JP6160516B2 - Protective sheet for electrophotographic photoreceptor - Google Patents
Protective sheet for electrophotographic photoreceptor Download PDFInfo
- Publication number
- JP6160516B2 JP6160516B2 JP2014041296A JP2014041296A JP6160516B2 JP 6160516 B2 JP6160516 B2 JP 6160516B2 JP 2014041296 A JP2014041296 A JP 2014041296A JP 2014041296 A JP2014041296 A JP 2014041296A JP 6160516 B2 JP6160516 B2 JP 6160516B2
- Authority
- JP
- Japan
- Prior art keywords
- protective sheet
- photosensitive member
- electrophotographic photosensitive
- mass
- member according
- 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.)
- Expired - Fee Related
Links
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Landscapes
- Photoreceptors In Electrophotography (AREA)
- Paper (AREA)
Description
本発明は、電子写真感光体用保護シートに関する。具体的には、電子写真方式のプリンタ、複写機、ファクシミリなどに搭載される電子写真感光体の保護シートであって、感光体の表面に傷をつけにくい電子写真感光体用保護シートに関する。 The present invention relates to a protective sheet for an electrophotographic photoreceptor. Specifically, the present invention relates to a protective sheet for an electrophotographic photosensitive member that is mounted on an electrophotographic printer, copying machine, facsimile, or the like, and that hardly damages the surface of the photosensitive member.
レーザープリンタ、ＬＥＤプリンタ、普通紙複写機などの電子写真装置には、感光体が搭載されている。感光体は、導電性基体に光導電性物質を含む感光層を備えている。感光体は、所定期間使用すると摩耗等により劣化することが知られており、摩耗した感光体を使用すると出力画像の画質低下が生じる。そこで、電子写真装置においては、劣化した感光体を新しい感光体に交換する作業が必要となる。 A photoconductor is mounted on an electrophotographic apparatus such as a laser printer, an LED printer, or a plain paper copier. The photoreceptor includes a photosensitive layer containing a photoconductive substance on a conductive substrate. It is known that the photoconductor deteriorates due to wear or the like when used for a predetermined period, and when the worn photoconductor is used, the image quality of the output image is lowered. Therefore, in the electrophotographic apparatus, it is necessary to replace the deteriorated photoconductor with a new photoconductor.
しかし、感光層は数十ミクロン程度と薄く、非常に傷付き易い材料から構成されている。このため、電子写真装置に感光体を搭載する際、または取り換え作業中などにおいて、打痕・傷跡・指紋などの損傷を受けることが多い。さらに、近年は、セレン系の無機化合物に替わって、有機系光導電性物質と層形成用有機樹脂とを主成分とする感光層が一般的になってきているため、感光層はより損傷等のダメージを受け易くなっている。このため、感光層が損傷等のダメージを受けないように、使用前の感光体を保護シートで覆うことが提案されている。
例えば、特許文献１には、感光体を被覆する保護シートが開示されている。保護シートとしては、カーボンブラック入導電紙が例示されている。ここでは、保護シートは感光体の露出を回避する働きをする。このように、感光体を感光体用保護シートで覆うことで、感光体に傷が付いたり、指紋等の汚染物質が付着することを抑制しようとしている。
However, the photosensitive layer is as thin as several tens of microns and is made of a material that is very easily damaged. For this reason, damages such as dents, scars, and fingerprints are often caused when a photoconductor is mounted on an electrophotographic apparatus or during replacement work. Furthermore, in recent years, instead of selenium-based inorganic compounds, a photosensitive layer mainly composed of an organic photoconductive substance and a layer-forming organic resin has become common. It is easy to receive damage. For this reason, it has been proposed to cover the photosensitive member before use with a protective sheet so that the photosensitive layer is not damaged.
For example, Patent Document 1 discloses a protective sheet for covering a photoconductor. As the protective sheet, carbon black-containing conductive paper is exemplified. Here, the protective sheet functions to avoid exposure of the photoreceptor. In this way, by covering the photosensitive member with the protective sheet for the photosensitive member, it is intended to prevent the photosensitive member from being damaged or contaminated substances such as fingerprints from adhering thereto.
上述したように、感光体を保護シートで覆うことにより、感光体の損傷をある程度は抑制することができる。しかしながら、本発明者らが検討したところ、紙基材を用いた保護シートを、感光体と接触する状態で積層した場合、輸送時等に振動が与えられることにより、感光体と感光体用保護シートが擦れ、感光体に微細な傷が付くという問題があることが判明した。 As described above, by covering the photoconductor with the protective sheet, damage to the photoconductor can be suppressed to some extent. However, the present inventors have examined that when a protective sheet using a paper base material is laminated in contact with the photoconductor, vibrations are applied during transportation, etc., thereby protecting the photoconductor and the photoconductor. It has been found that there is a problem that the sheet is rubbed and the photoconductor is finely scratched.
そこで本発明者らは、このような従来技術の課題を解決するために、感光体の上に感光体用保護シートを直接積層した場合であっても、感光体に傷を付けにくい感光体用保護シートを提供することを目的として検討を進めた。 Therefore, in order to solve such problems of the prior art, the present inventors have proposed a photoconductor for which the photoconductor is hardly damaged even when the photoconductor protective sheet is directly laminated on the photoconductor. The study was conducted with the aim of providing a protective sheet.
本発明者らは、紙基材を用いた保護シートで感光体を覆った際に感光体に傷が発生する原因について検討したところ、紙基材に含まれる硬いパルプによるものであると考え、紙基材にアクリル樹脂を塗布することにより、感光体の傷つきが改善されることを発見した。しかし、紙基材の種類によってはアクリル樹脂を塗布すると、樹脂粕が発生して、逆に感光体に傷がつきやすくなることを見出した。そこで、樹脂粕の発生の発生原因について検討したところ、電子写真用感光体保護シートからのアルミニウムイオンの溶出量を低減することで、アクリル樹脂粕の発生を抑制できることを見出し、本発明を完成するに至った。具体的に、本発明は、以下の各構成を包含する。 The inventors of the present invention have examined the cause of scratches on the photoconductor when the photoconductor is covered with a protective sheet using a paper base material, and believe that it is due to the hard pulp contained in the paper base material. It has been found that the scratches on the photoreceptor can be improved by applying an acrylic resin to the paper substrate. However, it has been found that depending on the type of paper substrate, application of acrylic resin causes resin wrinkles and conversely damages the photoreceptor. Then, when the cause of generation | occurrence | production of resin soot was examined, it discovered that generation | occurrence | production of acrylic resin soot could be suppressed by reducing the elution amount of the aluminum ion from the electrophotographic photoreceptor protective sheet, and completed this invention. It came to. Specifically, the present invention includes the following configurations.
