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JP2001342305A - Colorant composition for fiber reinforced olefinic resin and molded article prepared therefrom - Google Patents

Colorant composition for fiber reinforced olefinic resin and molded article prepared therefrom

Info

Publication number
JP2001342305A
JP2001342305A JP2000163338A JP2000163338A JP2001342305A JP 2001342305 A JP2001342305 A JP 2001342305A JP 2000163338 A JP2000163338 A JP 2000163338A JP 2000163338 A JP2000163338 A JP 2000163338A JP 2001342305 A JP2001342305 A JP 2001342305A
Authority
JP
Japan
Prior art keywords
weight
resin
molded article
glass fiber
parts
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.)
Pending
Application number
JP2000163338A
Other languages
Japanese (ja)
Inventor
Junichi Yoshioka
淳一 吉岡
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.)
Artience Co Ltd
Original Assignee
Toyo Ink Mfg 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 Toyo Ink Mfg Co Ltd filed Critical Toyo Ink Mfg Co Ltd
Priority to JP2000163338A priority Critical patent/JP2001342305A/en
Publication of JP2001342305A publication Critical patent/JP2001342305A/en
Pending legal-status Critical Current

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  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a colorant composition which does not degrade the mechanical properties of a glass fiber reinforced olefinic resin. SOLUTION: The colorant composition comprises an olefinic resin, zinc sulfide or a composite of zinc sulfide and barium sulfate as a white pigment, and a carboxylic-acid-modified polyolefin whose molecular chains are crosslinked by a metallic cation.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、機械物性の優れた
ガラス繊維強化オレフィン系樹脂用着色剤組成物及びこ
れを用いて成る成形品に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorant composition for glass fiber reinforced olefin resin having excellent mechanical properties, and a molded article using the same.

【0002】[0002]

【従来の技術】ガラス繊維で強化された熱可塑性樹脂
は、プラスチック材料固有の長所である軽量性、耐蝕性
等の性質を具備していることは勿論、強化されない熱可
塑性樹脂よりも機械物性の点で優れている。
2. Description of the Related Art Thermoplastic resins reinforced with glass fibers have properties inherent in plastic materials, such as light weight and corrosion resistance, as well as mechanical properties more than non-reinforced thermoplastic resins. Excellent in point.

【0003】汎用性のプラスチック樹脂、例えばポリエ
チレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニ
ール単独の耐熱性は、連続使用温度で言うならばたかだ
か100℃程度であるが、これらの樹脂に繊維状物質、
フレーク、フィラー等を含有せしめることにより耐熱性
が向上される。耐蝕性や機械物性能を併せると、少ない
添加量でガラス長繊維が良好な効果を与えることが知ら
れている。
The heat resistance of general-purpose plastic resins such as polyethylene, polypropylene, polystyrene and polyvinyl chloride alone is at most about 100 ° C. at a continuous use temperature.
By incorporating flakes, fillers and the like, heat resistance is improved. It is known that a long glass fiber gives a good effect with a small amount of addition in combination with corrosion resistance and mechanical property.

【0004】[0004]

【発明が解決しようとする課題】しかしながら、ガラス
長繊維を含有せしめた汎用樹脂組成物、具体的にはポリ
プロピレン複合材料では、射出速度、ゲート形状等の射
出成形条件によっては繊維の切断が起こり、所望の機械
物性が得られないことがある。更に、成形品の着色を目
的とし、各種顔料を組成物中に配合し成形に供する場
合、使用顔料のモース硬度がガラス繊維より高い場合、
例えば白色顔料で汎用的な二酸化チタン(モース硬度6
〜7)では、その含有量がたとえ1重量%以下であって
も混練時にガラス繊維を損傷するためアイゾット衝撃値
は無着色品の半分程度に落ち込んでしまう。
However, in the case of a general-purpose resin composition containing glass long fibers, specifically, a polypropylene composite material, fiber cutting occurs depending on injection molding conditions such as injection speed and gate shape. Desired mechanical properties may not be obtained. Further, for the purpose of coloring the molded article, when blending various pigments in the composition and providing for molding, when the Mohs hardness of the pigment used is higher than glass fiber,
For example, general-purpose titanium dioxide (Mohs hardness 6
In the cases (7) to (7), even if the content is 1% by weight or less, the glass fiber is damaged at the time of kneading, so that the Izod impact value drops to about half that of the uncolored product.

【0005】アイゾット衝撃値の向上には、酸化チタン
よりモース硬度が低い白色顔料である硫化亜鉛(モース
硬度約3.5)が有効であることが特公昭55−244
66号公報等に開示されているが、発明者らがポリプロ
ピレン樹脂にガラス繊維30重量%を配合した組成物1
00重量部に硫化亜鉛1.5重量部を添加し、射出成形
により得られた試験片のアイゾット衝撃値を確認したと
ころ、無着色品の75%程度の保持率しか得られなかっ
た。
To improve the Izod impact value, it is effective that zinc sulfide (Mohs hardness of about 3.5), which is a white pigment having a Mohs hardness lower than that of titanium oxide, is effective.
No. 66, etc., a composition 1 in which the inventors blended 30% by weight of glass fiber with polypropylene resin.
When 1.5 parts by weight of zinc sulfide was added to 00 parts by weight, and the Izod impact value of the test piece obtained by injection molding was confirmed, only a retention of about 75% of the non-colored product was obtained.

