JP2013040252A - Resin material for sliding object to be printed and molding for sliding object to be printed - Google Patents
Resin material for sliding object to be printed and molding for sliding object to be printed Download PDFInfo
- Publication number
- JP2013040252A JP2013040252A JP2011176760A JP2011176760A JP2013040252A JP 2013040252 A JP2013040252 A JP 2013040252A JP 2011176760 A JP2011176760 A JP 2011176760A JP 2011176760 A JP2011176760 A JP 2011176760A JP 2013040252 A JP2013040252 A JP 2013040252A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- printed
- polymer
- sliding
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 239000011347 resin Substances 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 61
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- 125000003277 amino group Chemical group 0.000 description 1
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- 239000003830 anthracite Substances 0.000 description 1
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- 239000012736 aqueous medium Substances 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
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- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
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- 239000001110 calcium chloride Substances 0.000 description 1
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- 239000004917 carbon fiber Substances 0.000 description 1
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- 238000005227 gel permeation chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 235000019341 magnesium sulphate Nutrition 0.000 description 1
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- 239000004579 marble Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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Abstract
Description
本発明は、被印刷体（例えば、紙、樹脂シート等）が摺動する部品として使用される成形体、その成形体の材料になる被印刷体摺動用樹脂材料に関する。 The present invention relates to a molded body used as a part on which a printing body (for example, paper, a resin sheet, etc.) slides, and a resin material for sliding the printing body to be a material of the molded body.
プリンター等においては、印刷不良（印刷のずれやにじみ）を減らすために、紙等の被印刷体を所定の印刷位置に供給することが求められる。そのため、被印刷体に接する部品（例えば、フィーダー等）においては、被印刷体に対する摺動性が高いことが要求される。
また、プリンターを長期間使用すると、被印刷体との摺動によって被印刷体に接する部品が磨耗し、その磨耗によって被印刷体との隙間距離が広がるため、印刷の画質（鮮明性）を損ねることがあった。そのため、被印刷体に接する部品としては、耐磨耗性に優れるものが求められていた。
In a printer or the like, it is required to supply a printing medium such as paper to a predetermined printing position in order to reduce printing defects (print deviation and blurring). For this reason, a component (for example, a feeder or the like) in contact with the printing medium is required to have high slidability with respect to the printing medium.
Also, if the printer is used for a long period of time, the parts that come into contact with the printing medium will be worn by sliding with the printing medium, and the gap distance with the printing medium will be widened by the wear, so the image quality (clearness) of printing will be impaired. There was a thing. For this reason, parts that are in contact with the substrate to be printed have been required to have excellent wear resistance.
そこで、被印刷体に対する摺動性および耐磨耗性が高い材料として、摺動性を向上させるコーティング剤が表面に塗布された鋼板が開示されている（例えば、特許文献１）。しかし、特許文献１に記載の鋼板では、長期間、連続的に使用すると、コーティング剤が摩耗するため、依然として摺動性が損なわれることがあった。
また、近年、製品のデザインが複雑化・多機能化しているため、鋼板に代わって熱可塑性樹脂が広く使用されるようになってきている。
摺動性の高い熱可塑性樹脂としては、例えば、ＡＥＳ樹脂等の熱可塑性樹脂にシリコーンオイル等の潤滑剤やポリエチレン等のポリオレフィン樹脂を添加したものが知られている（特許文献２〜４参照）。
また、特許文献５には、ゴム変性スチレン樹脂にポリオレフィン系樹脂、スチレン−オレフィングラフト共重合体、ジメチルシリコーンを混合した摺動性スチレン系樹脂組成物が開示されている。
Then, the steel plate by which the coating agent which improves slidability was apply | coated to the surface as a material with high slidability with respect to a to-be-printed body and abrasion resistance is disclosed (for example, patent document 1). However, in the steel sheet described in Patent Document 1, when continuously used for a long period of time, the coating agent is worn, so that the slidability may still be impaired.
In recent years, the design of products has become more complex and multifunctional, so that thermoplastic resins have been widely used in place of steel plates.
As a highly slidable thermoplastic resin, for example, a resin obtained by adding a lubricant such as silicone oil or a polyolefin resin such as polyethylene to a thermoplastic resin such as AES resin is known (see Patent Documents 2 to 4). .
Further, Patent Document 5 discloses a slidable styrene resin composition obtained by mixing a rubber-modified styrene resin with a polyolefin resin, a styrene-olefin graft copolymer, and dimethyl silicone.
一方、合成樹脂の耐磨耗性を向上させる添加剤として、特許文献６に、特定のポリエチレン成分を添加する方法が開示されている。
また、ガラス繊維やガラスビーズ等の充填材を配合する方法も知られている。例えば、特許文献７に、ガラスビーズを配合して、耐摩耗性、耐久性、耐衝撃性、耐化学薬品性ならびに光沢を向上させる方法が開示されている。また、特許文献８には、ポリカプロラクトン樹脂やポリメタクリル酸メチル樹脂を配合して、成形品の表面を平滑にし、摩擦・磨耗特性、耐擦傷性等を改善する方法が開示されている。
On the other hand, Patent Document 6 discloses a method of adding a specific polyethylene component as an additive for improving the abrasion resistance of a synthetic resin.
A method of blending fillers such as glass fibers and glass beads is also known. For example, Patent Document 7 discloses a method for improving wear resistance, durability, impact resistance, chemical resistance and gloss by blending glass beads. Patent Document 8 discloses a method of blending a polycaprolactone resin or a polymethyl methacrylate resin to smooth the surface of a molded product and improving friction / wear characteristics, scratch resistance, and the like.
また、プリンターの被印刷体に接する部品においては、インクヘッドに紙粉が付着することを防止するために、供給時に発生する静電気を抑制することが求められている。その要求に対しては、特許文献９に、帯電防止剤であるポリエーテルエステルアミド成分を添加して帯電防止性を向上させることが開示されている。 In addition, in a part that comes into contact with a printing body of a printer, it is required to suppress static electricity generated during supply in order to prevent paper dust from adhering to the ink head. In response to this requirement, Patent Document 9 discloses that a polyether ester amide component as an antistatic agent is added to improve antistatic properties.
特許文献２〜５に記載の樹脂材料は、近年の印刷の高速化に対しても摺動性を満たしているが、耐磨耗性が不充分になりやすく、印刷数が多くなると、磨耗が進んで画質に影響を与えることがあった。また、特許文献２〜５に記載の樹脂材料の中には充分な耐磨耗性を有するものもあるが、その場合には、摺動性が低下する傾向にあり、印刷の際に被印刷体を傷付けることがあった。被印刷体に傷が付くと、印刷物としての品質が低下する問題が生じる。
特許文献６，７に記載の樹脂材料では、摺動性および耐磨耗性に優れるものの、ガラス繊維やガラスビーズによって被印刷体に傷を付けることがあった。特許文献８に記載の樹脂材料では、摺動性が不充分であった。
特許文献９の樹脂材料においても、耐磨耗性が不充分であり、耐磨耗性を向上させる対策を採ると、摺動性が低下する傾向にあった。
これらのことから、被印刷体に対する摺動性と帯電防止性とを有しつつ、耐磨耗性と被印刷体の傷付き防止性とを両立できる被印刷体摺動用樹脂材料および成形品が求められていた。
そこで、本発明は、被印刷体の摺動性および帯電防止性が高い上に、耐磨耗性に優れ、しかも被印刷体の傷付きを防止できる被印刷体摺動用樹脂材料および被印刷体摺動用成形体を提供することを目的とする。
The resin materials described in Patent Documents 2 to 5 satisfy slidability even for recent high-speed printing, but wear resistance tends to be insufficient, and wear increases when the number of printing increases. In some cases, the image quality was affected. In addition, some of the resin materials described in Patent Documents 2 to 5 have sufficient wear resistance, but in that case, the sliding property tends to be reduced, and printing is performed at the time of printing. It could hurt the body. If the printed material is scratched, there is a problem that the quality of the printed material is deteriorated.
Although the resin materials described in Patent Documents 6 and 7 are excellent in slidability and wear resistance, the printed material may be damaged by glass fibers or glass beads. The resin material described in Patent Document 8 has insufficient slidability.
Even in the resin material of Patent Document 9, the wear resistance is insufficient, and if measures are taken to improve the wear resistance, the slidability tends to decrease.
Therefore, there is provided a resin material for sliding a printed material and a molded product that have both slidability and antistatic properties with respect to the printed material, and that can achieve both wear resistance and scratch resistance of the printed material. It was sought after.
Accordingly, the present invention provides a resin material for sliding a printing medium and a printing body that have high sliding properties and antistatic properties of the printing body and are excellent in wear resistance and can prevent the printing body from being damaged. It aims at providing the molded object for sliding.