（１） 紙基材の少なくとも一方の面にアクリル系樹脂を有する電子写真用感光体保護シートであって、前記電子写真用感光体保護シートを、ＪＩＳ Ｐ ８１３３ ６（１９９８）に準拠する方法で試料調製し、ＪＩＳ Ｐ ８１４４ ９ａ（１９９８）に準拠する方法で熱水抽出して抽出されるアルミニウムイオンの質量割合が１５質量ｐｐｍ以下である電子写真感光体用保護シート。
（２） 前記熱水抽出により抽出されるアルミニウムイオンの質量割合が１０質量ｐｐｍ以下である（１）記載の電子写真感光体用保護シート。
（３） 前記紙基材は、パルプ固形分の１００質量部に対し、硫酸バンド固形量を０．０６〜０．３３質量部含有する（１）または（２）記載の電子写真感光体用保護シート。
（４） 前記紙基材は、パルプ固形分の１００質量部に対し、硫酸バンド固形量を０．１９〜０．３１質量部含有する（１）〜（３）のいずれかに記載の電子写真感光体用保護シート。
（５） 前記アクリル系樹脂の固形分量は、０．１〜２０ｇ／ｍ2である（１）〜（４）のいずれかに記載の電子写真感光体用保護シート。
（６） 前記熱水抽出により抽出されるアンモニウムイオンの質量割合が３００質量ｐｐｍ以下である（１）〜（５）のいずれかに記載の電子写真感光体用保護シート。
（７） 前記熱水抽出により抽出されるアンモニウムイオンの質量割合が２００質量ｐｐｍ以下である（１）〜（６）のいずれかに記載の電子写真感光体用保護シート。
（８） 前記紙基材は、導電填料を含む（１）〜（７）のいずれかに記載の電子写真感光体用保護シート。
（９） 前記導電填料は、カーボンブラックである（８）に記載の電子写真感光体用保護シート。
（１０） 前記紙基材は、パルプ固形分の１００質量部に対し、前記カーボンブラックを１〜２０質量部含有する（９）に記載の電子写真感光体用保護シート。
（１１） ＪＩＳ Ｋ ７１９４（１９９４）に準拠する方法による表面電気抵抗が１×１０8Ω／□以下である（１）〜（１０）のいずれかに記載の電子写真感光体用保護シート。
（１２） 前記電子写真感光体用保護シート表面の黒色の分光濃度が０．９０以上である（１）〜（１１）のいずれかに記載の電子写真感光体用保護シート。
（１３） 前記保護シートの波長３００〜８５０ｎｍの領域における光透過率が０．０５％以下である（１）〜（１２）のいずれかに記載の電子写真感光体用保護シート。
（１４） 前記電子写真感光体用保護シートのＪＡＰＡＮ ＴＡＰＰＩ Ｎｏ．５−２：２０００に準拠した方法で測定した表面平滑度が、２００秒以下である（１）〜（１３）のいずれかに記載の電子写真感光体用保護シート。
（１５） 前記電子写真感光体用保護シートは、積層されるシート状電子写真感光体の合紙として使用される（１）〜（１４）のいずれかに記載の電子写真感光体用保護シート。
（１６） 前記紙基材の片方の面のみにアクリル系樹脂を有する（１）〜（１５）のいずれかに記載の電子写真感光体用保護シート。
（１７） 前記電子写真感光体用保護シートは、抄紙機のサイズプレスパートにて、前記アクリル系樹脂を前記紙基材に塗布して得られたものである（１）〜（１６）のいずれかに記載の電子写真感光体用保護シート。
(1) An electrophotographic photosensitive member protective sheet having an acrylic resin on at least one surface of a paper substrate, wherein the electrophotographic photosensitive member protective sheet is a method based on JIS P 8133 6 (1998). A protective sheet for an electrophotographic photosensitive member, in which the mass ratio of aluminum ions prepared by sample extraction and extracted by hot water extraction according to JIS P 8144 9a (1998) is 15 ppm by mass or less.
(2) The protective sheet for an electrophotographic photosensitive member according to (1), wherein a mass ratio of aluminum ions extracted by the hot water extraction is 10 mass ppm or less.
(3) The protection for an electrophotographic photosensitive member according to (1) or (2), wherein the paper base material contains 0.06 to 0.33 parts by mass of sulfuric acid band solids with respect to 100 parts by mass of pulp solids. Sheet.
(4) The electrophotographic photograph according to any one of (1) to (3), wherein the paper base material contains 0.19 to 0.31 parts by mass of sulfuric acid band solids with respect to 100 parts by mass of pulp solids. Photoconductor protective sheet.
(5) The protective sheet for an electrophotographic photosensitive member according to any one of (1) to (4), wherein the acrylic resin has a solid content of 0.1 to 20 g / m 2 .
(6) The protective sheet for an electrophotographic photosensitive member according to any one of (1) to (5), wherein a mass ratio of ammonium ions extracted by the hot water extraction is 300 ppm by mass or less.
(7) The protective sheet for an electrophotographic photosensitive member according to any one of (1) to (6), wherein a mass ratio of ammonium ions extracted by the hot water extraction is 200 mass ppm or less.
(8) The protective sheet for an electrophotographic photosensitive member according to any one of (1) to (7), wherein the paper substrate includes a conductive filler.
(9) The protective sheet for an electrophotographic photosensitive member according to (8), wherein the conductive filler is carbon black.
(10) The protective sheet for an electrophotographic photosensitive member according to (9), wherein the paper base contains 1 to 20 parts by mass of the carbon black with respect to 100 parts by mass of pulp solids.
(11) The protective sheet for an electrophotographic photoreceptor according to any one of (1) to (10), wherein the surface electrical resistance by a method according to JIS K 7194 (1994) is 1 × 10 8 Ω / □ or less.
(12) The electrophotographic photosensitive member protective sheet according to any one of (1) to (11), wherein a black spectral density of the surface of the protective sheet for the electrophotographic photosensitive member is 0.90 or more.
(13) The protective sheet for an electrophotographic photosensitive member according to any one of (1) to (12), wherein the light transmittance in a wavelength region of 300 to 850 nm of the protective sheet is 0.05% or less.
(14) JAPAN TAPPI No. of the protective sheet for electrophotographic photosensitive member. The protective sheet for an electrophotographic photosensitive member according to any one of (1) to (13), wherein the surface smoothness measured by a method based on 5-2: 2000 is 200 seconds or less.
(15) The protective sheet for an electrophotographic photosensitive member according to any one of (1) to (14), wherein the protective sheet for an electrophotographic photosensitive member is used as a slip sheet of a laminated sheet-shaped electrophotographic photosensitive member.
(16) The protective sheet for an electrophotographic photosensitive member according to any one of (1) to (15), which has an acrylic resin only on one surface of the paper substrate.
(17) The electrophotographic photoreceptor protective sheet is obtained by applying the acrylic resin to the paper base material in a size press part of a paper machine. A protective sheet for an electrophotographic photosensitive member according to claim 1.
本発明によれば、感光体に傷を付けにくい電子写真感光体用保護シートを得ることができる。このような、電子写真感光体用保護シートは、感光体上に直接積層した場合であっても、感光体に傷を付けることがない。 According to the present invention, it is possible to obtain a protective sheet for an electrophotographic photosensitive member that hardly damages the photosensitive member. Such a protective sheet for an electrophotographic photoreceptor does not damage the photoreceptor even when it is directly laminated on the photoreceptor.
以下において、本発明について詳細に説明する。以下に記載する構成要件の説明は、代表的な実施形態や具体例に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。なお、本明細書において「〜」を用いて表される数値範囲は「〜」前後に記載される数値を下限値および上限値として含む範囲を意味する。また、（メタ）アクリル酸は、アクリル酸とメタクリル酸の両方を含む意味で使われる。また、熱水抽出は、「ＪＩＳ Ｐ ８１３３：１９９８ 紙、板紙及びパルプ −水抽出液ｐＨの試験方法 ６．試料の採取及び試験片の調製」に準拠して調製した試料を、「ＪＩＳ Ｐ ８１４４（１９９８） 紙、板紙及びパルプ−水溶性塩化物の分析方法 ９．ａ 抽出操作」に準拠する方法で熱水抽出することを意味する。また、「紙基材の少なくとも一方の面にアクリル系樹脂を有する」とは、「アクリル系樹脂が、紙基材の表面に隣接するように層状に設けられている状態」、および、「アクリル系樹脂の少なくとも一部が紙基材に含浸される状態」のことを意味する。 Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. Moreover, (meth) acrylic acid is used in the meaning containing both acrylic acid and methacrylic acid. In addition, hot water extraction was performed using a sample prepared according to “JIS P 8133: 1998 Paper, paperboard and pulp-water extract pH test method 6. Sample collection and test piece preparation” as “JIS P 8144. (1998) Paper, paperboard, and pulp-water-soluble chloride analysis method 9. It means hot water extraction by a method according to “Extraction operation”. In addition, “having an acrylic resin on at least one surface of a paper substrate” means “a state where the acrylic resin is provided in a layer so as to be adjacent to the surface of the paper substrate” and “acrylic” It means a state in which at least a part of the resin is impregnated in the paper substrate.
（電子写真感光体用保護シート）
本発明は、紙基材の少なくとも一方の面にアクリル系樹脂を有する電子写真用感光体保護シートであって、電子写真用感光体保護シートの熱水抽出により抽出されるアルミニウムイオンの質量割合が１５質量ｐｐｍ以下であることを特徴とする。
本発明の電子写真感光体用保護シートは、熱水抽出により抽出されるアルミニウムイオンの質量割合が１５質量ｐｐｍ以下であることが必要であり、１０質量ｐｐｍ以下であることがより好ましい。下限値は、特に限定はないが、例えば、０質量ｐｐｍ、好ましくは０．１０質量ｐｐｍ、より好ましくは０．３質量ｐｐｍ、さらにより好ましくは０．６質量ｐｐｍを採用できる。熱水抽出により抽出されるアルミニウムイオンの質量割合を、１５質量ｐｐｍ以下とすることにより、アクリル系樹脂粕などの粕の発生を抑制でき、電子写真感光体用保護シートに樹脂粕などが混入することを抑制できる。このため、輸送時等に振動が与えられて感光体と感光体用保護シートとが擦れても、感光体に傷をつくことを抑制できる。
アルミニウムイオンの質量割合を上記範囲内とするためには、紙基材の製造時において、硫酸バンドなど、アルミニウムを含有する添加剤の使用量を調整することで達成できる。なお、熱水抽出液に含まれるアルミニウムイオン濃度は、ＩＣＰ−ＯＥＳ（誘導結合プラズマ発光分光）などで測定できる。
(Protective sheet for electrophotographic photoreceptor)
The present invention is an electrophotographic photoreceptor protective sheet having an acrylic resin on at least one surface of a paper substrate, and the mass ratio of aluminum ions extracted by hot water extraction of the electrophotographic photoreceptor protective sheet is It is characterized by being 15 mass ppm or less.