【0006】また、マレイン酸変性ポリプロピレンのよ
うな接着性樹脂を用いてガラス繊維とオレフィン樹脂と
の接着性を向上させることによりアイゾット衝撃値の改
善を図る手法が特開昭62−36428号公報に開示さ
れているが、樹脂の変性化に伴うコストアップは避けら
れなった。
Japanese Patent Application Laid-Open No. Sho 62-36428 discloses a technique for improving the Izod impact value by improving the adhesion between glass fibers and an olefin resin by using an adhesive resin such as maleic acid-modified polypropylene. Although disclosed, an increase in cost due to denaturation of the resin could not be avoided.

【0007】[0007]

【課題を解決するための手段】即ち、本発明の第1の発
明は、オレフィン系樹脂と、白色顔料として硫化亜鉛又
は硫化亜鉛と硫酸バリウムの複合体と、金属陽イオンに
よって分子鎖間が架橋されたカルボン酸変性ポリオレフ
ィンとを含有することを特徴とする着色剤組成物であ
る。
That is, the first invention of the present invention is to provide an olefin resin, zinc sulfide or a composite of zinc sulfide and barium sulfate as a white pigment, and a crosslink between molecular chains by a metal cation. And a carboxylic acid-modified polyolefin.

【0008】第2の発明は、金属陽イオンによって分子
鎖間が架橋されたカルボン酸変性ポリオレフィンが、N
a又はZnイオンで架橋されたエチレン−メタクリル酸
共重合体であることを特徴とする第1の発明に記載の着
色剤組成物である。
In a second aspect, the carboxylic acid-modified polyolefin in which the molecular chains are cross-linked by a metal cation is N-type.
The colorant composition according to the first invention, which is an ethylene-methacrylic acid copolymer cross-linked with a or Zn ions.

【0009】第3の発明は、ガラス繊維とオレフィン系
樹脂とから成る被着色体と、第1の発明に記載の着色剤
組成物とから成る成形品であって、ガラス繊維100重
量部に対し金属陽イオンによって分子鎖間が架橋された
カルボン酸変性ポリオレフィンが1〜10重量部である
ことを特徴とする成形品である。
A third aspect of the present invention is a molded article comprising a body to be colored comprising glass fiber and an olefin resin, and a colorant composition according to the first aspect, wherein the molded article is based on 100 parts by weight of glass fiber. A molded article characterized in that the carboxylic acid-modified polyolefin in which the molecular chains are crosslinked by a metal cation is 1 to 10 parts by weight.

【0010】第4の発明は、ガラス繊維とオレフィン系
樹脂とから成る被着色体と、第2の発明に記載の着色剤
組成物とから成る成形品であって、ガラス繊維100重
量部に対しNa又はZnイオンで架橋されたエチレン−
メタクリル酸共重合体が1〜10重量部であることを特
徴とする成形品である。
[0010] A fourth invention is a molded article comprising a colorant comprising glass fiber and an olefin resin, and a colorant composition according to the second invention, wherein the molded article is based on 100 parts by weight of glass fiber. Ethylene-crosslinked with Na or Zn ions
A molded article characterized in that the amount of the methacrylic acid copolymer is 1 to 10 parts by weight.

【0011】[0011]

【発明の実施の形態】本発明における被着色体とは、ガ
ラス繊維を含有したオレフィン系樹脂のことをいう。オ
レフィン系樹脂であればいかなる樹脂でも可能である
が、具体的には射出成形及び押出成形用として広く上市
されているポリプロピレン、プロピレン−エチレンのブ
ロック共重合体及びそのランダム共重合体、高密度ポリ
エチレン、直鎖状低密度ポリエチレン、低密度ポリエチ
レン等が挙げられる。
BEST MODE FOR CARRYING OUT THE INVENTION The object to be colored in the present invention refers to an olefin resin containing glass fibers. Any resin can be used as long as it is an olefin-based resin. Specifically, polypropylene, a propylene-ethylene block copolymer and a random copolymer thereof, which are widely marketed for injection molding and extrusion molding, and high-density polyethylene , Linear low density polyethylene, low density polyethylene and the like.

【0012】ガラス繊維は、繊維長が3〜30mmであ
ることが好ましい。繊維長が3mm未満であると長繊維
の添加効果であるアイゾット衝撃強度等の機械物性が充
分に発現できず、30mmを越えると繊維の絡みにより
射出成形や押出成形時にノズル、ダイでのつまりの原因
となるため、円滑な成形が出来なくなってしまう。
The glass fiber preferably has a fiber length of 3 to 30 mm. If the fiber length is less than 3 mm, mechanical properties such as Izod impact strength, which is the effect of adding long fibers, cannot be sufficiently exhibited. If the fiber length exceeds 30 mm, clogging of the nozzle or die during injection molding or extrusion molding due to fiber entanglement may occur. Because of the cause, smooth molding cannot be performed.