本発明は、以下の態様を包含する。
［１］スチレン系樹脂と、導電性ポリマーと、モース硬度４以下の無機充填材とを含有することを特徴とする被印刷体摺動用樹脂材料。
［２］前記スチレン系樹脂がＡＥＳ樹脂である［１］に記載の被印刷体摺動用樹脂材料。
［３］前記無機充填材が炭酸カルシウムである［１］または［２］に記載の被印刷体摺動用樹脂材料。
[４]前記導電性ポリマーが、ポリアミドまたはポリオレフィンのブロックと、ポリエーテルおよび／またはポリエステルのブロックとを有している［１］〜［３］のいずれか１項に記載の被印刷体摺動用樹脂材料。
［５］［１］〜［４］のいずれか１項に記載の被印刷体摺動用樹脂材料が成形されたことを特徴とする被印刷体摺動用成形体。
The present invention includes the following aspects.
[1] A resin material for sliding a printing medium, comprising a styrene resin, a conductive polymer, and an inorganic filler having a Mohs hardness of 4 or less.
[2] The resin material for sliding a printing medium according to [1], wherein the styrene resin is an AES resin.
[3] The resin material for sliding a printing medium according to [1] or [2], wherein the inorganic filler is calcium carbonate.
[4] The printed material sliding object according to any one of [1] to [3], wherein the conductive polymer has a polyamide or polyolefin block and a polyether and / or polyester block. Resin material.
[5] A printed body sliding molded body, wherein the printed body sliding resin material according to any one of [1] to [4] is molded.
本発明の被印刷体摺動用樹脂材料および被印刷体摺動用成形体は、被印刷体の摺動性および帯電防止性が高い上に、耐磨耗性に優れ、しかも被印刷体の傷付きを防止できる。 The printed material sliding resin material and the printed material sliding molded body of the present invention have high slidability and antistatic properties of the printed material, and are excellent in wear resistance, and the printed material is scratched. Can be prevented.
＜被印刷体摺動用樹脂材料＞
本発明の被印刷体摺動用樹脂材料（以下、「樹脂材料」と略す。）は、スチレン系樹脂と、導電性ポリマーと、無機充填材とを含有する。
<Sliding resin material for printing material>
The printed material sliding resin material (hereinafter abbreviated as “resin material”) of the present invention contains a styrene resin, a conductive polymer, and an inorganic filler.
（スチレン系樹脂）
スチレン系樹脂は、芳香族スチレン単量体単位を有する重合体を含む樹脂である。
具体的には、ポリスチレン（ＰＳ）、アクリロニトリル−スチレン共重合体（ＡＳ樹脂）、ゴムにより強化されたゴム強化スチレン系樹脂等が挙げられる。
ゴム強化スチレン系樹脂としては、ハイインパクトポリスチレン（ＨＩＰＳ）、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、エチレン系のゴム質重合体を用いたアクリロニトリル−エチレン−スチレン共重合体（ＡＥＳ樹脂）等が挙げられる。これらの中でも、被印刷体の摺動性および耐磨耗性がより高くなることから、ＡＥＳ樹脂が好ましい。
ゴム強化スチレン系樹脂は、成形性に優れることから、芳香族スチレン系単量体単位を有するグラフト重合体（Ｃ）と、芳香族スチレン系単量体単位を有する共重合体（Ｄ）とを含有するものが好ましい。
(Styrene resin)
The styrene resin is a resin containing a polymer having an aromatic styrene monomer unit.
Specific examples include polystyrene (PS), acrylonitrile-styrene copolymer (AS resin), rubber-reinforced styrene-based resin reinforced with rubber, and the like.
Examples of rubber-reinforced styrene resins include high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), and acrylonitrile-ethylene-styrene copolymer (AES resin) using an ethylene rubbery polymer. Etc. Among these, AES resin is preferable because the slidability and wear resistance of the printing medium are further increased.
Since the rubber-reinforced styrene resin has excellent moldability, a graft polymer (C) having an aromatic styrene monomer unit and a copolymer (D) having an aromatic styrene monomer unit are used. What is contained is preferable.
［グラフト重合体（Ｃ）］
グラフト重合体（Ｃ）の製造方法としては、例えば、ゴム質重合体（Ａ）に単量体混合物（Ｂ）を乳化グラフト重合させる方法が挙げられる。
[Graft polymer (C)]
Examples of the method for producing the graft polymer (C) include a method in which the rubber mixture (A) is subjected to emulsion graft polymerization of the monomer mixture (B).
（ｉ）ゴム質重合体（Ａ）
ゴム質重合体（Ａ）としては、ポリブタジエン、ポリブタジエンの水素添加物、ポリイソプレン、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体、ブタジエン−アクリロニトリル共重合体、エチレン−プロピレン−非共役ジエン共重合体などのエチレン系ゴム質重合体、イソブチレン−イソプレン共重合体、アクリルゴム、スチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、ＳＥＢＳ等の水素添加ジエン系（ブロック、ランダムおよびホモ）（共）重合体、ポリウレタンゴムおよびシリコーンゴム等が挙げられる。
これらの中でも、樹脂材料の摺動性をより高くできることから、エチレン−プロピレン−非共役ジエン共重合体（以下、「ＥＰＤＭ」という。）が好ましい。
(I) Rubber polymer (A)
Examples of the rubber polymer (A) include polybutadiene, hydrogenated polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene-nonconjugated diene copolymer. Hydrogenated diene systems (blocks) such as ethylene rubber polymers such as polymers, isobutylene-isoprene copolymers, acrylic rubber, styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, SEBS , Random and homo) (co) polymers, polyurethane rubber, silicone rubber and the like.
Among these, an ethylene-propylene-nonconjugated diene copolymer (hereinafter referred to as “EPDM”) is preferable because the slidability of the resin material can be further improved.
ＥＰＤＭは、エチレン含量が７５〜９０質量％であることが好ましい。エチレン含量が７５〜９０質量％であれば、長期にわたって使用しても安定した摺動性（動摩擦係数）が得られる。また、摺動性を高くできるため、無機充填材の添加量を少なくすることができ、無機充填材の分散不良による外観不良を防止できる。
ＥＰＤＭにおける非共役ジエン成分としては特に制限はなく、例えば、１，４−ヘキサジエン、５−エチリデン−２−ノルボルネン、５−ビニルノルボルネンおよびジシクロペンタジエン等が挙げられる。
EPDM preferably has an ethylene content of 75 to 90% by mass. If the ethylene content is 75 to 90% by mass, stable slidability (dynamic friction coefficient) can be obtained even when used over a long period of time. Moreover, since slidability can be made high, the addition amount of an inorganic filler can be decreased and the appearance defect by the dispersion | distribution defect of an inorganic filler can be prevented.
The non-conjugated diene component in EPDM is not particularly limited, and examples thereof include 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, and dicyclopentadiene.
ゴム質重合体（Ａ）としてＥＰＤＭを用いる場合には、変性α−オレフィン共重合体を併用することが好ましい。変性α−オレフィン共重合体をＥＰＤＭと併用すると、乳化時の乳化安定性を高くできるので、製造安定性が高くなる。また、変性α−オレフィン共重合体は摺動性を改善する効果も有する。
変性α−オレフィン共重合体は、α−オレフィン共重合体に官能基を有する化合物が付加された重合体であって、質量平均分子量が１０００〜５０００のものである。例えば、α−オレフィン９９．８〜８０質量％と不飽和カルボン酸系化合物０．２〜２０質量％とが共重合した変性ポリエチレン等が挙げられる。ここで、α−オレフィンとしては、エチレン等が挙げられ、不飽和カルボン酸系化合物としては、例えば、アクリル酸、マレイン酸、イタコン酸、無水マレイン酸、無水イタコン酸およびマレイン酸モノアミドが挙げられる。
変性α−オレフィン共重合体の含有量は、ＥＰＤＭ１００質量部に対して０．１〜３０質量部であることが好ましい。変性α−オレフィン共重合体の含有量が０．１質量部以上３０質量部以下であれば、乳化安定性をより高くでき、より安定に乳化グラフト重合できる。
When EPDM is used as the rubbery polymer (A), it is preferable to use a modified α-olefin copolymer in combination. When the modified α-olefin copolymer is used in combination with EPDM, the emulsion stability at the time of emulsification can be increased, and thus the production stability is increased. The modified α-olefin copolymer also has an effect of improving sliding properties.
The modified α-olefin copolymer is a polymer obtained by adding a compound having a functional group to an α-olefin copolymer, and has a mass average molecular weight of 1000 to 5000. Examples thereof include modified polyethylene obtained by copolymerizing 99.8 to 80% by mass of an α-olefin and 0.2 to 20% by mass of an unsaturated carboxylic acid compound. Here, examples of the α-olefin include ethylene, and examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, and maleic acid monoamide.
The content of the modified α-olefin copolymer is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of EPDM. When the content of the modified α-olefin copolymer is 0.1 parts by mass or more and 30 parts by mass or less, the emulsion stability can be further increased, and emulsion graft polymerization can be more stably performed.