In the protective sheet for an electrophotographic photoreceptor of the present invention, the mass ratio of aluminum ions extracted by hot water extraction is required to be 15 mass ppm or less, and more preferably 10 mass ppm or less. The lower limit is not particularly limited, and for example, 0 mass ppm, preferably 0.10 mass ppm, more preferably 0.3 mass ppm, and still more preferably 0.6 mass ppm can be employed. By setting the mass ratio of aluminum ions extracted by hot water extraction to 15 mass ppm or less, generation of soot such as acrylic resin soot can be suppressed, and resin soot is mixed into the protective sheet for electrophotographic photosensitive member. This can be suppressed. For this reason, even if vibration is given during transportation or the like and the photosensitive member and the protective sheet for the photosensitive member are rubbed, it is possible to prevent the photosensitive member from being damaged.
In order to make the mass ratio of aluminum ions within the above range, it can be achieved by adjusting the amount of an additive containing aluminum such as a sulfuric acid band during the production of a paper base material. The aluminum ion concentration contained in the hot water extract can be measured by ICP-OES (inductively coupled plasma emission spectroscopy) or the like.
また、本発明の電子写真感光体用保護シートは、熱水抽出により抽出されるアンモニウムイオンの質量割合が３００質量ｐｐｍ以下であることが好ましい。より好ましくは２００質量ｐｐｍである。下限値は、特に限定はないが、検出限界値以下が好ましく、例えば、０．０１質量ｐｐｍが好ましい。アンモニウムイオンの質量割合が３００ｐｐｍ以下とすることにより、電子写真感光体用保護シートが感光体と接触させた際に、電子写真感光体用保護シート中のアンモニウムイオンが感光体表面に転移することを抑制でき、出力画像ボケ等の不具合の無い印刷が可能である。
アンモニウムイオンの質量割合を上記範囲内とするためには、紙基材の製造時にアンモニアの使用を抑制したり、アンモニアの代わりにアミノアルコール化合物等を中和剤として使用したアクリル系樹脂を用いることで達成できる。なお、熱水抽出液に含まれるアンモニウムイオン濃度は、イオンクロマトグラフィーなどで測定できる。
Moreover, it is preferable that the mass ratio of the ammonium ion extracted by hot water extraction is 300 mass ppm or less in the protective sheet for electrophotographic photoreceptors of the present invention. More preferably, it is 200 mass ppm. The lower limit value is not particularly limited, but is preferably not more than the detection limit value, for example, 0.01 ppm by mass. By setting the mass ratio of ammonium ions to 300 ppm or less, when the protective sheet for an electrophotographic photoreceptor is brought into contact with the photoreceptor, ammonium ions in the protective sheet for an electrophotographic photoreceptor are transferred to the surface of the photoreceptor. It can be suppressed, and printing without defects such as output image blur is possible.
In order to make the mass ratio of ammonium ions within the above range, use of an acrylic resin that suppresses the use of ammonia at the time of manufacturing a paper base material or uses an amino alcohol compound or the like as a neutralizing agent instead of ammonia is used. Can be achieved. The ammonium ion concentration contained in the hot water extract can be measured by ion chromatography or the like.
本発明において、アクリル系樹脂は、紙基材の少なくとも一方の面側に有していればよく、紙基材の片方の面のみに有していることが好ましい。紙基材の片方の面のみにアクリル樹脂を有している場合、アクリル系樹脂は、紙基材のＷ面（ワイヤー面）及びＦ面（フェルト面）のいずれの面に有してもよい。 In the present invention, the acrylic resin may be provided on at least one surface side of the paper substrate, and is preferably provided only on one surface of the paper substrate. When the acrylic resin is provided only on one side of the paper base, the acrylic resin may be provided on any of the W side (wire side) and F side (felt side) of the paper base. .
本発明の電子写真感光体用保護シートを適用する電子写真感光体は、円筒状であってもよく、シート状であってもよい。電子写真感光体が円筒状である場合、電子写真感光体用保護シートは円筒状の電子写真感光体の外周を覆うように巻きつけて使用される。また、電子写真感光体がシート状である場合は、電子写真感光体用保護シートは積層されるシート状電子写真感光体の合紙（間紙）として使用される。 The electrophotographic photosensitive member to which the protective sheet for an electrophotographic photosensitive member of the present invention is applied may be a cylindrical shape or a sheet shape. When the electrophotographic photosensitive member is cylindrical, the protective sheet for the electrophotographic photosensitive member is used by being wound so as to cover the outer periphery of the cylindrical electrophotographic photosensitive member. When the electrophotographic photosensitive member is a sheet, the protective sheet for the electrophotographic photosensitive member is used as an interleaf (interleaf) for the laminated sheet-like electrophotographic photosensitive member.
本発明の電子写真感光体用保護シートの表面電気抵抗は、「ＪＩＳ Ｋ ７１９４（１９９４）導電性プラスチックの４探針法による抵抗率試験方法」により２３℃・５０％ＲＨの条件下で測定されるものである。該表面電気抵抗は、１×１０8Ω／□以下であることが好ましく、１×１０7Ω／□以下であることがより好ましく、１×１０6Ω／□以下であることがさらに好ましい。因みに、表面電気抵抗が１×１０8Ω／□より高い場合、静電気が生じることで埃が感光体用保護シートに付着しやすい傾向となる。埃が硬い物質の場合、電子写真用感光体に傷をつけやすい傾向となる。表面電気抵抗を１×１０8Ω／□以下とするには、例えば、紙基材に配合する導電填剤の配合量を調整する等の方法が挙げられる。なお、本発明において、電子写真感光体用保護シートの表面電気抵抗は、２３℃・５０％ＲＨの環境下で、四探針法で測定した値である。 The surface electrical resistance of the protective sheet for an electrophotographic photosensitive member of the present invention is measured under conditions of 23 ° C. and 50% RH according to “JIS K 7194 (1994) Conductivity plastic resistivity test method by four-probe method”. Is. The surface electrical resistance is preferably 1 × 10 8 Ω / □ or less, more preferably 1 × 10 7 Ω / □ or less, and further preferably 1 × 10 6 Ω / □ or less. Incidentally, when the surface electrical resistance is higher than 1 × 10 8 Ω / □, dust tends to adhere to the protective sheet for the photoreceptor due to static electricity. When dust is a hard substance, the electrophotographic photoreceptor tends to be easily damaged. In order to set the surface electrical resistance to 1 × 10 8 Ω / □ or less, for example, a method of adjusting the blending amount of the conductive filler blended in the paper substrate can be mentioned. In the present invention, the surface electrical resistance of the electrophotographic photosensitive member protective sheet is a value measured by a four-probe method in an environment of 23 ° C. and 50% RH.
本発明の電子写真感光体用保護シートは、波長３００〜８５０ｎｍの領域における光透過率の最大値が０．０５％以下であることが感光体の感光特性を保護する上で好ましい。上記波長における光の透過率の最大値を、が０．０５％以下とすることにより、長期間の保管でも感光体の感光特性が良好である。
上記の光の透過率を達成するためには、例えば、電子写真感光体用保護シートの表面を分光濃度計で測定した黒色の分光濃度を０．９０以上とすることにより達成できる。
すなわち、本発明の電子写真感光体用保護シートは、黒色の分光濃度が、０．９０以上であることが好ましく、１．１５以上であることがより好ましく、１．２０以上がさらに好ましく、１．３０以上であることがさらにより好ましく、１．３５以上であることが特に好ましい。電子写真感光体用保護シートの黒色の分光濃度を上記範囲とすることにより、電子写真感光体用保護シートの遮光性を十分に高めることができ、電子写真用感光体の感光特性の性能劣化を防止できる。電子写真感光体用保護シートの黒色の分光濃度を０．９０以上とするには、例えば、紙基材に配合するカーボンブラックなどの配合量を調整する等の方法が挙げられる。
The protective sheet for an electrophotographic photoreceptor of the present invention preferably has a maximum light transmittance of 0.05% or less in the wavelength region of 300 to 850 nm in order to protect the photosensitive properties of the photoreceptor. By setting the maximum value of the light transmittance at the above wavelength to 0.05% or less, the photosensitive characteristics of the photosensitive member are good even during long-term storage.