【0013】被着色体におけるガラス繊維の含有量は1
0〜40重量%が好ましい。10重量%未満であると機
械物性が充分に発現せず、また、40重量%を越えると
成形品の外観が悪くなるばかりか、樹脂の流動性が悪化
して成形性が悪化する。
The content of the glass fiber in the object to be colored is 1
0-40% by weight is preferred. If the content is less than 10% by weight, the mechanical properties are not sufficiently exhibited, and if it exceeds 40% by weight, not only the appearance of the molded product is deteriorated, but also the fluidity of the resin is deteriorated and the moldability is deteriorated.

【0014】本発明の繊維強化オレフィン系樹脂用着色
剤組成物(以下、着色剤と略す)においてベースレジン
となり得るものは、被着色体におけるオレフィン系樹脂
と同一または相溶性があることは勿論、同一もしくは若
干高いメルトフローレートを有するものが望ましい。ベ
ースレジンのメルトフローレートが被着色体樹脂に比べ
て低いと、成形の際、着色剤が充分に被着色体中に分散
することが出来なくなり、結果として成形品表面に色む
らのおそれがある。
In the colorant composition for a fiber-reinforced olefin resin of the present invention (hereinafter abbreviated as a colorant), those which can be used as a base resin are, of course, the same as or compatible with the olefin resin in the object to be colored. Those having the same or slightly higher melt flow rate are desirable. If the melt flow rate of the base resin is lower than that of the resin to be colored, during molding, the colorant cannot be sufficiently dispersed in the material to be colored, and as a result, there is a possibility that the surface of the molded article may have uneven color. .

【0015】着色剤におけるベ−スレジンの含有量は3
0〜90重量%であることが望ましい。30重量%未満
であるとペレット状の形状を保持することが難しく、ま
た、90重量%を越えると顔料の含有量が低くなり、結
果として成形品への着色効果が減少してしまうため好ま
しくない。
The content of the base resin in the colorant is 3
It is desirably 0 to 90% by weight. If it is less than 30% by weight, it is difficult to maintain a pellet-like shape, and if it exceeds 90% by weight, the content of the pigment becomes low, and as a result, the coloring effect on the molded article is reduced, which is not preferable. .

【0016】本発明の着色剤に用いられる、ガラス繊維
とオレフィン系樹脂とを接着する役割を有する、金属陽
イオンによって分子鎖間が架橋されたカルボン酸変性ポ
リオレフィン(以下、アイオノマ−樹脂と略す)とは、
エチレン、プロピレン等のα−オレフィンと、アクリル
酸、メタクリル酸、マレイン酸等のカルボン酸を持った
モノマ−とから成る共重合体において、カルボキシル基
を利用して金属イオンで分子鎖間を架橋した構造を持つ
ポリマ−のことをいう。金属陽イオンとしてはNa、
K、Ag、Cu、Ca、Ba、Zn、Feイオン等が挙
げられ、これらイオンの種類によりアイオノマ−の物性
は変化するが、エチレン−メタクリル酸共重合体の分子
鎖間をNa又はZnイオンで架橋した構造が特に望まし
い。
A carboxylic acid-modified polyolefin (hereinafter abbreviated as ionomer resin) having a function of adhering a glass fiber and an olefin resin and having a molecular chain cross-linked by a metal cation used in the colorant of the present invention. Is
In a copolymer consisting of α-olefins such as ethylene and propylene and a monomer having a carboxylic acid such as acrylic acid, methacrylic acid, and maleic acid, a molecular ion was crosslinked between metal chains using a carboxyl group. A polymer having a structure. Na as a metal cation,
K, Ag, Cu, Ca, Ba, Zn, Fe ions, and the like are listed. The physical properties of the ionomer vary depending on the type of these ions, but Na or Zn ions are used between the molecular chains of the ethylene-methacrylic acid copolymer. Crosslinked structures are particularly desirable.

【0017】アイオノマ−樹脂の製造方法としては、酢
酸塩、アルコキシド等を共重合体とともにロ−ルで練る
方法、及び共重合体のキシレン温溶液に金属塩の溶液を
加えゲル化させる方法があるが、これらに限定されな
い。
As a method for producing an ionomer resin, there are a method of kneading an acetate, an alkoxide and the like together with a copolymer by a roll, and a method of gelling by adding a solution of a metal salt to a hot xylene solution of the copolymer. However, it is not limited to these.

【0018】金属イオンによる架橋結合は、共有結合の
ような一般の化学結合による架橋と異なり、熱によって
結合力が変わる。加熱によりイオン架橋が弱くなるため
結合力が弱くなって熱流動性があらわれ、一般の熱可塑
性樹脂と同様に成形でき、かつ架橋の存在のために熔融
時でも熔融強度、溶融延伸性といった点で低密度ポリエ
チレンより優れているという特性を有する。また、冷却
するとイオン結合が強くなるため結合力が強くなり、強
靱性、弾力性が大きい強固なポリマ−になるという特徴
を有する。
Crosslinking by a metal ion differs from crosslinking by a general chemical bond such as a covalent bond, and the bonding force is changed by heat. Heat weakens the ionic cross-linking, weakens the bonding force, and shows thermofluidity.It can be molded in the same manner as general thermoplastic resins, and because of the presence of cross-linking, it has a melt strength and melt stretchability even during melting. It has the property of being superior to low density polyethylene. Further, when cooled, the ionic bond is strengthened, so that the bonding force is strengthened, and a strong polymer having high toughness and elasticity is obtained.