乳化グラフト重合においては、ゴム質重合体（Ａ）に単量体混合物（Ｂ）を重合するに際し、ゴム質重合体（Ａ）をラテックス状にする。
ゴム質重合体（Ａ）がＥＰＤＭと変性α−オレフィン共重合体とを含む場合のゴム質重合体ラテックスを調製する方法としては、公知の溶融混練手段でＥＰＤＭと変性α−オレフィン共重合体とを所定の割合で配合、混練し、機械的剪断力を与えて充分に分散させ、その混練物を、乳化剤を含む水性媒体に添加する方法が挙げられる。この方法によれば、安定なゴム質重合体（Ａ）のラテックスを得ることができる。
In the emulsion graft polymerization, when the monomer mixture (B) is polymerized with the rubber polymer (A), the rubber polymer (A) is made into a latex.
As a method for preparing a rubbery polymer latex when the rubbery polymer (A) contains EPDM and a modified α-olefin copolymer, EPDM and the modified α-olefin copolymer can be prepared by a known melt-kneading means. Can be blended and kneaded at a predetermined ratio, sufficiently dispersed by applying a mechanical shear force, and the kneaded product added to an aqueous medium containing an emulsifier. According to this method, a stable latex of the rubbery polymer (A) can be obtained.
上記ラテックスの調製方法における溶融混練手段としては特に制限はないが、汎用的であることから、ニーダー、バンバリーミキサー、多軸スクリュー押出機が好ましい。
乳化剤としては、例えば、オレイン酸カリウムや不均化ロジン酸カリウム等のアニオン系界面活性剤などが用いられる。乳化剤の添加量は、ＥＰＤＭ１００質量部に対して１〜１０質量部とすることが好ましい。乳化剤は、例えばオレイン酸をＥＰＤＭと低分子量変性α−オレフィン共重合体にあらかじめ混合しておき、これに水酸化カリウム水溶液を添加して、オレイン酸カリウムを生成させることにより、添加することもできる。
The melt kneading means in the method for preparing the latex is not particularly limited, but a kneader, a Banbury mixer, and a multi-screw extruder are preferable because they are versatile.
As the emulsifier, for example, an anionic surfactant such as potassium oleate or disproportionated potassium rosinate is used. The amount of the emulsifier added is preferably 1 to 10 parts by mass with respect to 100 parts by mass of EPDM. The emulsifier can be added, for example, by mixing oleic acid in advance with EPDM and a low molecular weight modified α-olefin copolymer, and adding potassium hydroxide aqueous solution thereto to form potassium oleate. .
ＥＰＤＭと変性α−オレフィン共重合体を含むゴム質重合体（Ａ）は、未架橋のまま使用してもよいし、架橋処理してもよい。架橋処理する方法としては、未架橋のゴム質重合体ラテックスの固形分１００質量部に対して、ジ−t−ブチル−オキシトリメチルシクロヘキサン等の有機過酸化物を０．１〜５質量部およびジビニルベンゼン等の多官能性化合物を０．１〜５質量部添加して、６０〜１４０℃で、０．５〜５時間程度反応させる方法などが挙げられる。 The rubbery polymer (A) containing EPDM and a modified α-olefin copolymer may be used as it is uncrosslinked or may be subjected to a crosslinking treatment. As a method for the crosslinking treatment, 0.1 to 5 parts by mass of an organic peroxide such as di-t-butyl-oxytrimethylcyclohexane and divinyl are used with respect to 100 parts by mass of the solid content of the uncrosslinked rubber polymer latex. Examples include a method in which 0.1 to 5 parts by mass of a polyfunctional compound such as benzene is added and reacted at 60 to 140 ° C. for about 0.5 to 5 hours.
ラテックスに含まれるゴム質重合体（Ａ）は、平均粒子径が０．２〜１μｍの粒子であることが好ましい。ゴム質重合体（Ａ）の平均粒子径が０．２μｍ以上であれば、得られる樹脂材料の耐衝撃性が高くなり、１μｍ以下であれば、光沢低下を抑制し、表面外観を良好にできる。
ここで、ゴム質重合体（Ａ）の平均粒子径とは、レーザー回折・散乱法で測定した体積 基準の平均粒子径のことである。
The rubbery polymer (A) contained in the latex is preferably particles having an average particle size of 0.2 to 1 μm. If the average particle diameter of the rubber polymer (A) is 0.2 μm or more, the resulting resin material has high impact resistance, and if it is 1 μm or less, the gloss can be suppressed and the surface appearance can be improved. .
Here, the average particle size of the rubber polymer (A) is a volume-based average particle size measured by a laser diffraction / scattering method.
（ii）単量体混合物（Ｂ）
単量体混合物（Ｂ）は、芳香族ビニル系単量体を必須成分として含み、シアン化ビニル系単量体、芳香族ビニル系単量体およびシアン化ビニル系単量体と重合可能な他のビニル単量体を任意成分として含む混合物である。
芳香族ビニル系単量体としては、例えば、スチレン、α−メチルスチレン、ｐ−メチルスチレン等が挙げられる。
シアン化ビニル系単量体としては、例えば、アクリロニトリル、メタクリロニトリル等が挙げられる。
他のビニル系単量体としては、例えば、アクリル酸アルキルエステル（例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピルおよびアクリル酸ブチル等）、メタクリル酸アルキルエステル（例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピルおよびメタクリル酸ブチル等）、Ｎ−置換マレイミド系単量体（例えば、マレイミド、Ｎ−メチルマレイミド、Ｎ−ブチルマレイミド、Ｎ−フェニルマレイミド、Ｎ−（２−メチルフェニル） マレイミド、Ｎ−（４−ヒドロキシフェニル）マレイミド、Ｎ−シクロヘキシルマレイミド等）が挙げられる。これらの中でも、アクリル酸ブチルまたはメタクリル酸メチルが好ましく用いられる。
単量体混合物（Ｂ）の組成は、得られる樹脂材料の物性バランスに優れることから、芳香族ビニル系単量体が６０〜７６質量％、シアン化ビニル系単量体が４０〜２４質量％、他のビニル系単量体が０〜２０質量％であることが好ましい。
(Ii) Monomer mixture (B)
The monomer mixture (B) contains an aromatic vinyl monomer as an essential component, and can be polymerized with a vinyl cyanide monomer, an aromatic vinyl monomer and a vinyl cyanide monomer. This is a mixture containing the vinyl monomer as an optional component.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, and the like.
Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.
Examples of other vinyl monomers include, for example, alkyl acrylate esters (for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), alkyl methacrylate esters (for example, methyl methacrylate, methacrylic acid). Ethyl, propyl methacrylate and butyl methacrylate), N-substituted maleimide monomers (eg, maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide) N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide, etc.). Among these, butyl acrylate or methyl methacrylate is preferably used.
Since the composition of the monomer mixture (B) is excellent in the balance of physical properties of the resin material obtained, the aromatic vinyl monomer is 60 to 76% by mass, and the vinyl cyanide monomer is 40 to 24% by mass. The other vinyl monomers are preferably 0 to 20% by mass.
（iii）グラフト重合体（Ｃ）の製造方法
グラフト重合体（Ｃ）を製造する方法としては、ゴム質重合体（Ａ）のラテックスに単量体混合物（Ｂ）を添加し、所定の重合温度に加熱して乳化グラフト重合させる方法が挙げられる。中でも、単量体混合物（Ｂ）にレドックス系開始剤を混合した上で、単量体混合物（Ｂ）を１時間以上にわたって、ゴム質重合体（Ａ）のラテックスに連続的に添加することが好ましい。単量体混合物（Ｂ）の添加時間が１時間未満の場合、ラテックス安定性が低下して重合収率が低下することがある。
重合後のグラフト重合体（Ｃ）には、必要に応じて酸化防止剤を添加してもよい。ここで使用されるレドックス系開始剤としては、油溶性有機過酸化物と硫酸第一鉄−キレート剤−還元剤とが組み合わされたものが好ましい。油溶性有機過酸化物としては、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、ターシャリーブチルハイドロパーオキサイド等が挙げられる。より好ましいレドックス系開始剤としては、クメンハイドロパーオキサイド、硫酸第一鉄、ピロリン酸ナトリウム、デキストロースからなるものである。
グラフト重合体（Ｃ）においては、ゴム質重合体（Ａ）４０〜８０質量％（固形分として）に、単量体混合物（Ｂ）６０〜２０質量％を重合する〔（Ａ）と（Ｂ）の合計１００質量％〕ことが好ましい。ゴム質重合体（Ａ）が４０質量％未満である（単量体混合物が６０質量％を超える）場合、ゴム質重合体（Ａ） が８０質量％を超える（単量体混合物が２０質量％未満である）場合のいずれも、耐衝撃性が低下する傾向にある。
上記グラフト重合体の製造方法によりグラフト重合体ラテックスが得られる。グラフト重合体ラテックスからグラフト重合体（Ｃ）を回収する方法としては、例えば、グラフト重合体ラテックスに析出剤を添加し、加熱、攪拌した後、析出剤を分離し、これを水洗、脱水、乾燥する析出法が採用される。
析出法における析出剤としては、例えば、硫酸、酢酸、塩化カルシウムまたは硫酸マグネシウム等の水溶液を単独で使用あるいは併用できる。
(Iii) Method for Producing Graft Polymer (C) As a method for producing the graft polymer (C), the monomer mixture (B) is added to the latex of the rubber polymer (A), and a predetermined polymerization temperature is obtained. And emulsion graft polymerization by heating. In particular, the monomer mixture (B) may be continuously added to the latex of the rubbery polymer (A) over a period of 1 hour or more after mixing the redox initiator with the monomer mixture (B). preferable. When the addition time of the monomer mixture (B) is less than 1 hour, the latex stability may be lowered and the polymerization yield may be lowered.