The light transmittance can be achieved, for example, by setting the black spectral density measured by a spectral densitometer to 0.90 or more on the surface of the electrophotographic photosensitive member protective sheet.
That is, the protective sheet for an electrophotographic photosensitive member of the present invention preferably has a black spectral density of 0.90 or more, more preferably 1.15 or more, further preferably 1.20 or more, and 1 Is more preferably 30 or more, and particularly preferably 1.35 or more. By setting the black spectral density of the protective sheet for electrophotographic photoreceptors within the above range, the light shielding property of the protective sheet for electrophotographic photoreceptors can be sufficiently increased, and the performance deterioration of the photosensitive characteristics of the electrophotographic photoreceptor is reduced. Can be prevented. In order to set the black spectral density of the electrophotographic photosensitive member protective sheet to 0.90 or more, for example, a method of adjusting the blending amount of carbon black or the like to be blended with the paper substrate can be mentioned.
本発明の電子写真感光体用保護シートは、ＪＡＰＡＮ ＴＡＰＰＩ Ｎｏ．５−２：２０００に準拠した方法で測定した表面平滑度が、２００秒以下であることが好ましい。下限値は０秒が好ましい。上記表面平滑度は、測定ヘッドに試料を重ねてその隙間を一定容量の空気が通過する時間（秒）で表したものであって、その数値が小さいほど試料の表面の凹凸が大きいことを意味する。表面平滑度が２００秒以下であれば、空気中の異物等が電子写真感光体用保護シートに付着しても、電子写真感光体用保護シートと感光体の表面に異物を吸収する空間があるため、感光体の傷つきをより効果的に防止できる。表面の平滑度については、オンマシンまたはオフマシンのカレンダー処理等で調整することができる。
本発明の電子写真感光体用保護シートのこわさについては、特に限定するものではないが、ＪＡＰＡＮ ＴＡＰＰＩ Ｎｏ．４０に準拠した方法で測定したこわさは、抄紙方向と平行（縦）方向、抄紙方向と直角（横）方向とも０．２０〜２．０ｍＮが好ましい。上記範囲であれば、感光体と重ねあわせる際に折れなどを発生せず、また重ね合わせ作業性も良好となるため好ましい。
The protective sheet for an electrophotographic photosensitive member of the present invention is JAPAN TAPPI No. It is preferable that the surface smoothness measured by the method based on 5-2: 2000 is 200 seconds or less. The lower limit is preferably 0 seconds. The above surface smoothness is expressed by the time (seconds) that a certain volume of air passes through the gap between the sample on the measuring head. The smaller the value, the larger the surface roughness of the sample. To do. If the surface smoothness is 200 seconds or less, even if foreign matter or the like in the air adheres to the electrophotographic photosensitive member protective sheet, there is a space for absorbing the foreign matter on the electrophotographic photosensitive member protective sheet and the surface of the photosensitive member. Therefore, it is possible to more effectively prevent the photoreceptor from being damaged. The surface smoothness can be adjusted by on-machine or off-machine calendaring.
The stiffness of the protective sheet for an electrophotographic photosensitive member of the present invention is not particularly limited. The stiffness measured by the method according to No. 40 is preferably 0.20 to 2.0 mN in both the direction parallel to the paper making direction (longitudinal direction) and the direction perpendicular to the paper making direction (lateral direction). If it is the said range, since a folding etc. will not generate | occur | produce at the time of superimposing with a photoconductor, and superimposition workability | operativity will become favorable, it is preferable.
本発明の電子写真感光体用保護シートは、アクリル系樹脂を有する。アクリル系樹脂の固形分量は、０．１〜２０ｇ／ｍ2が好ましく、０．２〜１８ｇ／ｍ2がより好ましく、０．３〜１５ｇ／ｍ2がさらに好ましく、０．５〜１０ｇ／ｍ2が最も好ましい。アクリル系樹脂の固形分量を上記範囲内とすることにより、電子写真感光体用保護シートを、電子写真感光体の感光体と直接重ね合わせた場合であっても、感光体の表面に傷が付くことを防止することができる。なお、上記のアクリル系樹脂の固形分量は、電子写真感光体用保護シートが含有するアクリル系樹脂の合計の固形分量であり、紙基材の両面にアクリル系樹脂を有する場合は、両面に存在するアクリル系樹脂の固形分量の合計が上記範囲内であることが好ましい。
アクリル系樹脂が紙基材の片面にのみ有する場合は、アクリル系樹脂の固形分量は、０．０５〜１０ｇ／ｍ2が好ましく、０．１〜９ｇ／ｍ2がより好ましく、０．１５〜７．５ｇ／ｍ2がさらに好ましく、０．２５〜５ｇ／ｍ2が最も好ましい。
The protective sheet for an electrophotographic photosensitive member of the present invention has an acrylic resin. Solid content of the acrylic resin is preferably 0.1 to 20 g / m 2, more preferably 0.2~18g / m 2, more preferably 0.3~15g / m 2, 0.5~10g / m 2 is most preferred. By setting the solid content of the acrylic resin within the above range, the surface of the photoreceptor is scratched even when the protective sheet for the electrophotographic photoreceptor is directly overlapped with the photoreceptor of the electrophotographic photoreceptor. This can be prevented. The solid content of the acrylic resin is the total solid content of the acrylic resin contained in the protective sheet for an electrophotographic photosensitive member. If the acrylic resin is present on both sides of the paper substrate, the solid content is present on both sides. It is preferable that the total solid content of the acrylic resin is within the above range.
If the acrylic resin has only one surface of the paper substrate, the solid content of the acrylic resin is preferably 0.05 to 10 g / m 2, more preferably 0.1~9g / m 2, 0.15~ 7.5 g / m 2 is more preferable, and 0.25 to 5 g / m 2 is most preferable.
本発明で用いられるアクリル系樹脂のガラス転移温度（Ｔｇ）は、−５０〜５℃であることが好ましく、−４５〜０℃であることがより好ましく、−４０〜−５℃であることがさらに好ましい。アクリル系樹脂のガラス転移温度（Ｔｇ）を上記範囲内とすることにより、電子写真感光体用保護シートを感光体に直接積層した場合であっても感光体に傷が付くことを効果的に抑制することができる。アクリル系樹脂のガラス転移温度（Ｔｇ）が−５０℃以上の場合、感光体用保護シート表面に粘着性が発現することがなく、感光体を汚染することがなく好ましい。また、ガラス転移温度（Ｔｇ）が５℃以下の場合は、傷発生防止効果を十分得ることができる。なお、本発明でいうガラス転移温度（Ｔｇ）とは、例えば、妹尾学・栗田公夫・矢野彰一郎・澤口孝志著『基礎高分子科学』（共立出版株式会社）に記載されているような非晶領域における高分子鎖のセグメントがミクロブラウン運動を開始する温度で、共重合体の場合は、同書１３１〜１３２頁に記載されているＦｏｘの式により計算されるガラス転移温度である。 The glass transition temperature (Tg) of the acrylic resin used in the present invention is preferably −50 to 5 ° C., more preferably −45 to 0 ° C., and preferably −40 to −5 ° C. Further preferred. By setting the glass transition temperature (Tg) of the acrylic resin within the above range, it is possible to effectively prevent the photoreceptor from being damaged even when the protective sheet for the electrophotographic photoreceptor is directly laminated on the photoreceptor. can do. When the glass transition temperature (Tg) of the acrylic resin is −50 ° C. or higher, it is preferable that the surface of the protective sheet for the photosensitive member does not exhibit adhesiveness and does not contaminate the photosensitive member. Further, when the glass transition temperature (Tg) is 5 ° C. or less, the effect of preventing scratches can be sufficiently obtained. The glass transition temperature (Tg) in the present invention is, for example, an amorphous material as described in Manabu Senoo, Kimio Kurita, Shoichiro Yano, Takashi Sawaguchi, “Basic Polymer Science” (Kyoritsu Publishing Co., Ltd.). This is the temperature at which the polymer chain segment in the region starts micro-Brownian motion, and in the case of a copolymer, it is the glass transition temperature calculated by the Fox equation described on pages 131-132 of the same book.