【0019】アイオノマー樹脂の含有量は、成形品中の
ガラス繊維100重量部に対して1〜10重量部である
ことが必要であり、特には1〜7重量部が好ましい。着
色剤中の含有量は、着色剤の被着色体への添加量により
調整すればよいが、5〜60重量%が好ましい。例えば
ガラス繊維30重量%含有の被着色体100重量部に1
0重量部の着色剤を添加する場合、ガラス繊維に対し2
重量部の添加であるならば6重量%、ガラス繊維に対し
5重量部の添加であるならば15重量%の含有量が算出
される。
The content of the ionomer resin must be 1 to 10 parts by weight, particularly preferably 1 to 7 parts by weight, based on 100 parts by weight of the glass fiber in the molded article. The content of the coloring agent may be adjusted by the amount of the coloring agent added to the object to be colored, but is preferably 5 to 60% by weight. For example, 1 part per 100 parts by weight of the object to be colored containing 30% by weight of glass fiber
When 0 parts by weight of the colorant is added, 2
The content is calculated to be 6% by weight if added by weight and 15% by weight if added to 5 parts by weight of glass fiber.

【0020】1重量部未満であると、ガラス繊維とオレ
フィン樹脂との界面を濡らすのに充分でなく、機械物
性、例えばアイゾット衝撃値はアイオノマー樹脂無添加
のものと大して変わらない。また、10重量部を越える
と、添加量に見合ったアイゾット衝撃値の向上が期待で
きないばかりでなく、成形機中のヤケの発生や曲げ弾性
率、熱変形温度の低下、コストアップ等の弊害が顕著と
なる。また、ガラス繊維の接着に関与しない過剰量のア
イオノマー樹脂は、オレフィン系樹脂、特にポリプロピ
レン樹脂中である一定の大きさを持つゴム粒子として存
在しているが、ポリプロピレンとゴム粒子の界面接着強
度は不充分なため、却ってアイゾット衝撃強度を悪化さ
せてしまうおそれがある。
If the amount is less than 1 part by weight, it is not sufficient to wet the interface between the glass fiber and the olefin resin, and the mechanical properties, for example, the Izod impact value are not much different from those without the ionomer resin. If the amount exceeds 10 parts by weight, not only the improvement of the Izod impact value commensurate with the added amount cannot be expected, but also adverse effects such as generation of burns in the molding machine, lowering of the flexural modulus, lowering of the thermal deformation temperature, and increase in the cost. Will be noticeable. In addition, an excessive amount of the ionomer resin that does not contribute to the adhesion of the glass fiber is present as rubber particles having a certain size in the olefin resin, particularly the polypropylene resin, but the interfacial adhesive strength between the polypropylene and the rubber particles is low. Because of insufficient strength, the Izod impact strength may be rather deteriorated.

【0021】上記のような接着性樹脂を含有した着色剤
を、被着色体であるガラス繊維含有オレフィン系樹脂に
添加して成る成形品のアイゾット衝撃強度の向上の理由
は以下の通り解釈される。ガラス繊維、特にガラス長繊
維を含んだ系での衝撃破壊モデルは、電線の被覆むきに
例えられる。この系での成形品が外部から衝撃を受け、
破壊に至る仮定を説明すると、樹脂中での破断が起きる
と同時にガラス繊維の切断が起こる。
The reason for the improvement of the Izod impact strength of a molded product obtained by adding a colorant containing an adhesive resin as described above to a glass fiber-containing olefin-based resin to be colored is interpreted as follows. . An impact fracture model in a system containing glass fibers, particularly long glass fibers, is likened to stripping of electric wires. The molded product in this system receives an external impact,
To explain the assumptions leading to fracture, breakage in the resin occurs and, at the same time, glass fiber cutting occurs.

【0022】また、一部のガラス繊維は破断面で瞬時に
切断されずに、樹脂との界面を抜ける挙動を示すことが
ある。このため、繊維が長いものでは樹脂との界面を抜
けるのに要する力が余分に必要となり(電線の被覆むき
で、むきしろが長くなるにつれて大きな力が必要となる
ことと同じ)、結果として衝撃吸収エネルギーが大きく
なる。ガラス繊維の含有量が同じであっても、長繊維は
短繊維のものよりもアイゾット衝撃強度が増すのはこの
ためである。接着性樹脂を用いることにより樹脂と繊維
との界面の密着力が強化されて衝撃強度が増すことも、
この電線の被覆むきモデルを用いれば充分に説明出来
る。しかしながら、繊維の切断が激しく短繊維になって
いる場合はこの補強効果も充分に発現されず、繊維の損
傷が低いことが必要である。
Further, some glass fibers may not be cut instantaneously at the fractured surface, but may exhibit a behavior of passing through the interface with the resin. For this reason, if the fiber is long, an extra force is required to pass through the interface with the resin (similar to the case where the wire is stripped and the longer the gap, the greater the force required). Absorbed energy increases. This is why the long fibers have higher Izod impact strength than the short fibers, even with the same glass fiber content. By using an adhesive resin, the adhesive strength at the interface between the resin and the fiber is strengthened, and the impact strength is increased.
This model can be sufficiently explained by using the stripping model. However, when the fibers are severely cut into short fibers, this reinforcing effect is not sufficiently exhibited, and it is necessary that the fibers be damaged little.