You may add antioxidant to the graft polymer (C) after superposition | polymerization as needed. The redox initiator used here is preferably a combination of an oil-soluble organic peroxide and a ferrous sulfate-chelating agent-reducing agent. Examples of the oil-soluble organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, and tertiary butyl hydroperoxide. More preferred redox initiators include cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.
In the graft polymer (C), 60 to 20% by mass of the monomer mixture (B) is polymerized to 40 to 80% by mass (as a solid content) of the rubbery polymer (A) [(A) and (B ) Is preferably 100% by mass. When the rubber polymer (A) is less than 40% by mass (monomer mixture exceeds 60% by mass), the rubber polymer (A) exceeds 80% by mass (monomer mixture is 20% by mass). In any case, the impact resistance tends to decrease.
A graft polymer latex is obtained by the above-described method for producing a graft polymer. As a method for recovering the graft polymer (C) from the graft polymer latex, for example, a precipitant is added to the graft polymer latex, and after heating and stirring, the precipitant is separated, washed with water, dehydrated and dried. A precipitation method is employed.
As the precipitation agent in the precipitation method, for example, an aqueous solution of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate, or the like can be used alone or in combination.
［共重合体（Ｄ）］
共重合体（Ｄ）は、芳香族ビニル系単量体単位を必須成分として含み、シアン化ビニル系単量体単位、芳香族ビニル系単量体単位およびシアン化ビニル系単量体単位と重合可能な他のビニル単量体単位を任意成分として有する重合体である。
芳香族ビニル系単量体、シアン化ビニル系単量体、他のビニル系単量体の具体例としては、単量体混合物（Ｂ）と同様のものが挙げられる。
共重合体（Ｄ）の組成には特に制限はないが、芳香族ビニル系単量体単位６０〜７６質量％およびシアン化ビニル系単量体単位４０〜２４質量％を含むものが好ましい。芳香族ビニル系単量体単位６０〜７６質量％およびシアン化ビニル系単量体単位４０〜２４質量％を含む共重合体（Ｄ）においては、他のビニル系単量体単位を２０質量％以下の範囲で含んでも構わない。
[Copolymer (D)]
The copolymer (D) contains an aromatic vinyl monomer unit as an essential component and is polymerized with a vinyl cyanide monomer unit, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit. It is a polymer having other possible vinyl monomer units as optional components.
Specific examples of the aromatic vinyl monomer, vinyl cyanide monomer, and other vinyl monomers include the same as the monomer mixture (B).
Although there is no restriction | limiting in particular in a composition of a copolymer (D), What contains 60-76 mass% of aromatic vinyl-type monomer units and 40-24 mass% of vinyl cyanide-type monomer units is preferable. In the copolymer (D) containing 60 to 76% by mass of aromatic vinyl monomer units and 40 to 24% by mass of vinyl cyanide monomer units, 20% by mass of other vinyl monomer units is used. You may include in the following ranges.
共重合体（Ｄ）の製造には、乳化重合や懸濁重合等の重合法が採用される。共重合体（Ｄ）を乳化重合で製造する場合、反応器内に各単量体と乳化剤と重合開始剤と連鎖移動剤とを仕込み、加熱して重合し、得られた共重合体ラテックスから析出法により共重合体（Ｄ）を回収する。
ここで、乳化剤としては、ロジン酸カリウムおよびアルキルベンゼンスルホン酸ナトリウム等の一般的な乳化重合用乳化剤を用いることができる。また、重合開始剤としては、有機、無機の過酸化物系開始剤を用いることができ、連鎖移動剤としては、メルカプタン類、α−メチルスチレンダイマー、テルペン類等を用いることができる。析出法としては、グラフト重合体ラテックスからグラフト重合体（Ｃ）を回収するのと同様の方法を採用できる。
懸濁重合で製造する場合、反応器内に各単量体と懸濁剤と懸濁助剤と重合開始剤と連鎖移動剤とを仕込み、加熱して重合し、得られた共重合体スラリーを脱水して共重合体（Ｄ）を回収する。
ここで、懸濁剤としては、トリカルシウムフォスファイト、ポリビニルアルコール等を用いることができ、懸濁助剤としては、アルキルベンゼンスルホン酸ナトリウム等が用いることができる。また、重合開始剤としては、有機パーオキサイド類を用いることができ、連鎖移動剤としては、メルカプタン類、α−メチルスチレンダイマー、テルペン類等を用いることができる。
For the production of the copolymer (D), a polymerization method such as emulsion polymerization or suspension polymerization is employed. When the copolymer (D) is produced by emulsion polymerization, each monomer, an emulsifier, a polymerization initiator, and a chain transfer agent are charged into the reactor and polymerized by heating. From the obtained copolymer latex The copolymer (D) is recovered by a precipitation method.
Here, general emulsifiers for emulsion polymerization such as potassium rosinate and sodium alkylbenzenesulfonate can be used as the emulsifier. Moreover, organic and inorganic peroxide initiators can be used as the polymerization initiator, and mercaptans, α-methylstyrene dimers, terpenes, and the like can be used as the chain transfer agent. As the precipitation method, a method similar to the method of recovering the graft polymer (C) from the graft polymer latex can be employed.
In the case of producing by suspension polymerization, each monomer, suspending agent, suspending aid, polymerization initiator and chain transfer agent are charged into the reactor and polymerized by heating to obtain a copolymer slurry. And the copolymer (D) is recovered.
Here, as the suspending agent, tricalcium phosphite, polyvinyl alcohol or the like can be used, and as the suspending aid, sodium alkylbenzene sulfonate or the like can be used. Further, organic peroxides can be used as the polymerization initiator, and mercaptans, α-methylstyrene dimer, terpenes, and the like can be used as the chain transfer agent.
［（Ｃ）成分と（Ｄ）成分との配合］
本発明の摺動用材料は、摺動性、耐摩耗性、紙に対する耐傷付き性、表面外観、機械的強度のバランスが特に良くなることから、グラフト重合体（Ｃ）と共重合体（Ｄ）の合計１００質量部に対し、グラフト重合体（Ｃ）の含有量が５〜７０質量部（共重合体（Ｄ）の含有量が９５〜３０質量部）であることが好ましく、１０〜５０質量部（共重合体（Ｄ）の含有量が９０〜５０質量部）であることがより好ましい。
[Composition of component (C) and component (D)]
The sliding material of the present invention has a particularly good balance of slidability, abrasion resistance, scratch resistance to paper, surface appearance, and mechanical strength, so that the graft polymer (C) and copolymer (D) It is preferable that the content of the graft polymer (C) is 5 to 70 parts by mass (the content of the copolymer (D) is 95 to 30 parts by mass) with respect to 100 parts by mass in total. It is more preferable that it is a part (content of a copolymer (D) is 90-50 mass parts).
［他の重合体（Ｅ）］
スチレン系樹脂は、グラフト重合体（Ｃ）および共重合体（Ｄ）以外に、スチレン系単量体単位を有さない他の重合体（Ｅ）が含まれてもよい。ただし、他の重合体（Ｅ）の含有割合は、スチレン系樹脂に対して２０質量％以下であることが好ましく、１０質量％以下であることが好ましい。
他の重合体（Ｅ）としては、例えば、ポリメチルメタクリレート系樹脂、ナイロン６樹脂、ナイロン６６樹脂、ポリブチレンテレフタレート系樹脂、ポリエチレンテレフタレート系樹脂、ポリカーボネート樹脂等が挙げられる。これら他の重合体（Ｅ）は単独で用いてもよいし、２種類以上を混合して用いてもよい。
[Other polymer (E)]
In addition to the graft polymer (C) and the copolymer (D), the styrene resin may include other polymers (E) having no styrene monomer units. However, the content ratio of the other polymer (E) is preferably 20% by mass or less, and preferably 10% by mass or less, based on the styrene resin.
Examples of the other polymer (E) include polymethyl methacrylate resin, nylon 6 resin, nylon 66 resin, polybutylene terephthalate resin, polyethylene terephthalate resin, and polycarbonate resin. These other polymers (E) may be used alone or in combination of two or more.