本発明において、アクリル系樹脂は、（ａ）エチレン性不飽和カルボン酸含有モノマー由来の繰り返し単位を必須成分として含むことが好ましい。また、アクリル系樹脂は、（ａ）エチレン性不飽和カルボン酸含有モノマー由来の繰り返し単位と、（ｂ）（メタ）アクリル酸アルキルエステルモノマー由来の繰り返し単位とを含み、さらに（ａ）及び（ｂ）のモノマーと共重合可能なモノマー由来の繰り返し単位を含む共重合体であることが好ましい。 In the present invention, the acrylic resin preferably contains (a) a repeating unit derived from an ethylenically unsaturated carboxylic acid-containing monomer as an essential component. The acrylic resin contains (a) a repeating unit derived from an ethylenically unsaturated carboxylic acid-containing monomer and (b) a repeating unit derived from a (meth) acrylic acid alkyl ester monomer, and (a) and (b It is preferable that the copolymer contains a repeating unit derived from a monomer copolymerizable with the monomer (ii).
上述した（ａ）エチレン性不飽和カルボン酸含有モノマーとしては、例えば（メタ）アクリル酸、クロトン酸、マレイン酸、イタコン酸、フマル酸、モノアルキルマレイン酸、モノアルキルフマル酸、モノアルキルイタコン酸等が挙げられ、これらのうちから少なくとも１種を用いることができる。
上述した（ｂ）（メタ）アクリル酸アルキルエステルモノマーとしては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸デシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル等が挙げられ、これらのうちから少なくとも１種を用いることができる。
Examples of the above-mentioned (a) ethylenically unsaturated carboxylic acid-containing monomer include (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, monoalkylmaleic acid, monoalkylfumaric acid, monoalkylitaconic acid and the like. And at least one of them can be used.
Examples of the (b) (meth) acrylic acid alkyl ester monomer described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, n-nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, (meth) acrylic Examples include dodecyl acid, and at least one of them can be used. That.
上述した（ａ）及び（ｂ）のモノマーと共重合可能なモノマーとしては、スチレン、酢酸ビニル、塩化ビニル、塩化ビニリデン、（メタ）アクリロニトリル、エチレン、プロピレン、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリルレート、グリセロールモノ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、１，２−プロピレングリコールジ（メタ）アクリレート、１，３−プロピレングリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ジビニルベンゼン、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジアリル（メタ）アクリレート、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ'−メチレンビス（メタ）アクリルアミド、ビニルスルホン酸ナトリウム、ｐ−スチレンスルホン酸ナトリウム、２−アクリルアミド−２−メチルプロパンスルホン酸、酸ホスホキシエチル（メタ）アクリレートエタノールアミンハーフ塩、３−アリロキシ−２−ヒドロキシプロパンスルホン酸ナトリウム、ポリオキシエチレンスチレン化フェニル硫酸ナトリウム、グリセリンモノアリルエーテルモノスルホコハク酸ナトリウム、２−スルホエチル（メタ）アクリル酸ナトリウム、（メタ）アクリルアミドステアリン酸ナトリウム、ｎ−アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、カプロラクトン変性（メタ）アクリレート、アクロレイン、ジアセトン（メタ）アクリルアミド、ホルミルスチロール、ビニルメチルケトン、ビニルエチルケトン、（メタ）アクリロオキシアルキルプロペナール、ジアセトン（メタ）アクリレート、アセトニル（メタ）アクリレート、アセトアセトキシエチル（メタ）アクリレート、３，４−エポキシシクロヘキシル（メタ）アクリレート、ジアリルフタレート、トリアリルシアヌレート等が挙げられ、これらのうちから少なくとも１種を用いることができる。 Monomers that can be copolymerized with the monomers (a) and (b) described above include styrene, vinyl acetate, vinyl chloride, vinylidene chloride, (meth) acrylonitrile, ethylene, propylene, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, tetramethylol methane tetra (meth) acrylate, divinylbenzene, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol Propane tri (meth) acrylate, diallyl (meth) acrylate, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, N-methylol (meth) acrylamide, N-methoxymethyl (meth) Acrylamide, N-butoxymethyl (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, sodium vinylsulfonate, sodium p-styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, phosphoxyethyl acid ( (Meth) acrylate ethanolamine half salt, sodium 3-allyloxy-2-hydroxypropanesulfonate, sodium polyoxyethylene styrenated phenylsulfate, sodium glyceryl monoallyl ether monosulfosuccinate, sodium 2-sulfoethyl (meth) acrylate, (meta ) Sodium acrylamide stearate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate , Ethyl carbitol (meth) acrylate, caprolactone modified (meth) acrylate, acrolein, diacetone (meth) acrylamide, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, (meth) acrylooxyalkylpropenal, diacetone (meth) Examples include acrylate, acetonyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, diallyl phthalate, triallyl cyanurate, and the like. it can.
本発明において用いられるアクリル系樹脂は、公知の乳化重合法によって得ることができる。例えば、所定の反応容器に上記の各種モノマー類、乳化剤および水を仕込み、ラジカル重合開始剤を加え、攪拌下、加温することにより得られる。 The acrylic resin used in the present invention can be obtained by a known emulsion polymerization method. For example, it can be obtained by charging the above-mentioned various monomers, emulsifier and water in a predetermined reaction vessel, adding a radical polymerization initiator, and heating with stirring.
ラジカル重合開始剤としては、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、ｔ−ブチルハイドロオキサイド、ｔ−ブチルパーオキシベンゾエート等の過酸化物、２，２−アゾビスイソブチロニトリル、２，２−アゾビス（２−ジアミノプロパン）ハイドロクロライド、２，２−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ系化合物が挙げられる。なお、重合速度の促進や低温反応を望む場合には、重亜硫酸ナトリウム、塩化第一鉄、アスコルビン酸、ホルムアルデヒドスルホオキシレート塩等の還元剤を前記ラジカル重合開始剤と組合せて（レドックス系重合開始剤）用いることができる。 Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, peroxides such as hydrogen peroxide, t-butyl hydroxide, and t-butyl peroxybenzoate, and 2,2-azo. Examples thereof include azo compounds such as bisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, and 2,2-azobis (2,4-dimethylvaleronitrile). If acceleration of polymerization rate or low temperature reaction is desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, formaldehyde sulfooxylate salt is combined with the radical polymerization initiator (redox polymerization initiation). Agent).
ラジカル重合開始剤の配合量は、モノマー成分１００質量部に対して、０．０２〜３質量部であることが好ましく、０．０５〜１質量部であることがより好ましい。 The blending amount of the radical polymerization initiator is preferably 0.02 to 3 parts by mass and more preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the monomer component.
乳化剤としては、特に限定はなく、アニオン性乳化剤、ノニオン性乳化剤、反応性乳化剤が挙げられる。
アニオン性乳化剤としては、オレイン酸カリウム等の脂肪酸金属塩、ラウリル硫酸ナトリウム等のアルキル硫酸塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸ナトリウム等のアルキルスルホン酸塩、ジアルキルスルホコハク酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルアリルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルエーテルリン酸エステル、ポリオキシエチレンアルキルアリルエーテルリン酸エステル等が挙げられる。
ノニオン性乳化剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレン−ポリオキシプロピレンブロックコポリマー、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等が挙げられる。
反応性乳化剤としては、種々の分子量（ＥＯ付加モル数の異なる）のポリエチレングリコールモノ（メタ）アクリレート、ポリオキシエチレンアルキルフェノールエーテル（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルスルホン酸アンモニウム、ポリエチレングリコールのモノマレイン酸エステルおよびその誘導体、（メタ）アクリロイルポリオキシアルキレンアルキルエーテルリン酸エステル等が挙げられる。
The emulsifier is not particularly limited, and examples thereof include an anionic emulsifier, a nonionic emulsifier, and a reactive emulsifier.
Examples of anionic emulsifiers include fatty acid metal salts such as potassium oleate, alkyl sulfates such as sodium lauryl sulfate, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfonates such as sodium alkyl naphthalene sulfonate, and dialkyl sulfosuccinates. Examples thereof include sodium acid, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl allyl ether phosphate, and the like.
Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene-polyoxypropylene block copolymer, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like.
As reactive emulsifiers, polyethylene glycol mono (meth) acrylate, polyoxyethylene alkylphenol ether (meth) acrylate, ammonium 2- (meth) acryloyloxyethylsulfonate, polyethylene glycol having various molecular weights (different EO addition mole numbers) Monomaleic acid esters and derivatives thereof, (meth) acryloyl polyoxyalkylene alkyl ether phosphates, and the like.
乳化剤の配合量は、モノマー成分１００質量部に対して、０．１〜１０質量部であることが好ましく、０．２〜５質量部であることがより好ましい。乳化剤の配合量を上記範囲内とすることにより、凝固物を生じることなく、適度な平均粒子径のアクリル系樹脂エマルションが得られる。 The blending amount of the emulsifier is preferably 0.1 to 10 parts by mass and more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the monomer component. By setting the blending amount of the emulsifier within the above range, an acrylic resin emulsion having an appropriate average particle diameter can be obtained without producing a coagulated product.
本発明において用いられるアクリル系樹脂は上述したように水媒体中で乳化重合法により得られる。アクリル系樹脂エマルションの固形分濃度は、３０〜７５質量％が好ましく、４０〜６５質量％がより好ましい。重合反応は、単一重合開始の場合では、好ましくは４０〜９５℃、より好ましくは６０〜９０℃程度の反応温度で、好ましくは１〜１０時間、より好ましくは４〜８時間程度行えばよい。また、レドックス系重合開始剤の場合では、反応温度はより低くできる。好ましくは、５〜９０℃、より好ましくは２０〜７０℃である。モノマーの添加方法としては、一括添加法、分割添加法、連続添加法等で、モノマータップ法、モノマープレ乳化タップ法等の方法で行うことができる。好ましくは連続添加法で、モノマープレ乳化タップ法である。 The acrylic resin used in the present invention is obtained by an emulsion polymerization method in an aqueous medium as described above. 30-75 mass% is preferable and, as for the solid content density | concentration of an acrylic resin emulsion, 40-65 mass% is more preferable. The polymerization reaction is preferably carried out at a reaction temperature of about 40 to 95 ° C., more preferably about 60 to 90 ° C., preferably about 1 to 10 hours, more preferably about 4 to 8 hours in the case of starting single polymerization. . In the case of a redox polymerization initiator, the reaction temperature can be further lowered. Preferably, it is 5-90 degreeC, More preferably, it is 20-70 degreeC. As a monomer addition method, a batch addition method, a divided addition method, a continuous addition method, or the like, such as a monomer tap method or a monomer pre-emulsification tap method can be used. The monomer pre-emulsification tapping method is preferred by the continuous addition method.
本発明において用いられるアクリル系樹脂は、平均粒子径が０．０１〜１．０μｍであることが好ましい。平均粒子径がこの範囲にあれば水分散性が良好となる。また、平均粒子径を上記範囲内とすることにより、塗工時の機械的安定性を高めることができ、所望の塗工量となるように調節が容易となり、塗工ムラが発生することも抑制することができる。なお、平均粒子径については、乳化剤や重合開始剤の種類および添加量、添加方法、攪拌条件等を適宜設定することにより容易に調整することができる。ここで、アクリル系樹脂の平均粒子径は光散乱法粒子径分布測定機（ＨＯＲＩＢＡ社製、商品名：ＬＢ−５５０）で測定したものである。 The acrylic resin used in the present invention preferably has an average particle size of 0.01 to 1.0 μm. If the average particle diameter is within this range, water dispersibility will be good. In addition, by making the average particle diameter within the above range, the mechanical stability at the time of coating can be increased, the adjustment can be facilitated to achieve a desired coating amount, and uneven coating may occur. Can be suppressed. In addition, about an average particle diameter, it can adjust easily by setting suitably the kind and addition amount of an emulsifier and a polymerization initiator, the addition method, stirring conditions, etc. Here, the average particle diameter of the acrylic resin is measured with a light scattering particle size distribution measuring machine (trade name: LB-550, manufactured by HORIBA).
本発明において用いられるアクリル系樹脂は、モノマー組成が異なる複数のモノマー成分の個々が重合する過程で一体化してなる樹脂複合体、すなわち、モノマーが異なる複数のモノマー成分を各段で用いた多段の乳化重合により得られる、いわゆるコアシェル型のエマルションであることが好ましい（以下コア部を構成する重合体をコア部、シェル部を構成する重合体をシェル部と略す場合がある）。コアシェル型のエマルションは、そのコア部には低いガラス転移温度（Ｔｇ）の樹脂を配置することが可能で、それにより感光体の傷付きを防止する効果が高められる。また、シェル部に高いガラス転移温度（Ｔｇ）の水溶性樹脂を配置することにより硬度を高くすることが可能になり、感光体汚染防止効果が向上する。このようなコアシェル型のエマルションは以下のようにして容易に得ることができる。 The acrylic resin used in the present invention is a resin composite formed by integrating a plurality of monomer components having different monomer compositions, that is, a multistage using a plurality of monomer components having different monomers at each stage. A so-called core-shell type emulsion obtained by emulsion polymerization is preferred (hereinafter, the polymer constituting the core part may be abbreviated as the core part and the polymer constituting the shell part may be abbreviated as the shell part). In the core-shell type emulsion, a resin having a low glass transition temperature (Tg) can be disposed in the core portion, thereby enhancing the effect of preventing the photoreceptor from being damaged. Further, by disposing a water-soluble resin having a high glass transition temperature (Tg) in the shell portion, it is possible to increase the hardness, and the effect of preventing the photoreceptor contamination is improved. Such a core-shell type emulsion can be easily obtained as follows.
アクリル系樹脂をコアシェル型エマルションとする場合、モノマー組成の異なる複数のモノマー成分を各段で用いた多段の乳化重合工程を経て製造する。ここで、多段の乳化重合とは、第１段階に用いたモノマー成分の８０質量％以上、好ましくは９０質量％以上が重合してから、新たにモノマー成分を加えて次の段（第２段階以降）の重合を行う重合方法をいう。乳化重合の段数は、特に限定されないが、製造工程を簡略化するためには、２段または３段が好ましい。 When the acrylic resin is made into a core-shell type emulsion, it is produced through a multi-stage emulsion polymerization process in which a plurality of monomer components having different monomer compositions are used in each stage. Here, multi-stage emulsion polymerization means that 80% by mass or more, preferably 90% by mass or more, of the monomer component used in the first stage is polymerized, and then the monomer component is added to the next stage (second stage). (Hereinafter referred to as “polymerization method”). The number of stages of emulsion polymerization is not particularly limited, but two or three stages are preferable in order to simplify the production process.
本発明において、アクリル系樹脂は、塗液の形態で紙基材の上に塗布されることが好ましい。アクリル系樹脂の塗液にはアクリル系樹脂の他に、さらにバインダー、顔料などを含んでもよい。また、必要に応じて、分散剤、増粘剤、保水剤、消泡剤、着色剤等の通常用いられている各種助剤が適宜使用できる。 In this invention, it is preferable that acrylic resin is apply | coated on a paper base material with the form of a coating liquid. In addition to the acrylic resin, the acrylic resin coating liquid may further contain a binder, a pigment, and the like. Moreover, various auxiliary agents normally used, such as a dispersing agent, a thickener, a water retention agent, an antifoaming agent, and a coloring agent, can be used as needed.
バインダーとしては、カゼイン、澱粉、変性澱粉、ポリビニルアルコールなどの水溶性高分子、ポリエステル系樹脂、ポリウレタン系樹脂、スチレン−ブタジエン系樹脂、酢酸ビニル系樹脂、エチレン−酢酸ビニル系樹脂、アクリロニトリル−ブタジエン系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、カルボキシメチルセルロース系樹脂、ポリアミド系樹脂、塩化ビニル系樹脂、塩化ビニリデン系樹脂等の水分散液が使用できる。 Binders include water-soluble polymers such as casein, starch, modified starch, polyvinyl alcohol, polyester resins, polyurethane resins, styrene-butadiene resins, vinyl acetate resins, ethylene-vinyl acetate resins, acrylonitrile-butadiene resins. Aqueous dispersions such as resins, polyethylene resins, polypropylene resins, carboxymethyl cellulose resins, polyamide resins, vinyl chloride resins, vinylidene chloride resins can be used.