【0023】本発明の着色剤に用いられる白色顔料は硫
化亜鉛、又は硫化亜鉛と硫酸バリウムの混合物の少なく
ともいずれかである。これらの顔料の屈折率(約4)は
樹脂の屈折率(約1.5)と差があるため高度な隠蔽性
や白色度が得られ、更に、これらの顔料のモ−ス硬度
(硫化亜鉛:約3.5、硫酸バリウム:約3.0〜3.
5)はガラス繊維のモース硬度(約4〜6)より低いた
め、加工時におけるガラス繊維の切断はそれほど問題に
ならない。従って機械強度の低下を抑えることが出来
る。着色剤における白色顔料の含有量は10〜50重量
%が好ましい。
The white pigment used in the colorant of the present invention is at least either zinc sulfide or a mixture of zinc sulfide and barium sulfate. Since the refractive index (about 4) of these pigments is different from the refractive index (about 1.5) of the resin, a high degree of concealment and whiteness can be obtained, and the Mohs hardness (zinc sulfide) of these pigments : About 3.5, barium sulfate: about 3.0 to 3.0.
Since 5) is lower than the Mohs hardness (about 4 to 6) of the glass fiber, cutting of the glass fiber during processing is not so problematic. Therefore, a decrease in mechanical strength can be suppressed. The content of the white pigment in the colorant is preferably from 10 to 50% by weight.

【0024】白色顔料以外に必要に応じて用いられる顔
料としては、オレフィン系樹脂に汎用的に使用されるも
のであればよいが、白色顔料と同様にモース硬度がガラ
ス樹脂より低いことが必須条件となる。従って有彩色顔
料としては有機顔料が望ましく、例えば、モノアゾイエ
ロー、ジスアゾイエロー、ポリアゾイエロー、イソイン
ドリノンイエロー、モノアゾレッド、キナクリドンレッ
ド、ペリレンレッド、ジケトピロロピロールレッド、フ
タロシアニングリーン、フタロシアニンブルー、アンス
ラキノンブルー、ジオキサジンバイオレット、キナクリ
ドンバイオレット、黒色顔料としてカーボンブラック、
アニリンブラック等が挙げられる。着色剤における白色
顔料以外の顔料の含有量は、1〜30重量%が好まし
い。
The pigment used as needed other than the white pigment may be any pigment generally used for olefin resins, but it is essential that the Mohs' hardness is lower than that of the glass resin like the white pigment. Becomes Therefore, organic pigments are preferable as the chromatic color pigments. Quinone blue, dioxazine violet, quinacridone violet, carbon black as a black pigment,
Aniline black and the like. The content of the pigment other than the white pigment in the colorant is preferably 1 to 30% by weight.

【0025】本発明の着色剤は顔料分散剤としてポリエ
チレンワックスを用いることが望ましい。ポリエチレン
ワックス以外の顔料分散剤、例えば金属石鹸を分散剤と
して用いた場合、金属石鹸がアイオノマー樹脂のカルボ
ン酸部分を中和してしまう現象が起きてしまう。ポリエ
チレンワックスは化学的にも安定であり、オレフィン樹
脂の成形温度にも充分耐えうる耐熱性を持っていること
も鑑みると、本発明品の顔料分散剤としての要求は充分
満たされる。
The colorant of the present invention preferably uses polyethylene wax as a pigment dispersant. When a pigment dispersant other than polyethylene wax, for example, a metal soap is used as the dispersant, a phenomenon occurs in which the metal soap neutralizes the carboxylic acid portion of the ionomer resin. In view of the fact that polyethylene wax is chemically stable and has heat resistance enough to withstand the molding temperature of the olefin resin, the requirements of the present invention as a pigment dispersant are sufficiently satisfied.

【0026】ポリエチレンワックスを添加する場合その
含有量は、着色剤に含有される顔料1重量%に対し、
0.5〜1重量%が好ましい。0.5重量%を下回ると
顔料の濡れ性が悪くなり、所望の分散効果が得られな
い。1重量%を越えた含有量では顔料の分散は充分なも
のの、過剰量のワックスがアイゾット衝撃値、引張伸
び、熱変形温度等の機械物性の低下を引き起こすおそれ
があり好ましくない。
When the polyethylene wax is added, its content is based on 1% by weight of the pigment contained in the colorant.
0.5-1% by weight is preferred. When the amount is less than 0.5% by weight, the wettability of the pigment becomes poor, and the desired dispersing effect cannot be obtained. If the content exceeds 1% by weight, the pigment is sufficiently dispersed, but an excessive amount of the wax may cause a decrease in mechanical properties such as an Izod impact value, tensile elongation, and heat deformation temperature, which is not preferable.

【0027】本発明の着色剤には、オレフィン系樹脂、
アイオノマ−樹脂、顔料の3成以外に、必要に応じてプ
ラスチック成形加工に一般的に用いられる各種添加剤、
具体的にはフエノール系酸化防止剤、リン系酸化防止
剤、チオビス系酸化防止剤、紫外線吸収剤等を添加する
ことができる。
The coloring agent of the present invention includes an olefin resin,
In addition to the three components of ionomer resin and pigment, various additives commonly used in plastic molding as required,
Specifically, a phenol-based antioxidant, a phosphorus-based antioxidant, a thiobis-based antioxidant, an ultraviolet absorber, and the like can be added.