（導電性ポリマー）
導電性ポリマーは、電子伝導性を有する構造（例えば、π共役系構造）またはイオン伝導性を有する構造（例えば、ポリエーテル構造）を有するポリマーであり、帯電防止性を付与するものである。導電性ポリマーは１種を単独で使用してもよいし、２種類以上を混合して用いてもよい。
導電性ポリマーの中でも、スチレン系樹脂の共存下で帯電防止性をより発揮できることから、ポリアミドまたはポリオレフィンのブロックと、ポリエーテルおよび／またはポリエステルのブロックとを有するポリマーが好ましい。
さらには、インクの漏れ対策として求められる耐水性に優れていることから、ポリアミドのブロックとポリエーテルのブロックがエステル結合を介して繰り返し交互に結合したポリエーテルエステルアミドブロックポリマーが好ましい。なお、ポリエーテルエステルアミドブロックポリマーとしては、例えば、三洋化成工業株式会社製ペレスタット ＮＣ６３２１が挙げられる。
上記好ましい導電性ポリマーを構成するポリアミドとしては、ラクタムの開環重合体、アミノカルボン酸の自己重縮合体、ジアミンとジカルボン酸の重縮合体、およびこれらの混合物が挙げられる。
ポリオレフィンとしては、ポリエチレン、ポリプロピレン、ポリブタジエン、ポリイソプレン、あるいはこれらを２つ以上含む共重合体が挙げられる。
ポリエーテルとしては、ポリエチレンオキシド（ポリエチレングリコール）、ポリプロピレンオキシド、ポリオキシアルキレングリコールが挙げられる。
なお、上記ポリアミドおよびポリオレフィンとポリエーテルとの結合方法は、両末端に、ポリエーテルのヒドロキシ基と反応可能な反応性官能基（カルボキシ基、ヒドロキシ基、アミノ基等）を有するポリアミドまたはポリオレフィンと、ポリエーテルとを反応させる方法が挙げられる。
(Conductive polymer)
The conductive polymer is a polymer having a structure having electronic conductivity (for example, a π-conjugated structure) or a structure having ionic conductivity (for example, a polyether structure), and imparts antistatic properties. A conductive polymer may be used individually by 1 type, and may mix and use 2 or more types.
Among conductive polymers, a polymer having a polyamide or polyolefin block and a polyether and / or polyester block is preferable because it can exhibit antistatic properties in the presence of a styrene resin.
Furthermore, a polyether ester amide block polymer in which polyamide blocks and polyether blocks are repeatedly and alternately bonded through ester bonds is preferable because of excellent water resistance required as a measure against ink leakage. In addition, as a polyether ester amide block polymer, Sanyo Chemical Industries Ltd. perestat NC6321 is mentioned, for example.
Examples of the polyamide constituting the preferable conductive polymer include a ring-opening polymer of lactam, a self-polycondensation product of aminocarboxylic acid, a polycondensation product of diamine and dicarboxylic acid, and a mixture thereof.
Examples of the polyolefin include polyethylene, polypropylene, polybutadiene, polyisoprene, and copolymers containing two or more of these.
Examples of the polyether include polyethylene oxide (polyethylene glycol), polypropylene oxide, and polyoxyalkylene glycol.
In addition, the method for bonding the polyamide and the polyolefin to the polyether includes a polyamide or a polyolefin having a reactive functional group (carboxy group, hydroxy group, amino group, etc.) capable of reacting with the hydroxy group of the polyether at both ends; The method of making it react with polyether is mentioned.
導電性ポリマーの含有量は、スチレン系樹脂１００質量部に対して５〜３０質量部であることが好ましく、１０〜２０質量部であることがより好ましい。導電性ポリマーの含有量が５質量部以上であれば、被印刷体が摺動する部分においても充分に高い帯電防止性を得ることができ、３０質量部以下であれば、充分な耐磨耗性を確保できる。 The content of the conductive polymer is preferably 5 to 30 parts by mass and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the styrene resin. If the content of the conductive polymer is 5 parts by mass or more, a sufficiently high antistatic property can be obtained even in a portion where the printing medium slides, and if it is 30 parts by mass or less, sufficient wear resistance is obtained. Can be secured.
（無機充填材）
本発明の樹脂材料は、無機充填材を含有することにより、耐磨耗性が向上する。本発明で使用される無機充填材は、モース硬度が４以下、好ましくは３以下のものである。
ここで、モース硬度は、標準物質に対するひっかき傷の有無で硬さの順列を決定する。
無機充填材のモース硬度が４以下であることにより、被印刷体の傷付き防止性を向上させることができる。
(Inorganic filler)
The resin material of the present invention improves the wear resistance by containing an inorganic filler. The inorganic filler used in the present invention has a Mohs hardness of 4 or less, preferably 3 or less.
Here, the Mohs hardness determines the permutation of hardness according to the presence or absence of scratches on the standard material.
When the inorganic filler has a Mohs hardness of 4 or less, it is possible to improve the scratch resistance of the printing medium.
モース硬度４以下の無機充填材としては、例えば、リン青銅、銅、フッ化カルシウム、鐘青銅、白雲石、銀、蛇紋石、大理石、真鍮、重晶石、アンチモン、ウッド合金、方解石、炭酸カルシウム、ホウ酸、雲母、金、セピオライト、亜鉛、方鉛鉱、ビスマス、アルミニウム、テルル、含水珪酸アルミニウム、ミョウバン、琥珀、無煙炭、硫黄、銀、マグネシウム、セレン、岩塩、カドミウム、石膏、ストロンチウム、錫、鉛、ガリウム、カルシウム、塩化銀、珪藻土、インジウム、タルク、黒鉛、リチウム、リン、カリウム、ナトリウム、黄土、ルビジウム、セシウム等の物質を粉体状にしたものが挙げられる。これらの無機充填材は単独で用いてもよいし、２種類以上を混合して用いてもよい。
上記無機充填材のなかでも、耐摩耗性および被印刷体の傷付き防止性がより高いことから、炭酸カルシウムが好ましい
Examples of inorganic fillers having a Mohs hardness of 4 or less include phosphor bronze, copper, calcium fluoride, bell bronze, dolomite, silver, serpentine, marble, brass, barite, antimony, wood alloy, calcite, calcium carbonate. , Boric acid, mica, gold, sepiolite, zinc, galena, bismuth, aluminum, tellurium, hydrous aluminum silicate, alum, firewood, anthracite, sulfur, silver, magnesium, selenium, rock salt, cadmium, gypsum, strontium, tin, Examples include lead, gallium, calcium, silver chloride, diatomaceous earth, indium, talc, graphite, lithium, phosphorus, potassium, sodium, loess, rubidium, cesium and the like in powder form. These inorganic fillers may be used alone or in combination of two or more.
Among the above inorganic fillers, calcium carbonate is preferred because of higher wear resistance and prevention of scratches on the substrate.
無機充填材の形状としては、樹脂材料中での分散性に優れ、摺動性、耐摩耗性のバランスが良くなることから、粉体状が好ましい。無機充填材粉体の平均粒子径としては０．４〜１０μｍであることが好ましく、０．７〜５μｍであることがより好ましい。無機充填材の平均粒子径が０．４μｍ以上であれば、溶融混錬時に凝集して外観不良の原因となる可能性が低減され、１０μｍ以下であれば、耐衝撃性低下の懸念も最小限に留められる。
ここで、無機充填材の平均粒子径とは、島津製作所製粉体比表面積測定装置ＳＳ−１００型で測定した粉末１ｇ当たりの比表面積値を下記計算式に用いて算出した粉末の平均粒径である。
平均粒子径＝６／（比重×比表面積）×１００００ 〔μｍ〕
The inorganic filler is preferably in the form of a powder because it is excellent in dispersibility in the resin material and has a good balance between slidability and wear resistance. The average particle size of the inorganic filler powder is preferably 0.4 to 10 μm, and more preferably 0.7 to 5 μm. If the average particle size of the inorganic filler is 0.4 μm or more, the possibility of agglomeration at the time of melt-kneading and causing appearance defects is reduced, and if it is 10 μm or less, there is minimal concern about a decrease in impact resistance. To be held in.
Here, the average particle diameter of the inorganic filler is the average particle diameter of the powder calculated using the specific surface area value per 1 g of the powder measured with a powder specific surface area measuring apparatus SS-100 manufactured by Shimadzu Corporation using the following formula. is there.
Average particle size = 6 / (specific gravity × specific surface area) × 10000 [μm]
無機充填材の含有量は、スチレン系樹脂１００質量部に対して５〜３０質量部であることが好ましく、１０〜２０質量部であることがより好ましい。無機充填材の含有量が５質量部以上であれば、耐摩耗性がより高くなり、３０質量部以下であれば、摺動性がより優れる。 The content of the inorganic filler is preferably 5 to 30 parts by mass and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the styrene resin. If the content of the inorganic filler is 5 parts by mass or more, the wear resistance is higher, and if it is 30 parts by mass or less, the slidability is more excellent.