顔料としてはカオリン、タルク、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、水酸化アルミニウム、アルミナ、シリカ、アルミノ珪酸マグネシウム、珪酸カルシウム、ホワイトカーボン、ベントナイト、ゼオライト、セリサイト、スメクタイト、硫酸カルシウム、硫酸バリウム、合成マイカ、二酸化チタン、酸化亜鉛などの無機顔料、さらにはポリイソプレン、ポリネオプレン、ポリブタジエン等のポリジエン類、ポリブテン、ポリイソブチレン、ポリプロピレン等のポリアルケン類、酢酸ビニル、スチレン、（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル、（メタ）アクリルアミド、メチルビニルエーテル等のビニル系モノマーの重合体や共重合体類、ポリウレタン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、尿素系樹脂、メラミン系樹脂、ベンゾグアナミン系樹脂等の各種の密実型、中空型、あるいは貫通孔型粒子等の有機顔料が挙げられ、上記の顔料の１種又は２種以上を使用することができる。 As pigments, kaolin, talc, calcium carbonate, magnesium carbonate, magnesium oxide, aluminum hydroxide, alumina, silica, magnesium aluminosilicate, calcium silicate, white carbon, bentonite, zeolite, sericite, smectite, calcium sulfate, barium sulfate, synthetic Inorganic pigments such as mica, titanium dioxide and zinc oxide, and polydienes such as polyisoprene, polyneoprene and polybutadiene, polyalkenes such as polybutene, polyisobutylene and polypropylene, vinyl acetate, styrene, (meth) acrylic acid, (meta ) Polymers and copolymers of vinyl monomers such as alkyl acrylates, (meth) acrylamides, methyl vinyl ethers, polyurethane resins, polyester resins, polyamide resins And organic pigments such as various solid-type, hollow-type, or through-hole type particles such as urea-based resin, melamine-based resin, and benzoguanamine-based resin, and the use of one or more of the above-mentioned pigments Can do.
アクリル系樹脂の塗布方法は、特に限定されるものではないが、例えばブレードコーター、エアーナイフコーター、ロールコーター、リバースロールコーター、バーコーター、カーテンコーター、スロットダイコーター、グラビアコーター、チャンプレックスコーター、ブラシコーター、ツーロール、並びにメータリングブレード式のサイズプレスコーター、ビルブレードコーター、ショートドウェルコーター、ゲートロールコーター等の塗工装置を適宜に用いて行うことができる。中でも、コストや、生産効率の観点からオンマシン方式での塗布が好ましく、サイズプレスコーターでの塗布が電子写真感光体用保護シートの表面改質には最も好ましい。すなわち、アクリル系樹脂は、抄紙機のサイズプレスパートにて塗布されることが好ましい。 The application method of the acrylic resin is not particularly limited, but for example, blade coater, air knife coater, roll coater, reverse roll coater, bar coater, curtain coater, slot die coater, gravure coater, Champlex coater, brush Coating apparatuses such as a coater, a two-roll, a metering blade type size press coater, a bill blade coater, a short dwell coater, and a gate roll coater can be used as appropriate. Of these, on-machine coating is preferable from the viewpoint of cost and production efficiency, and coating with a size press coater is most preferable for surface modification of the protective sheet for an electrophotographic photoreceptor. That is, the acrylic resin is preferably applied by a size press part of a paper machine.
抄紙機のサイズプレスパートとは、通常、抄紙した紙の表面に機能性を付与するための表面処理をする工程をいう。例えば、表面強度を増強させたり、インキの滲みを抑制するための処理を行うことができる。抄紙機においては、抄紙された紙をドライヤパートである程度乾燥させ、サイズプレスを行う。その後、再度のドライヤパートにて、乾燥処理を行う。
サイズプレスパートにおけるサイズプレス処理方法は、ポンド型サイズプレスと転写型サイズプレスに大別することができる。ポンド型サイズプレスは、抄紙されたシート基材が液溜まりの中を通過する方法であり、この方法ではサイズ液が紙基材の内部に浸透しやすくなる。一方、転写型サイズプレスは、ロール表面に形成された塗液膜がシート基材に転写される方法であり、サイズ液は紙基材の表面に留まることができる。本発明では、いずれのサイズプレスの処理方法を採用することができる。
The size press part of a paper machine usually refers to a step of surface treatment for imparting functionality to the surface of paper that has been made. For example, a treatment for increasing the surface strength or suppressing ink bleeding can be performed. In a paper machine, the paper that has been made is dried to some extent by a dryer part, and a size press is performed. Then, a drying process is performed in the dryer part again.
The size press processing method in the size press part can be roughly classified into a pound type size press and a transfer type size press. The pound-type size press is a method in which a paper sheet base material passes through a liquid reservoir, and in this method, the size liquid easily penetrates into the paper base material. On the other hand, the transfer type size press is a method in which the coating liquid film formed on the roll surface is transferred to the sheet base material, and the size liquid can remain on the surface of the paper base material. In the present invention, any size press processing method can be adopted.
本発明では、アクリル系樹脂を紙基材の片面のみ塗工する場合も規定しているが、その場合、反対面にはカール矯正やその他の機能を付与するために、水若しくは他の材料を塗布することも可能である。 The present invention also stipulates that the acrylic resin is applied only to one side of the paper base. In that case, water or other material is added to the opposite side in order to provide curl correction or other functions. It is also possible to apply.
本発明では、上述した処理に加え、平滑化処理を施すことも可能である。例えば、通常のスーパーカレンダー、グロスカレンダー、ソフトニップカレンダー等の平滑化処理を施すことができる。平滑化処理はオンマシンやオフマシンで適宜施されてもよく、加圧装置の形態、加圧ニップの数、加温等も通常の平滑化処理装置に応じて適宜調節される。 In the present invention, it is possible to perform a smoothing process in addition to the processes described above. For example, a smoothing process such as a normal super calendar, gloss calendar, and soft nip calendar can be performed. The smoothing process may be appropriately performed on-machine or off-machine, and the form of the pressure device, the number of pressure nips, heating, and the like are appropriately adjusted according to a normal smoothing device.
（紙基材）
本発明の電子写真感光体用保護シートの紙基材は、パルプを主成分として構成される。紙基材を構成するパルプについては、その製法及び種類等に特に限定はない。例えば、広葉樹及び／又は針葉樹のクラフトパルプ（ＫＰ）等の化学パルプ、ＳＧＰ、ＲＧＰ、ＢＣＴＭＰ及びＣＴＭＰ等の機械パルプ、脱墨パルプ等の古紙パルプ、ケナフ、竹、藁、麻等の非木材パルプなどが挙げられる。また、ポリアミド繊維、ポリエステル繊維等の有機合成繊維、再生繊維、例えばポリノジック繊維並びにガラス繊維、セラミック繊維、カーボン繊維等の無機質繊維も混用することができる。また、ＥＣＦパルプ、ＴＣＦパルプ等の塩素フリーパルプを用いることもできる。
なかでも広葉樹晒クラフトパルプ（ＬＢＫＰ）と針葉樹クラフトパルプ（ＮＢＫＰ）が好ましく用いられる。その使用比率については特に限定するものではないか、ＬＢＬＰ：ＮＢＫＰが、質量比で、２０：８０〜８０：２０が好ましく、より好ましくは３０：７０〜７０：３０の範囲で調整される。 パルプの叩解については、進めることにより電子写真感光体用保護シートがしなやかになり、作業中の折れやシワ入りが防げるが、叩解を進めすぎると湿度変化における寸法安定性が低下する恐れがあるため。このため、パルプの叩解度としては、ＪＩＳ Ｐ ８１２１−２：２ パルプ −ろ水度試験方法− 第２部：カナダ標準ろ水度法で規定されるカナディアンスタンダードフリーネスで２００〜４００ｍｌが好ましく、２５０〜３５０ｍｌがより好ましい。
(Paper substrate)
The paper base material of the protective sheet for an electrophotographic photoreceptor of the present invention is composed mainly of pulp. About the pulp which comprises a paper base material, there is no limitation in particular in the manufacturing method and kind. For example, chemical pulp such as kraft pulp (KP) of hardwood and / or conifers, mechanical pulp such as SGP, RGP, BCTMP and CTMP, waste paper pulp such as deinked pulp, non-wood pulp such as kenaf, bamboo, straw and hemp Etc. In addition, organic synthetic fibers such as polyamide fibers and polyester fibers, recycled fibers such as polynosic fibers, and inorganic fibers such as glass fibers, ceramic fibers, and carbon fibers can also be used. Moreover, chlorine free pulps, such as ECF pulp and TCF pulp, can also be used.