【0028】本発明の着色剤は、上記3成分と必要に応
じた添加剤とを一般的な熱可塑性樹脂用のペレット状着
色剤に用いられる溶融混練方法、例えば単軸及び2軸押
出機、FCM、コニーダー等の連続式混練機、加圧ニー
ダー、バンバリーミキサー等のバッチ式混練機を用いて
製造される。但し、着色剤中にアイオノマー樹脂が完全
な形で分散させるべく、その混練状態には充分注意を払
う必要がある。
The colorant of the present invention can be prepared by melt-kneading the above-mentioned three components and optional additives into a general colorant for a thermoplastic resin pellet, such as a single-screw or twin-screw extruder. It is manufactured using a continuous kneader such as an FCM or a co-kneader, or a batch kneader such as a pressure kneader or a Banbury mixer. However, in order to completely disperse the ionomer resin in the coloring agent, it is necessary to pay close attention to the kneading state.

【0029】本発明の着色剤は成形品製造の際に被着色
体と混合、熔融混練され、射出成形又は押出成形等によ
り成形品とされる。成形品としては自動車用部品、家電
製品用部品、OA機器用部品等の機械的強度や耐熱性の
高いことが要求されるプラスチック製品が挙げられる。
The colorant of the present invention is mixed and melt-kneaded with a material to be colored during the production of a molded article, and is formed into a molded article by injection molding or extrusion molding. Examples of the molded product include plastic products that are required to have high mechanical strength and heat resistance, such as parts for automobiles, parts for home electric appliances, parts for OA equipment, and the like.

【0030】成形品におけるオレフィン樹脂(着色剤及
び被着色体由来のもの)の含有量は30〜70重量%が
望ましく、白色顔料の含有量は0.1〜5重量%が望ま
しい。0.1重量%を下回ると白色度、隠蔽性が得られ
ず添加の意味がなく、5重量%を越えると白色度、隠蔽
性は充分なもののアイゾット衝撃値、引張伸び等の機械
物性の低下が顕著となり好ましくない。また、白色顔料
以外の顔料の含有量は、成形品に要求される色調により
決定されるが、概ね成形品中に0.01〜3重量%が望
ましい。また、アイオノマ−樹脂は、成形品中のガラス
繊維100重量部に対して1〜10重量部の割合で含有
されることが必要である。
The content of the olefin resin (derived from the colorant and the object to be colored) in the molded article is desirably 30 to 70% by weight, and the content of the white pigment is desirably 0.1 to 5% by weight. If it is less than 0.1% by weight, whiteness and hiding properties cannot be obtained, and there is no meaning in addition. If it exceeds 5% by weight, mechanical properties such as Izod impact value and tensile elongation are deteriorated, although whiteness and hiding properties are sufficient. Becomes remarkable, which is not preferable. The content of the pigment other than the white pigment is determined depending on the color tone required for the molded article, but is preferably 0.01 to 3% by weight in the molded article. It is necessary that the ionomer resin is contained in a ratio of 1 to 10 parts by weight based on 100 parts by weight of the glass fiber in the molded article.

【0031】[0031]

【実施例】以下に、本発明を実施例及び比較例を挙げて
具体的に説明するが、本発明はこれらの具体例に限定さ
れない。 [実施例1]陽イオンに亜鉛原子を有するアイオノマー
樹脂(ハイミラン1557 三井デュポンポリケミカル
社製)5重量%、平均粒子径=0.3μmの硫化亜鉛
(サクトリスHD ザハトレーベン社製)15重量%、
カーボンブラック(三菱カーボン950B 三菱化学社
製)5重量%、ポリエチレンワックス(サンワックス1
31P 三洋化学社製)10重量%、ブロックポリプロ
ピレン(メルトフローレート=50)65重量%を2軸
押出機にて200℃の温度にて溶融混練し、ペレット状
の着色剤を作製した。得られた着色剤は、被着色体とし
てガラス繊維(繊維長=12mm、ガラス繊維含有量=
30重量%)含有ポリプロピレン樹脂(メルトフローレ
ート=50)100重量部に対し10重量部添加し、射
出成形により各種物性試験片を成形した(ガラス繊維1
00重量部に対しアイオノマー樹脂1.7重量部の割
合)。成形後の試験片はアイゾット衝撃試験(ASTM
D256)、曲げ弾性率(ASTM D790)、熱
変形温度(ASTM D648)の機械物性試験を行
い、無着色品(上記の被着色体のみから成るもの)との
物性値を比較した。
EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 5% by weight of an ionomer resin having a zinc atom as a cation (Himilan 1557, manufactured by DuPont Mitsui Polychemicals), 15% by weight of zinc sulfide having an average particle diameter of 0.3 μm (Sactris HD, manufactured by Zahat Reben),
5% by weight of carbon black (Mitsubishi Carbon 950B manufactured by Mitsubishi Chemical Corporation), polyethylene wax (Sunwax 1
31P 10% by weight (manufactured by Sanyo Chemical Co., Ltd.) and 65% by weight of block polypropylene (melt flow rate = 50) were melt-kneaded at a temperature of 200 ° C. using a twin-screw extruder to prepare a colorant in the form of pellets. The obtained coloring agent is a glass fiber (fiber length = 12 mm, glass fiber content =
10 parts by weight per 100 parts by weight of a polypropylene resin (melt flow rate = 50) containing 30% by weight), and various physical property test pieces were formed by injection molding (glass fiber 1).
(A ratio of 1.7 parts by weight of the ionomer resin to 00 parts by weight). The test piece after molding is an Izod impact test (ASTM
D256), flexural modulus (ASTM D790), and heat distortion temperature (ASTM D648) were subjected to mechanical property tests to compare the property values with non-colored products (those composed of only the above-mentioned coloring object).