（製造方法）
本発明の摺動用材料は、スチレン系樹脂、導電性ポリマー、モース硬度４以下の無機充填材、必要に応じて帯電防止剤、紫外線吸収剤、酸化防止剤、滑剤、加工助剤、顔料を混合し、例えば、押出機、バンバリーミキサーまたは混練ロール等にてペレット化することで容易に製造される。
(Production method)
The sliding material of the present invention is a mixture of a styrene resin, a conductive polymer, an inorganic filler having a Mohs hardness of 4 or less, and an antistatic agent, an ultraviolet absorber, an antioxidant, a lubricant, a processing aid, and a pigment as necessary. For example, it is easily manufactured by pelletizing with an extruder, a Banbury mixer, a kneading roll or the like.
＜被印刷体摺動用成形体＞
次に、本発明の被印刷体摺動用成形体について説明する。
本発明の被印刷体摺動用成形体は、上記被印刷体摺動用樹脂材料を成形したものである。成形方法としては、例えば、射出成形法、プレス成形法、押出成形法、真空成形法、ブロー成形法などが挙げられる。
本発明の被印刷体摺動用成形体は、上記被印刷体摺動用樹脂材料を成形したものであるから、被印刷体の摺動性や帯電防止性が高い上に、耐磨耗性に優れ、しかも被印刷体の傷付きを防止できる。このような被印刷体摺動用成形体は、例えば、プリンターのフィーダ等に使用され、特に紙と摺動する摺動部材等に好適である。
<Molded body for printing substrate sliding>
Next, the printing body sliding molded body of the present invention will be described.
The molded body for sliding the printing body of the present invention is obtained by molding the resin material for sliding the printed body. Examples of the molding method include an injection molding method, a press molding method, an extrusion molding method, a vacuum molding method, and a blow molding method.
Since the printed body sliding molded body of the present invention is formed by molding the above-mentioned printed body sliding resin material, the printed body has high slidability and antistatic properties and excellent wear resistance. In addition, the printed material can be prevented from being damaged. Such a printed body sliding molded body is used, for example, in a feeder of a printer, and is particularly suitable for a sliding member that slides on paper.
以下、実施例により本発明をさらに詳細に説明する。なお、以下において、「部」は「質量部」、「％」は「質量％」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. In the following, “part” means “part by mass” and “%” means “mass%”.
［製造例１］ゴム質重合体（Ａ−１）の製造
ＥＰＤＭ （デュポンダウエラストマー（株）製ＮＤＲ４８２０Ｐ、エチレン含量；８５％）８４部、低分子量変性ポリエチレン（三井化学（株）製ハイワックス２２０３Ａ）１６部、更に、オレイン酸カリウム５部を混合した。次いで、それらの混合物を２軸スクリュー押出機（池貝鉄鋼（株）製ＰＣＭ−３０型、Ｌ／Ｄ＝４０）のホッパーより４ｋｇ／時間で供給し、水酸化カリウム１５％水溶液を１１０ｇ／時間で連続的に供給しながら、加熱温度１８０℃で溶融混練して溶融物を押出した。引き続き、溶融物を前記押出機先端に取り付けた冷却用一軸押出機に連続的に供給し、９０℃まで冷却した。一軸押出機より取り出した固体を８０℃の温水中に投入し、連続的に分散させて、平均粒子径０．４５μｍのゴム質重合体ラテックスを得た。
このラテックスの固形分１００部に対してジ−ｔ−ブチルパーオキシトリメチルシクロヘキサンを１．１５部、ジビニルベンゼンを１．０部添加し、１２０℃で１時間反応させて、ゴム質重合体（Ａ−１）を調製した。
[Production Example 1] Production of rubber polymer (A-1) EPDM (NDR4820P manufactured by DuPont Dow Elastomer Co., Ltd., ethylene content: 85%) 84 parts, low molecular weight modified polyethylene (High Wax 2203A manufactured by Mitsui Chemicals, Inc.) 16 parts and 5 parts of potassium oleate were mixed. Then, the mixture was supplied at 4 kg / hour from the hopper of a twin screw extruder (Ikegai Steel Co., Ltd. PCM-30 type, L / D = 40), and a potassium hydroxide 15% aqueous solution was supplied at 110 g / hour. While continuously feeding, the melt was kneaded at a heating temperature of 180 ° C. to extrude the melt. Subsequently, the melt was continuously supplied to a cooling single screw extruder attached to the tip of the extruder and cooled to 90 ° C. The solid taken out from the single screw extruder was put into warm water at 80 ° C. and continuously dispersed to obtain a rubbery polymer latex having an average particle size of 0.45 μm.
1.15 parts of di-t-butylperoxytrimethylcyclohexane and 1.0 part of divinylbenzene are added to 100 parts of the solid content of the latex and reacted at 120 ° C. for 1 hour to give a rubbery polymer (A -1) was prepared.
［製造例２］ゴム質重合体（Ａ−２）の製造
ＥＰＤＭ （デュポンダウエラストマー（株）製ＮＤＲ４８２０Ｐ、エチレン含量；８５％）の代わりにＥＰＤＭ （三井化学（株）製ＴＰ３１８０、エチレン含量；７０％）を使用したこと以外は製造例１と同様にして、ゴム質重合体（Ａ−２）を調製した。
[Production Example 2] Production of rubbery polymer (A-2) EPDM (TP3180, Mitsui Chemicals, Inc., TP3180, ethylene content; 70) instead of EPDM (NDR4820P, DuPont Dow Elastomer Co., Ltd., ethylene content; 85%) %) Was used in the same manner as in Production Example 1 to prepare a rubbery polymer (A-2).
［製造例３］ゴム質重合体（Ａ−３）の製造
ＥＰＤＭ （デュポンダウエラストマー（株）製ＮＤＲ４８２０Ｐ、エチレン含量；８５％）の代わりにＥＰＤＭ （三井化学（株）製１４０３０、エチレン含量；５０％）を使用したこと以外は製造例１と同様にして、ゴム質重合体（Ａ−３）を調製した。
[Production Example 3] Production of rubber-like polymer (A-3) EPDM (Mitsui Chemicals, Inc. 14030, ethylene content; 50) instead of EPDM (NDR4820P, DuPont Dow Elastomer Co., Ltd., ethylene content; 85%) %) Was used in the same manner as in Production Example 1 to prepare a rubbery polymer (A-3).
［製造例４］グラフト重合体（Ｃ−１）の製造
窒素置換した攪拌機付きステンレス重合槽に、イオン交換水２００部、ゴム質重合体（Ａ−１）５０部（固形分換算）、オレイン酸カリウム２部、硫酸第一鉄０．００４部、ピロリン酸ナトリウム０．２部およびデキストロース０．２部を仕込み、温度を８０℃とした。これに、アクリロニトリル１７部およびスチレン３３部からなる単量体混合物とクメンハイドロパーオキサイド０．６部とを２時間連続的に添加し、重合温度を８０℃一定に保ち、乳化グラフト重合を行った。重合終了後に単量体の転化率を求めたところ、９３％であった。
重合後、得られたグラフト重合体ラテックスに酸化防止剤を添加し、さらに硫酸を添加して固形分を凝集させた。固形物を回収し、洗浄、脱水、乾燥の工程を経て、粉末状のグラフト重合体（Ｃ−１）を得た。
[Production Example 4] Production of graft polymer (C-1) In a stainless steel polymerization tank equipped with a stirrer substituted with nitrogen, 200 parts of ion-exchanged water, 50 parts of rubbery polymer (A-1) (in terms of solid content), oleic acid 2 parts of potassium, 0.004 part of ferrous sulfate, 0.2 part of sodium pyrophosphate and 0.2 part of dextrose were charged, and the temperature was set to 80 ° C. A monomer mixture consisting of 17 parts of acrylonitrile and 33 parts of styrene and 0.6 part of cumene hydroperoxide were continuously added thereto for 2 hours, and the polymerization temperature was kept constant at 80 ° C. to carry out emulsion graft polymerization. . When the conversion rate of the monomer was determined after completion of the polymerization, it was 93%.
After the polymerization, an antioxidant was added to the obtained graft polymer latex, and sulfuric acid was further added to agglomerate the solid content. The solid matter was collected, and the powdered graft polymer (C-1) was obtained through the steps of washing, dehydration and drying.
［製造例５］グラフト重合体（Ｃ−２）の製造
ゴム質重合体（Ａ−１）の代わりにゴム質重合体（Ａ−２）を使用したこと以外は製造例４と同様にして、粉末状のグラフト重合体（Ｃ−２）を得た。
[Production Example 5] Production of graft polymer (C-2) Except that rubbery polymer (A-2) was used instead of rubbery polymer (A-1), the same procedure as in Production Example 4 was carried out. A powdery graft polymer (C-2) was obtained.
［製造例６］グラフト重合体（Ｃ−３）の製造
ゴム質重合体（Ａ−１）の代わりにゴム質重合体（Ａ−３）を使用したこと以外は製造例４と同様にして、粉末状のグラフト重合体（Ｃ−３）を得た。
[Production Example 6] Production of graft polymer (C-3) Except that rubbery polymer (A-3) was used instead of rubbery polymer (A-1), the same procedure as in Production Example 4 was carried out. A powdery graft polymer (C-3) was obtained.
