in a blender and adhered to the bead surface to obtain colored expandable polystyrene beads.

得られた着色発泡性ポリスチレンビーズを予備発泡後、
50倍で発泡成形したところ、均一に着色した成形品が
得られ1表面仕上がシ、内部融着共に良好であった。な
お、予備発泡工程後での染料の脱離は皆無であった。
After pre-foaming the obtained colored expandable polystyrene beads,
When foam molding was carried out at a magnification of 50 times, a uniformly colored molded product was obtained with good surface finish and internal fusion. Note that there was no desorption of the dye after the pre-foaming step.

実施例2 実施例1で用いたミキサーに粒子径が0.4〜0,6■
のポリスチレンビーズ5000g及び染料としてスミプ
ラストオレンジHRP (住人化学製)o959を入れ
2000 rpmで2分間攪拌し、オレンジ色に着色さ
れたポリスチレンビーズtiた。
Example 2 The mixer used in Example 1 had a particle size of 0.4 to 0.6
5,000 g of polystyrene beads and Sumiplast Orange HRP (manufactured by Sumitomo Chemical Co., Ltd.) o959 as a dye were added and stirred at 2,000 rpm for 2 minutes to obtain orange-colored polystyrene beads.

次に、実施例1で用いたオートクレーブにリン酸3カル
シウム0.4重量%、ドデシルベンゼンスれ攪拌を行い
ながら60分で90℃まで昇温した。
Next, 0.4% by weight of tricalcium phosphate and dodecylbenzene were added to the autoclave used in Example 1, and the temperature was raised to 90° C. over 60 minutes while stirring.

10分間保持後ノルマル・ペンタン2009゜LPG4
00ml!を圧入し、4時間保温後40℃まで冷却した
After holding for 10 minutes, normal pentane 2009゜LPG4
00ml! was press-fitted, kept warm for 4 hours, and then cooled to 40°C.

40℃でオートクレーブから取りだした後、脱水、洗浄
、乾燥を行い、オレンジ色に着色した発泡性ポリスチレ
ンビーズを得た。これに対し、ステアリン酸亜鉛0.1
5重量%を混合し、予備発泡後、10倍でカップに発泡
成形したところ、均一に着色した成形品が得られ2表面
仕上がシ、内部融着共に良好な成形体であった。
After taking it out from the autoclave at 40°C, it was dehydrated, washed, and dried to obtain expandable polystyrene beads colored orange. In contrast, zinc stearate 0.1
When 5% by weight was mixed, and after pre-foaming, foam molding was carried out into a cup at a magnification of 10 times, a uniformly colored molded product was obtained, and the molded product had good surface finish and internal fusion.

又、予備発泡後の染料の脱離は皆無であった。Further, there was no desorption of the dye after pre-foaming.

実施例3 実施例1で用いたミキサーに粒子径が1.0〜1.4圓
のポリスチレンビーズ50009.及び染料としてプラ
ストイエローナ8040 (有本化学裂)2.09.グ
イレンブルーFSNO488(犬日本インキ製)t、s
gを入れ2分間攪拌し、緑色に着色されたポリスチレン
ビーズを4た。
Example 3 Polystyrene beads 50009 with a particle size of 1.0 to 1.4 circles were added to the mixer used in Example 1. and Plast Yellowna 8040 (Arimoto Kagaku) as a dye 2.09. Guillen Blue FSNO488 (manufactured by Inu Nippon Ink) t, s
After stirring for 2 minutes, 4 green colored polystyrene beads were added.

次に実施例1で用いたオートクレーブにリン酸3カルシ
ウム0.1重量%、炭酸カルシウム0.3重量%、ドデ
シルベンゼンスルホン酸ソータ0.012重量%を含む
分散液50009及び前記着色ポリスチレンビーズso
oog入れ攪拌しながら、室温でエチルベンゼン159
を入れ90分で100℃まで昇温した。100℃で30
分保温後、ノルマル・ヘキサン1009.ブタン600
rnlを圧入し、さらに5時間保温後40℃まで冷却し
た。
Next, in the autoclave used in Example 1, dispersion 50009 containing 0.1% by weight of tricalcium phosphate, 0.3% by weight of calcium carbonate, and 0.012% by weight of dodecylbenzenesulfonic acid sorter and the colored polystyrene beads so
Add ethylbenzene 159 at room temperature while stirring.
was added and the temperature was raised to 100°C in 90 minutes. 30 at 100℃
After keeping warm for 1 minute, normal hexane 1009. Butane 600
rnl was press-fitted, and the mixture was further kept warm for 5 hours and then cooled to 40°C.