【0032】[実施例2] 実施例1のアイオノマー樹
脂を10重量%、ポリプロピレンを60重量%とした以
外は実施例1と同様に着色剤を作製し、被着体と成形し
(ガラス繊維100重量部に対しアイオノマー樹脂3.
3重量部の割合)、機械物性試験を行った。
Example 2 A coloring agent was prepared in the same manner as in Example 1 except that the ionomer resin and the polypropylene in Example 1 were changed to 10% by weight and 60% by weight, respectively, and molded with an adherend (glass fiber 100). 2. Ionomer resin per part by weight
3 parts by weight) and a mechanical property test.

【0033】[実施例3] 実施例1中のアイオノマー
樹脂を20重量%、ポリプロピレンを50重量%とした
以外は実施例1と同様に着色剤を作製し、被着色体と成
形し(ガラス繊維100重量部に対しアイオノマー6.
6重量部)、機械物性試験を行った。
Example 3 A colorant was prepared in the same manner as in Example 1 except that the ionomer resin and the polypropylene in Example 1 were changed to 20% by weight and 50% by weight, respectively. 5. Ionomer per 100 parts by weight
6 parts by weight) and a mechanical property test.

【0034】[実施例4] 実施例1中のアイオノマー
樹脂を30重量%、ポリプロピレンを40重量%とした
以外は実施例1と同様に着色剤を作製し、被着色体と成
形し(ガラス繊維100重量部に対しアイオノマー10
重量部)、機械物性試験を行った。以上、実施例1〜4
の結果を表1に示した。
Example 4 A coloring agent was prepared in the same manner as in Example 1 except that the ionomer resin and the polypropylene in Example 1 were changed to 30% by weight and 40% by weight, respectively. 100 parts by weight of ionomer 10
Parts by weight) and a mechanical property test. As described above, Examples 1 to 4
Table 1 shows the results.

【0035】[0035]

【表1】 [Table 1]

【0036】[比較例1] アイオノマー樹脂を無添加
とし、ポリプロピレン樹脂を70重量%とした以外は実
施例1と同様に着色剤を作製し、被着色体と成形し、機
械物性試験を行った。
Comparative Example 1 A coloring agent was prepared in the same manner as in Example 1 except that the ionomer resin was not added and the amount of the polypropylene resin was changed to 70% by weight. .

【0037】[比較例2] 実施例1と同じアイオノマ
ー樹脂を2.5重量%、ポリプロピレンを67.5重量
%とした以外は実施例1と同様に着色剤を作製し、被着
色体と成形し(ガラス繊維100重量部に対しアイオノ
マー樹脂0.83重量部)、機械物性試験を行った。
Comparative Example 2 A colorant was prepared in the same manner as in Example 1 except that the same ionomer resin as in Example 1 was used in an amount of 2.5% by weight and polypropylene was used in an amount of 67.5% by weight. (1003 parts by weight of glass fiber and 0.83 parts by weight of ionomer resin), and a mechanical property test was performed.

【0038】[比較例3] 実施例1と同じアイオノマ
ー樹脂を40重量%、ポリプロピレンを30重量%とし
た以外は実施例1と同様に着色剤を作製し、被着色体と
成形し(ガラス繊維100重量部に対しアイオノマー樹
脂13.3重量部)、機械物性試験を行った。
Comparative Example 3 A coloring agent was prepared in the same manner as in Example 1 except that the same ionomer resin as in Example 1 was used in an amount of 40% by weight and that of polypropylene was used in an amount of 30% by weight. (13.3 parts by weight of the ionomer resin with respect to 100 parts by weight) and a mechanical property test.

【0039】[比較例4] 白色顔料として酸化チタン
(タイペークPF711 石原産業社製)を用いた以外
は比較例1と同様に着色剤を作製し、被着色体と成形
し、機械物性試験を行った。
Comparative Example 4 A coloring agent was prepared in the same manner as in Comparative Example 1 except that titanium oxide (Taipeku PF711, manufactured by Ishihara Sangyo Co., Ltd.) was used as a white pigment, molded into a material to be colored, and subjected to mechanical property tests. Was.

【0040】[比較例5] アイオノマー樹脂を10重
量%、ポリプロピレンを60重量%とした以外は比較例
4と同様に着色剤を作製し、被着色体と成形し(ガラス
繊維100重量部に対し3.3重量部)、機械物性試験
を行った。以上、比較例1〜5の結果を表2に示した。
Comparative Example 5 A coloring agent was prepared in the same manner as in Comparative Example 4 except that the amount of the ionomer resin was changed to 10% by weight and the amount of the polypropylene was changed to 60% by weight. 3.3 parts by weight), and a mechanical property test was performed. Table 2 shows the results of Comparative Examples 1 to 5.