［製造例７］グラフト重合体（Ｃ−４）の製造
ゴム質重合体（Ａ−１）の代わりにポリブタジエンラテックス（日本ゼオン（株）製 Ｎｉｐｏｌ ＬＸ１１１ＮＦ）を使用したこと以外は製造例４と同様にして、粉末状のグラフト重合体（Ｃ−４）を得た。
[Production Example 7] Production of graft polymer (C-4) The same as Production Example 4 except that polybutadiene latex (Nipol LX111NF manufactured by Nippon Zeon Co., Ltd.) was used instead of rubber polymer (A-1). Thus, a powdery graft polymer (C-4) was obtained.
［製造例８］共重合体の製造法（Ｄ−１）
窒素置換した攪拌機付きステンレス重合反応槽反応器に、イオン交換水１２０部、ポリビニルアルコール０．１部、アゾビスイソブチロニトリル０．３部、アクリロニトリル３０部、スチレン７０部、t−ドデシルメルカプタン０．３５部を仕込んだ。そして、その反応器の温度を６０℃にして５時間加熱した後、１２０℃に昇温し、４時間重合して共重合体（Ｄ）を得た。重合終了後に単量体の転化率を求めたところ、９８％であった。また、得られた共重合体（Ｄ）の質量平均分子量をゲルパーミエーションクロマトグラフィにより測定したところ、１．０×１０５（ポリスチレン換算値）であった。
[Production Example 8] Copolymer production method (D-1)
In a stainless steel polymerization reactor equipped with a stirrer substituted with nitrogen, 120 parts of ion exchange water, 0.1 part of polyvinyl alcohol, 0.3 part of azobisisobutyronitrile, 30 parts of acrylonitrile, 70 parts of styrene, t-dodecyl mercaptan 0 .35 parts were charged. The reactor was heated to 60 ° C. and heated for 5 hours, then heated to 120 ° C. and polymerized for 4 hours to obtain a copolymer (D). When the conversion rate of the monomer was determined after the completion of the polymerization, it was 98%. Moreover, it was 1.0 * 10 < 5 > (polystyrene conversion value) when the mass mean molecular weight of the obtained copolymer (D) was measured by the gel permeation chromatography.
［製造例９］共重合体の製造法（Ｄ−２）
アクリロニトリル１９部、スチレン５３部およびＮ−フェニルマレイミド２８部よりなり、Ｎ，Ｎ−ジメチルホルムアミド溶液から２５℃で測定した還元粘度が０.６５ｄｌ／ｇであるアクリロニトリル−スチレン−Ｎ−フェニルマレイミド三元共重合体を公知の連続溶液重合により製造した。
[Production Example 9] Copolymer production method (D-2)
An acrylonitrile-styrene-N-phenylmaleimide ternary comprising 19 parts of acrylonitrile, 53 parts of styrene and 28 parts of N-phenylmaleimide and having a reduced viscosity of 0.65 dl / g measured from an N, N-dimethylformamide solution at 25 ° C. The copolymer was prepared by known continuous solution polymerization.
上記製造例で得たグラフト重合体（Ｃ）と共重合体（Ｄ）と下記に示す材料とを、表１または表２に示す配合比率でタンブラーミキサーに一括投入し、５分間混合した。次いで、得られた混合物を、溶融温度２４０℃にて二軸押出機（神戸製鋼所製 ＫＴＸ３０）を用いて混練して、熱可塑性樹脂のペレットを得た。
なお、表１，２における配合の単位は「部」である。
The graft polymer (C) and copolymer (D) obtained in the above production example and the materials shown below were collectively charged into a tumbler mixer at the blending ratio shown in Table 1 or Table 2, and mixed for 5 minutes. Next, the obtained mixture was kneaded at a melting temperature of 240 ° C. using a twin-screw extruder (KTX 30 manufactured by Kobe Steel) to obtain thermoplastic resin pellets.
The unit of blending in Tables 1 and 2 is “parts”.
導電性ポリマー −１：三洋化成工業（株）製 ペレスタットＮＣ６３２１（ポリエーテルエステルアミドブロックポリマー）
導電性ポリマー −２：日本ゼオン（株）製 ゼオスパン−８１００Ｌ（エチレンオキサイド／プロピレンオキサイド共重合体）
Conductive polymer -1: Pelestat NC6321 (polyether ester amide block polymer) manufactured by Sanyo Chemical Industries
Conductive polymer-2: Zeospan-8100L manufactured by Nippon Zeon Co., Ltd. (ethylene oxide / propylene oxide copolymer)
・アクリル樹脂（表１では、「ＰＭＭＡ」と表記する。）：三菱レイヨン社製 アクリペット ＶＨＳＫ
・炭酸カルシウム−１：日東粉化工業社製 ＮＳ＃１０００ （平均粒子径：１．２μｍ）
・炭酸カルシウム−２：日東粉化工業社製 ＮＩＴＯＲＥＸ３０Ｐ （平均粒子径：０．７μｍ）
・炭酸カルシウム−３：日東粉化工業社製 ＮＮ＃２００ （平均粒子径：１４．８μｍ）
・炭酸カルシウム−４：日東粉化工業社製ＮＮ＃５００ （平均粒子径：４．４μｍ）
・炭酸カルシウム−５：日東粉化工業社製ＳＳ＃３０ （平均粒子径：７．４μｍ）
・硫酸バリウム：日本化学工業社製 沈降性硫酸バリウム１０
・タルク：富士タルク工業社製 ＴＰ−Ａ２５
・ガラス繊維：日東紡績社製 ガラスチョップドストランド ＣＳＦ ３ＰＥ−３３２
・マイクロビーズ：ポッターズ・バロティーニ社製 ＥＭＢ−１０
・ガラスビーズ：ポッターズ・バロティーニ社製 ＧＢ３０１ＳＣ
・カーボンファイバー（表１，２では、「ＣＦ」と表記する。）：三菱レイヨン社製 パイロフィル・チョップドファイバー ＴＲＯ６Ｕ−Ｂ４Ｊ
各無機充填材のモース硬度は、粉体にする前の各無機物質を標準物質でこすり、標準物質に対するひっかき傷の有無で硬さを測定した。繊維状、ビーズ状の無機充填剤はそのまま標準物質でこすり、標準物質に対するひっかき傷の有無で硬さを測定した。測定結果を表１，２に記す。
Acrylic resin (indicated as “PMMA” in Table 1): Acrypet VHSK manufactured by Mitsubishi Rayon Co., Ltd.
Calcium carbonate-1: NS # 1000 (average particle size: 1.2 μm) manufactured by Nitto Flour Industry Co., Ltd.
-Calcium carbonate-2: NITREX30P manufactured by Nitto Flour Chemical Co., Ltd. (average particle size: 0.7 μm)
-Calcium carbonate-3: NN # 200 (average particle diameter: 14.8 μm) manufactured by Nitto Flour Industry Co., Ltd.
Calcium carbonate-4: NN # 500 (average particle size: 4.4 μm) manufactured by Nitto Flour Industry Co., Ltd.
・ Calcium carbonate-5: SS # 30 (average particle size: 7.4 μm) manufactured by Nitto Flour Industry Co., Ltd.
Barium sulfate: Nippon Chemical Industry Co., Ltd., precipitated barium sulfate 10
-Talc: TP-A25 manufactured by Fuji Talc Industrial Co., Ltd.
・ Glass fiber: Nittobo glass chopped strand CSF 3PE-332
・ Microbeads: EMB-10 manufactured by Potters Ballotini
・ Glass beads: GB301SC manufactured by Potters Barotini
Carbon fiber (indicated in Tables 1 and 2 as “CF”): Mitsubishi Rayon Pyrofil Chopped Fiber TRO6U-B4J
The Mohs hardness of each inorganic filler was measured by rubbing each inorganic substance before making it into a powder with a standard substance and by checking for scratches on the standard substance. The fibrous and beaded inorganic fillers were rubbed as they were with a standard material, and the hardness was measured by the presence or absence of scratches on the standard material. The measurement results are shown in Tables 1 and 2.
［評価］
各実施例および各比較例により得た熱可塑性樹脂のペレットを溶融温度２４０℃の条件で成形加工して、表面抵抗値測定用試験片と耐磨耗性評価用試験片を作製した。ペレットの射出成形加工には、日本製鋼社製Ｊ７５Ｅ−Ｐ射出成形機を使用した。
得られた試験片を用い、下記の方法により磨耗深さ、紙の傷付き防止性、表面固有抵抗、耐水性を評価した。評価結果を表１，２に示す。
[Evaluation]
The thermoplastic resin pellets obtained in each of the examples and comparative examples were molded under the condition of a melting temperature of 240 ° C. to prepare a test piece for measuring surface resistance and a test piece for evaluating wear resistance. A J75E-P injection molding machine manufactured by Nippon Steel Co., Ltd. was used for the pellet injection molding process.
Using the obtained test pieces, the wear depth, paper scratch resistance, surface resistivity, and water resistance were evaluated by the following methods. The evaluation results are shown in Tables 1 and 2.