40℃でオートクレーブよシとシだした後、脱水、洗浄
及び乾燥を行い、ビーズに対してステアリン酸亜鉛0.
1重量%、ステアリン酸アマイド0.1重量%、ステア
リン酸トリグリセライド0.05重爺ヤまぶして、緑色
発泡性ポリスチレンビーズを得た。
After pouring out the autoclave at 40°C, the beads were dehydrated, washed and dried, and the beads were treated with 0.0% zinc stearate.
1% by weight of stearamide, 0.1% by weight of stearic acid triglyceride, and 0.05% of stearic acid triglyceride were coated to obtain green expandable polystyrene beads.

得られた緑色発泡性ポリスチレンビーズを予備発泡後4
5倍で発泡成形したところ、均一に着色してお92表面
仕上がシ、内部融着共に良好な成形品を得た。
After pre-foaming the obtained green expandable polystyrene beads,
When foam molding was performed at a magnification of 5 times, a molded product was obtained which was uniformly colored, had a good surface finish, and had good internal fusion.

又、染料の脱離は皆無であった。Moreover, there was no desorption of the dye.

実施例4 実施例1で用いたミキサーに粒子径が0.7〜1.2叩
のポリスチレンビーズ50009及び染料としてスミプ
ラストブラックH3B(住人化学製)59入れ1分間混
合したのちジオクチルフタレート2.5gを追加し、再
度1分間混合し灰色に着色されたポリスチレンビーズを
得た。
Example 4 Into the mixer used in Example 1, polystyrene beads 50009 with a particle size of 0.7 to 1.2 mm and Sumiplast Black H3B (manufactured by Sumitomo Chemical) 59 as a dye were added and mixed for 1 minute, followed by 2.5 g of dioctyl phthalate. was added and mixed again for 1 minute to obtain gray colored polystyrene beads.

次に、実施例1で用いたオートクレーブに、0.4重量
俤ポリビニルアルコール水溶液5000gt−入れ、6
0分で100℃まで昇温した。100℃で10分保温後
ブタン500ccを圧入し、さらに4時間保温したのち
40℃まで冷却した。
Next, 5000gt of 0.4wt polyvinyl alcohol aqueous solution was placed in the autoclave used in Example 1.
The temperature was raised to 100°C in 0 minutes. After keeping the temperature at 100°C for 10 minutes, 500 cc of butane was injected, and after keeping the temperature for an additional 4 hours, it was cooled to 40°C.

40℃でオートクレーブよりとりだした後、脱水、洗浄
及び乾燥を行い、ビーズに対してステアリン酸亜鉛0.
1重量%、ステアリン酸トリグリセライド0.08重量
%をまぶして灰色に着色された発泡性ポリスチレンビー
ズを得た。これを15倍で発泡成形したところ、均一に
着色した成形品が得られ表面仕上がシ、内部融着共に良
好であった。
After removing the beads from the autoclave at 40°C, they were dehydrated, washed and dried, and the beads were treated with 0.0% zinc stearate.
1% by weight of stearic acid triglyceride and 0.08% by weight of stearic acid triglyceride were sprinkled thereon to obtain expandable polystyrene beads colored gray. When this was foam-molded at a magnification of 15 times, a uniformly colored molded product was obtained with good surface finish and internal fusion.

又、染料の脱離は皆無であった。Moreover, there was no desorption of the dye.

比較例 着色されていない発泡性ポリスチレンビーズ(日立化成
社製ハイビーズ5SB−TK)に対してダイレンブルー
FSN 0488を0.07重量%をまぶして、青色発
泡性ポリスチレンビーズを得た。これを予備発泡後50
倍で発泡成形したところ、染料が予備発泡工程で一部脱
離し、予備発泡器が青色に汚染した。
Comparative Example Uncolored expandable polystyrene beads (HiBeads 5SB-TK manufactured by Hitachi Chemical Co., Ltd.) were sprinkled with 0.07% by weight of Dyren Blue FSN 0488 to obtain blue expandable polystyrene beads. After pre-foaming this, 50
When foam molding was carried out at a double magnification, some of the dye was removed during the pre-foaming process, and the pre-foamer was stained blue.