【0041】[0041]

【表2】 [Table 2]

【0042】[0042]

【発明の効果】本発明の着色剤組成物は、ガラス繊維強
化オレフィン系樹脂の着色用の組成物であって、オレフ
ィン系樹脂と、白色顔料として硫化亜鉛又は硫化亜鉛と
硫酸バリウムの複合体と、金属陽イオンによって分子鎖
間が架橋されたカルボン酸変性ポリオレフィンとを含有
し、白色顔料として硫化亜鉛又は硫化亜鉛と硫酸バリウ
ムの複合体を用いることにより良好な白色性及び隠蔽性
を有するとともに、着色のために被着色体と混練した際
にガラス繊維の損傷を抑えることが出来る。
The colorant composition of the present invention is a composition for coloring a glass fiber reinforced olefin resin, comprising a olefin resin and zinc sulfide or a composite of zinc sulfide and barium sulfate as a white pigment. Containing a carboxylic acid-modified polyolefin in which the molecular chains are cross-linked by a metal cation, and having good whiteness and hiding properties by using zinc sulfide or a composite of zinc sulfide and barium sulfate as a white pigment, When kneaded with the object to be colored for coloring, damage to glass fibers can be suppressed.

【0043】本発明の成形品は着色剤組成物と被着色体
とから成り、ガラス繊維100重量部に対し、金属陽イ
オンによって分子鎖間が架橋されたカルボン酸変性ポリ
オレフィンが1〜10重量部の割合で含有されることに
よって、ガラス繊維とオレフィン系樹脂との界面を接着
強化させ、優れたアイゾット衝撃値、曲げ弾性率及び熱
変形温度等の良好な物性が得られる。
The molded article of the present invention comprises a colorant composition and a material to be colored, and 1 to 10 parts by weight of a carboxylic acid-modified polyolefin in which molecular chains are crosslinked by a metal cation to 100 parts by weight of glass fiber. , The interface between the glass fiber and the olefin resin is strengthened by adhesion, and excellent physical properties such as excellent Izod impact value, flexural modulus and heat deformation temperature can be obtained.

【0044】そして、前記白色顔料と前記特定量比の金
属陽イオンによって分子鎖間が架橋されたカルボン酸変
性ポリオレフィンの相乗作用により、機械物性の優れた
繊維強化オレフィン系樹脂着色成形品が得られる。
By the synergistic action of the white pigment and the carboxylic acid-modified polyolefin in which the molecular chains are crosslinked by the metal cation having the specific ratio, a colored molded article of a fiber-reinforced olefin resin having excellent mechanical properties can be obtained. .

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】オレフィン系樹脂と、白色顔料として硫化
亜鉛又は硫化亜鉛と硫酸バリウムの複合体と、金属陽イ
オンによって分子鎖間が架橋されたカルボン酸変性ポリ
オレフィンとを含有することを特徴とする着色剤組成
物。
(1) An olefin resin, zinc sulfide or a composite of zinc sulfide and barium sulfate as a white pigment, and a carboxylic acid-modified polyolefin in which molecular chains are cross-linked by a metal cation. Colorant composition.
【請求項2】金属陽イオンによって分子鎖間が架橋され
たカルボン酸変性ポリオレフィンが、Na又はZnイオ
ンで架橋されたエチレン−メタクリル酸共重合体である
ことを特徴とする請求項1に記載の着色剤組成物。
2. The method according to claim 1, wherein the carboxylic acid-modified polyolefin in which the molecular chains are crosslinked by a metal cation is an ethylene-methacrylic acid copolymer crosslinked with Na or Zn ions. Colorant composition.
【請求項3】ガラス繊維とオレフィン系樹脂とから成る
被着色体と、請求項1記載の着色剤組成物とから成る成
形品であって、ガラス繊維100重量部に対し金属陽イ
オンによって分子鎖間が架橋されたカルボン酸変性ポリ
オレフィンが1〜10重量部であることを特徴とする成
形品。
3. A molded article comprising a colorant comprising glass fiber and an olefin-based resin, and the colorant composition according to claim 1, wherein a molecular chain is formed by a metal cation with respect to 100 parts by weight of glass fiber. A molded article characterized in that the amount of the carboxylic acid-modified polyolefin in which the space is crosslinked is 1 to 10 parts by weight.
【請求項4】ガラス繊維とオレフィン系樹脂とから成る
被着色体と、請求項2記載の着色剤組成物とから成る成
形品であって、ガラス繊維100重量部に対しNa又は
Znイオンで架橋されたエチレン−メタクリル酸共重合
体が1〜10重量部であることを特徴とする成形品。
4. A molded article comprising a colorant comprising glass fiber and an olefin resin, and a colorant composition according to claim 2, wherein 100 parts by weight of glass fiber are crosslinked with Na or Zn ions. A molded article characterized in that the amount of the ethylene-methacrylic acid copolymer is 1 to 10 parts by weight.
JP2000163338A 2000-05-31 2000-05-31 Colorant composition for fiber reinforced olefinic resin and molded article prepared therefrom Pending JP2001342305A (en)

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Publication number Priority date Publication date Assignee Title
WO2006006807A1 (en) * 2004-07-08 2006-01-19 Sambark Lft Co., Ltd. Long-fiber reinforced pol yolefin composition
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