・磨耗深さ・紙の傷付き防止性
ＲＣＡ磨耗試験機（米国Ｔｈｅ Ｎｏｒｍａｎ Ｔｏｏｌ＆Ｓｔａｍｐｉｎｇ Ｃｏｍｐａｎｙ製：紙テープ幅１７ｍｍ、紙テープ移動速度６５ｍｍ／秒）を使用し、無荷重で連続的に試験片に接触させて試験片の磨耗深さ（μｍ）を測定した。磨耗深さが浅い程、耐磨耗性に優れる。
また、試験後の紙の状態を目視で観察し、以下の基準で紙の傷付き防止性を評価した。
○：どの角度から見ても傷がない
△：ある角度から見ると傷が見える
×：どの角度から見ても傷が見える
-Depth of wear-Prevention of scratches on paper Using an RCA abrasion tester (manufactured by The Norman Tool & Stamping Company: paper tape width 17 mm, paper tape moving speed 65 mm / second), contact the test piece continuously without load. The wear depth (μm) of the test piece was measured. The shallower the wear depth, the better the wear resistance.
Moreover, the state of the paper after the test was visually observed, and the scratch resistance of the paper was evaluated according to the following criteria.
○: No scratches seen from any angle △: Scratches visible from a certain angle ×: Scratches visible from any angle
・表面固有抵抗
温度２３℃、相対湿度５０％の条件の雰囲気に４８時間静置後、超絶縁計（Ｒ８３４０Ａ アドバンテスト（株）製）を使用し、前記と同条件の雰囲気下で表面固有抵抗値（単位はΩ）を測定した。表面固有抵抗値が低い程、帯電防止性に優れる。
・ Surface specific resistance After standing for 48 hours in an atmosphere with a temperature of 23 ° C. and a relative humidity of 50%, use a superinsulator (R8340A manufactured by Advantest Co., Ltd.) and use the surface specific resistance value under the same conditions as above. (The unit is Ω). The lower the surface resistivity, the better the antistatic property.
・耐水性
試験片を７０℃の温水に１２０時間浸漬させた後、膨れなどの外観異常の発生の有無を目視により観察した。なお、本評価において、温水を使用したのは、ほとんどの市販のインクが水溶性のものであり、また、使用部品や使用環境にて高温の環境下を想定したためである。
-Water resistance After immersing a test piece in 70 degreeC warm water for 120 hours, the presence or absence of appearance abnormality, such as a swelling, was observed visually. In this evaluation, warm water was used because most commercially available inks were water-soluble and assumed to be used under high temperature in parts and environment.
・動摩擦係数
動摩擦係数を測定することによって、被印刷体摺動用樹脂材料を長期にわたって使用した際の、品質安定性を評価した。すなわち、動摩擦係数の変化を（株）オリエンテック製 ＥＦＭ−III−Ｎ型試験機、試験片形状：外寸直径２５．６ｍｍ、内寸直径２０ｍｍ、高さ１５ｍｍの円筒形（摺動面積２００ｍｍ２）、相手材としてコピー用紙を用いて、回転速度：３００ｍｍ／秒，試験荷重／１４．７Ｎ（試験機の荷重）／６０分の条件で測定時間３０分後、６０分後、２４０分後の動摩擦係数を測定した。動摩擦係数が試験時間に関係なく安定している程、長期にわたって品質安定性に優れる。
-Dynamic friction coefficient By measuring the dynamic friction coefficient, quality stability was evaluated when the printed material sliding resin material was used for a long time. That is, the change of the coefficient of dynamic friction was made by ETEC-III-N type tester manufactured by Orientec Co., Ltd., test piece shape: cylindrical shape with outer diameter 25.6 mm, inner diameter 20 mm, height 15 mm (sliding area 200 mm 2 ), Using copy paper as the mating material, rotation speed: 300 mm / second, test load / 14.7 N (load of test machine) / 60 minutes, measurement time 30 minutes, 60 minutes, 240 minutes later The dynamic friction coefficient was measured. The more stable the dynamic friction coefficient regardless of the test time, the better the quality stability over the long term.
・総合評価
また、摺動用樹脂材料として、以下の基準で総合評価した。
○：表面固有抵抗値が１０12Ω以下で、紙の傷付き防止性が○で、前記磨耗深さが２１０μｍ未満のもの
△：表面固有抵抗値が１０12Ω以下で、紙の傷付き防止性が○で、前記磨耗深さが２１０μｍ以上３００μｍ未満のもの
×：表面固有抵抗値が１０1２Ωを超えるもの、又は、前記磨耗深さが３００μｍ以上のもの、又は、紙の傷付き防止性が△、×のもの
-Comprehensive evaluation Moreover, as a resin material for sliding, comprehensive evaluation was carried out according to the following criteria.
○: The surface resistivity is 10 12 Ω or less, the paper scratch resistance is ○, and the wear depth is less than 210 μm. Δ: The surface resistivity is 10 12 Ω or less to prevent the paper from being scratched. ○: The wear depth is 210 μm or more and less than 300 μm ×: The surface specific resistance value exceeds 10 12 Ω, or the wear depth is 300 μm or more, or paper scratch resistance △, ×
グラフト共重合体（Ｃ）と共重合体（Ｄ）と導電性ポリマーとモース硬度４以下の無機充填材とを含有する実施例１〜１４の熱可塑性樹脂によれば、帯電防止性と、耐磨耗性に優れる上に、紙の傷付き防止性に優れる成形品を得ることができた。
これに対し、グラフト共重合体（Ｃ）および共重合体（Ｄ）と導電性ポリマーからなる比較例１，２の熱可塑性樹脂では、得られた成形品の磨耗深さが深く、耐磨耗性が低かった。
グラフト共重合体（Ｃ）と共重合体（Ｄ）と無機充填材とを含有するが、無機充填材のモース硬度が４を超えていた比較例３〜６の熱可塑性樹脂では、得られた成形品の紙の傷付き防止性が不充分であった。
導電性ポリマーを含まない比較例７の熱可塑性樹脂は、磨耗深さが浅く、動摩擦係数も低いが、帯電防止性が低かった。
According to the thermoplastic resins of Examples 1 to 14 containing the graft copolymer (C), the copolymer (D), a conductive polymer and an inorganic filler having a Mohs hardness of 4 or less, antistatic properties, In addition to being excellent in abrasion, a molded article having excellent resistance to scratching paper could be obtained.
On the other hand, in the thermoplastic resins of Comparative Examples 1 and 2 composed of the graft copolymer (C) and the copolymer (D) and a conductive polymer, the obtained molded product has a deep wear depth and wear resistance. The sex was low.
In the thermoplastic resins of Comparative Examples 3 to 6 containing the graft copolymer (C), the copolymer (D), and the inorganic filler, but the Mohs hardness of the inorganic filler exceeded 4, it was obtained. The scratch resistance of the molded article paper was insufficient.
The thermoplastic resin of Comparative Example 7 containing no conductive polymer had a low wear depth and a low coefficient of dynamic friction, but low antistatic properties.
また、ゴム質重合体（Ａ）がポリブタジエンである実施例７とＥＰＤＭである実施例６を対比すると、ＥＰＤＭを用いた実施例６は耐摩耗性がさらに優れ、動摩擦係数も試験時間に関係なく安定していた。
エチレン含量が８５％のゴム質重合体（Ａ−１）を用いたグラフト重合体（Ｃ−１）を含有する実施例１、エチレン含量が７０％のゴム質重合体（Ａ−２）を用いたグラフト共重合体（Ｃ−２）を含有する実施例５、エチレン含量が５０％のゴム質重合体（Ａ−３）を用いたグラフト重合体（Ｃ−３）を含有する実施例６を対比すると、実施例１，５では、炭酸カルシウムの配合量をより少ない状態でも実施例６と同等の耐摩耗性を発揮でき、さらに動摩擦係数もより低い値を示していた。
導電性ポリマー−１を使用した実施例１〜１１，１３，１４の熱可塑性樹脂は、導電性ポリマー−２を使用した実施例１２の熱可塑性樹脂よりも耐水性が優れていた。
Further, when Example 7 in which the rubbery polymer (A) is polybutadiene is compared with Example 6 in which EPDM is used, Example 6 using EPDM is more excellent in wear resistance and the dynamic friction coefficient is independent of the test time. It was stable.
Example 1 containing a graft polymer (C-1) using a rubbery polymer (A-1) having an ethylene content of 85%, and a rubbery polymer (A-2) having an ethylene content of 70% were used. Example 5 containing the graft copolymer (C-2), and Example 6 containing the graft polymer (C-3) using the rubbery polymer (A-3) having an ethylene content of 50%. In contrast, in Examples 1 and 5, the wear resistance equivalent to that in Example 6 could be exhibited even with a smaller amount of calcium carbonate, and the coefficient of dynamic friction was lower.
The thermoplastic resins of Examples 1 to 11, 13, and 14 using the conductive polymer-1 were superior in water resistance to the thermoplastic resin of Example 12 using the conductive polymer-2.
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