又、得られた成形品は少し色ムラが発生し、商品価値が
劣るものであった。
Moreover, the obtained molded product had some color unevenness and was inferior in commercial value.

(発明の効果) 本発明によって得られる着色発泡性スチレン系樹脂粒子
を用いれば2表面仕上がり及び内部融着が良好な成形体
が得られ、その色調及び濃度を広範に自由に選択しうる
ので、商品価値の高い成形体が得られる。
(Effects of the Invention) By using the colored expandable styrenic resin particles obtained by the present invention, a molded product with good surface finish and internal fusion can be obtained, and its color tone and density can be freely selected from a wide range. A molded article with high commercial value can be obtained.

代理人 弁理士 若 林 邦 鰺 (、」’:、’Agent Patent Attorney Kuni Wakabayashi Aji (,”’:,’

Claims (1)

【特許請求の範囲】 1、染料でコーティングされたスチレン系樹脂粒子を水
性媒体中に分散させ、易揮発性発泡剤を添加し、含浸さ
せることを特徴とする着色発泡性スチレン系樹脂粒子の
製造法。 2、染料でコーティングされたスチレン系樹脂粒子が、
染料が可塑剤とともにスチレン系樹脂粒子にコーティン
グされてなるものである特許請求の範囲第1項記載の着
色発泡性スチレン系樹脂粒子の製造法。 3、易揮発性発泡剤を添加する前に、スチレン系樹脂の
溶剤を水性媒体中に添加し、攪拌する特許請求の範囲第
1項又は第2項記載の着色発泡性スチレン系樹脂粒子の
製造法。
[Claims] 1. Production of colored expandable styrenic resin particles characterized by dispersing dye-coated styrenic resin particles in an aqueous medium and adding and impregnating them with an easily volatile foaming agent. Law. 2. Styrenic resin particles coated with dye,
The method for producing colored expandable styrenic resin particles according to claim 1, wherein the styrenic resin particles are coated with a dye and a plasticizer. 3. Production of colored expandable styrenic resin particles according to claim 1 or 2, in which a styrenic resin solvent is added to an aqueous medium and stirred before adding the easily volatile blowing agent. Law.
JP388986A 1986-01-10 1986-01-10 Production of colored expandable styrene resin bead Granted JPS62161843A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP388986A JPS62161843A (en) 1986-01-10 1986-01-10 Production of colored expandable styrene resin bead

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP388986A JPS62161843A (en) 1986-01-10 1986-01-10 Production of colored expandable styrene resin bead

Publications (2)

Publication Number Publication Date
JPS62161843A true JPS62161843A (en) 1987-07-17
JPH0464623B2 JPH0464623B2 (en) 1992-10-15

Family

ID=11569747

Family Applications (1)

Application Number Title Priority Date Filing Date
JP388986A Granted JPS62161843A (en) 1986-01-10 1986-01-10 Production of colored expandable styrene resin bead

Country Status (1)

Country Link
JP (1) JPS62161843A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4979963A (en) * 1988-03-25 1990-12-25 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for coloring expandable polystyrene beads
KR100433191B1 (en) * 2002-01-05 2004-05-27 주식회사 삼우기술에이엔씨 Manufacturing Method of Color EPS Boards with High Elasticity
JP2006213850A (en) * 2005-02-04 2006-08-17 Sekisui Plastics Co Ltd Foamable polystyrene-based resin particle
WO2010095444A1 (en) * 2009-02-19 2010-08-26 積水化成品工業株式会社 Expandable polystyrene resin particles for low-ratio expansion molding and method for producing same, low-ratio expanded particles, low-ratio expanded molded article, cushion material for hume pipe, and method for producing low-ratio expanded molded article and cushion material for hume pipe

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5222062A (en) * 1975-08-09 1977-02-19 Fuorei Patsukeejingu Ltd Process for porducing colored polystyrene foam
JPS58109538A (en) * 1981-12-24 1983-06-29 Hitachi Chem Co Ltd Preparation of foamable styrenic resin particle
JPS60250047A (en) * 1984-05-25 1985-12-10 Badische Yuka Co Ltd Production of expandable colored styrene resin particle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5222062A (en) * 1975-08-09 1977-02-19 Fuorei Patsukeejingu Ltd Process for porducing colored polystyrene foam
JPS58109538A (en) * 1981-12-24 1983-06-29 Hitachi Chem Co Ltd Preparation of foamable styrenic resin particle
JPS60250047A (en) * 1984-05-25 1985-12-10 Badische Yuka Co Ltd Production of expandable colored styrene resin particle

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4979963A (en) * 1988-03-25 1990-12-25 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for coloring expandable polystyrene beads
KR100433191B1 (en) * 2002-01-05 2004-05-27 주식회사 삼우기술에이엔씨 Manufacturing Method of Color EPS Boards with High Elasticity
JP2006213850A (en) * 2005-02-04 2006-08-17 Sekisui Plastics Co Ltd Foamable polystyrene-based resin particle
JP4653507B2 (en) * 2005-02-04 2011-03-16 積水化成品工業株式会社 Expandable styrene resin particles
WO2010095444A1 (en) * 2009-02-19 2010-08-26 積水化成品工業株式会社 Expandable polystyrene resin particles for low-ratio expansion molding and method for producing same, low-ratio expanded particles, low-ratio expanded molded article, cushion material for hume pipe, and method for producing low-ratio expanded molded article and cushion material for hume pipe
CN102405253A (en) * 2009-02-19 2012-04-04 积水化成品工业株式会社 Expandable polystyrene resin particles for low-ratio expansion molding and method for producing same, low-ratio expanded particles, low-ratio expanded molded article, cushion material for hume pipe, and method for producing low-ratio expanded molded
JP5552112B2 (en) * 2009-02-19 2014-07-16 積水化成品工業株式会社 Expandable polystyrene resin particles for low-magnification molding and manufacturing method thereof, low-magnification foamed particles, low-magnification foam moldings and fume tube cushion materials, low-magnification foam moldings and fume tube cushioning material manufacturing methods
KR101498336B1 (en) * 2009-02-19 2015-03-03 세키스이가세이힝코교가부시키가이샤 Expandable polystyrene resin particles for low-ratio expansion molding and method for producing same, low-ratio expanded particles, low-ratio expanded molded article, cushion material for hume pipe, and method for producing low-ratio expanded molded article and cushion material for hume pipe

Also Published As

Publication number Publication date
JPH0464623B2 (en) 1992-10-15

Similar Documents

Publication Publication Date Title
US2950261A (en) Process of making expansible particulate styrene polymer by diffusion of a volatile liquid hydrocarbon into said polymer particles
US3484262A (en) Polymer pigmentation
JPS62161843A (en) Production of colored expandable styrene resin bead
JP4935110B2 (en) Method for producing colored expandable styrene resin particles
JPH07179647A (en) Resin particle for production of flame retardant foam of good dimensional stability and its production
US3399025A (en) Process for dyeing thermoplastic styrene polymer granules
JPH02247234A (en) Production of expandable colored thermoplastic resin particle and colored expanded article
JPH0471418B2 (en)
JPH06122781A (en) Expandable styrenic resin particle and its production
JP3278347B2 (en) Expandable colored resin particles and method for producing the same
JPH0218329B2 (en)
KR0163433B1 (en) Process for the preparation of fire-retardant expandable thermoplastic beads
JPH06157805A (en) Production of colored foamable resin particle
JPS58109538A (en) Preparation of foamable styrenic resin particle
JPS6031536A (en) Production of expandable styrene resin particle
JPS59152933A (en) Colored expandable polystyrene bead
US3821138A (en) Pigmented polymeric resin castings
US3850860A (en) Process for dyeing expandable thermoplastic polymers
JPS63198970A (en) Hollow sphere of calcium phosphate
JPH0623266B2 (en) Method for producing colored expandable styrene resin particles
JPH08100006A (en) Production of monodisperse polymer particle
KR20230027400A (en) Expanded Styrene Flowerpot
JPS5842212B2 (en) Heat-expandable resin composition
JPS58204034A (en) Method for coloring expanded polystyrene particle
KR100198105B1 (en) Process for production of formable styrene resin particles having good water and oil resistance properties

Legal Events

Date Code Title Description
LAPS Cancellation because of no payment of annual fees