Of these, hardwood bleached kraft pulp (LBKP) and softwood kraft pulp (NBKP) are preferably used. The use ratio is not particularly limited, and LBLP: NBKP is preferably adjusted in a mass ratio of 20:80 to 80:20, more preferably 30:70 to 70:30. As pulp is beaten, the protective sheet for electrophotographic photosensitive member becomes supple and can be prevented from folding or wrinkling during work. However, if beating is advanced too much, the dimensional stability in humidity changes may be reduced. . Therefore, the beating degree of the pulp is preferably JIS P 8121-2: 2 Pulp-Freeness Test Method-Part 2: Canadian Standard Freeness stipulated by Canadian Standard Freeness Method, preferably 200-400 ml, 250 -350 ml is more preferred.
本発明では、紙基材は硫酸バンドを含むことが好ましい。より好ましくは、パルプ固形分の１００質量部に対して、硫酸バンドの固形分を０．３３質量部以下含有し、さらに好ましくは０．０６〜０．３３質量部含有し、さらにより好ましくは０．１９〜０．３１質量部含有し、特に好ましくは、０．２１〜０．３１質量部含有する。紙基材にカーボンブラックなどの填料を多く定着させる必要がある場合、従来では、硫酸バンドを大量に添加していたが、本発明者らによれば、紙基材に硫酸バンドを上記した範囲で添加することで、アルミニウムイオンの溶出量を抑えつつ、カーボンブラックなどの填料の定着性を高めて、遮光性を高めることができ、好ましい遮光性と導電性を備えた電子写真感光体用保護シートとすることができることを見出した。そして、硫酸バンドの配合量を上記した所定範囲とすることにより、電子写真感光体用保護シートの熱水抽出により抽出されるアルミニウムイオンの質量割合を１５質量ｐｐｍ以下にでき、アクリル樹脂系粕の発生を効果的に抑制できる。 In the present invention, the paper substrate preferably contains a sulfate band. More preferably, the solid content of the sulfuric acid band is 0.33 parts by mass or less, more preferably 0.06 to 0.33 parts by mass, and still more preferably 0 to 100 parts by mass of the pulp solid content. .19 to 0.31 part by mass, particularly preferably 0.21 to 0.31 part by mass. When it is necessary to fix a large amount of filler such as carbon black on a paper base material, conventionally, a large amount of a sulfuric acid band has been added. By adding in, it is possible to increase the fixing property of fillers such as carbon black while suppressing the elution amount of aluminum ions, to improve the light shielding property, and to protect the electrophotographic photosensitive member with preferable light shielding property and conductivity. It was found that it can be made into a sheet. And the mass ratio of the aluminum ion extracted by the hot water extraction of the protection sheet for electrophotographic photoreceptors can be reduced to 15 mass ppm or less by setting the blending amount of the sulfuric acid band to the above-described predetermined range. Generation can be effectively suppressed.
本発明では、紙基材は導電填料を含むことが好ましい。導電填料の中でも傷付き防止効果、遮光性、コストの面で、カーボンブラックを用いることが特に好ましい。
カーボンブラックの配合量は、乾燥状態のパルプ固形分の１００質量部に対して、１〜２０質量部であることが好ましく、３〜１５質量部であることがより好ましい。カーボンブラックの配合量を上記範囲内とすることにより、紙基材は十分な遮光性に加えて、導電性を備えることができる。更には、感光体の傷付きや汚染等を抑制できる。
In the present invention, the paper base material preferably contains a conductive filler. Among the conductive fillers, it is particularly preferable to use carbon black from the viewpoints of damage prevention effect, light shielding property, and cost.
The compounding amount of carbon black is preferably 1 to 20 parts by mass and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of dry pulp solids. By setting the blending amount of carbon black within the above range, the paper substrate can be provided with conductivity in addition to sufficient light shielding properties. Furthermore, scratches and contamination of the photoreceptor can be suppressed.
カーボンブラックの平均粒子径は、２０〜３００ｎｍであることが好ましく、３０〜２００ｎｍであることがより好ましい。カーボンブラックの平均粒子径を上記範囲内とすることにより、紙基材中における分散性を高めることができ、かつ、感光体の傷付きを抑制することができる。 The average particle size of carbon black is preferably 20 to 300 nm, and more preferably 30 to 200 nm. By setting the average particle size of the carbon black within the above range, dispersibility in the paper base material can be enhanced, and scratching of the photoreceptor can be suppressed.
本発明では、紙基材には、必要に応じてその他の填料が配合されていてもよい。填料としては、一般に上質紙等に用いられる各種の顔料を用いることができ、例えばカオリン、焼成カオリン、炭酸カルシウム、硫酸カルシウム、硫酸バリウム、二酸化チタン、タルク、酸化亜鉛、アルミナ、炭酸マグネシウム、酸化マグネシウム、シリカ、ホワイトカーボン、ベントナイト、ゼオライト、セリサイト及びスメクタイト等の鉱物質顔料、並びにポリスチレン系樹脂、尿素系樹脂、メラミン系樹脂、アクリル系樹脂及び塩化ビニリデン系樹脂の微小中空粒子、密実型粒子および貫通孔型粒子などの有機顔料が挙げられる。 In the present invention, the paper base material may be blended with other fillers as necessary. As the filler, various pigments generally used for fine paper can be used. For example, kaolin, calcined kaolin, calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, zinc oxide, alumina, magnesium carbonate, magnesium oxide , Silica, white carbon, bentonite, zeolite, mineral pigments such as sericite and smectite, and polystyrene resin, urea resin, melamine resin, acrylic resin and vinylidene chloride resin micro hollow particles, solid particles And organic pigments such as through-hole type particles.
本発明では、紙基材には、内添サイズ剤を使用することもできる。内添サイズ剤としては、ロジン系サイズ剤、合成サイズ剤、石油樹脂系サイズ剤、アルキルケテンダイマー、アルケニル無水コハク酸系の中性サイズ剤等が挙げられる。これらは、硫酸バンド、カチオン化デンプン等の定着剤を組み合わせて使用してもよい。 In the present invention, an internal sizing agent can also be used for the paper substrate. Examples of the internally added sizing agent include rosin sizing agents, synthetic sizing agents, petroleum resin sizing agents, alkyl ketene dimers, and alkenyl succinic anhydride neutral sizing agents. These may be used in combination with a fixing agent such as a sulfate band or cationized starch.
本発明では、紙基材には、内添バインダーや紙力増強剤を使用することもできる。内添バインダーとしては、例えば各種デンプン、ポリビニルアルコール、カルボキシメチルセルロース等の水溶性高分子が挙げられる。また、紙力増強剤としては、ポリアクリルアミド等が挙げられる。
本発明では、紙基材には、湿潤紙力増強剤を使用することができる。湿潤紙力増強剤としては、例えばポリアミド樹脂、メラミン−ホルムアルデヒド樹脂、尿素−ホルムアルデヒド樹脂、ポリアミド−ポリアミン−エピクロルヒドリン樹脂、ポリエチレンイミン樹脂等が挙げられる。なお、紙基材の抄紙時に、その紙料中に、本発明の所望の効果を損なわない範囲で、従来から使用されている各種のアニオン性、ノニオン性、カチオン性あるいは両性の歩留向上剤、濾水性向上剤等の各種抄紙用内添助剤を必要に応じて適宜選択して使用することができる。さらに染料、蛍光増白剤、ｐＨ調整剤、消泡剤、ピッチコントロール剤、スライムコントロール剤等の抄紙用内添助剤も必要に応じて適宜添加することができる。
In the present invention, an internally added binder or a paper strength enhancer can also be used for the paper substrate. Examples of the internally added binder include water-soluble polymers such as various starches, polyvinyl alcohol, and carboxymethyl cellulose. Examples of paper strength enhancers include polyacrylamide.
In the present invention, a wet paper strength enhancer can be used for the paper substrate. Examples of the wet paper strength enhancer include polyamide resin, melamine-formaldehyde resin, urea-formaldehyde resin, polyamide-polyamine-epichlorohydrin resin, and polyethyleneimine resin. It should be noted that various anionic, nonionic, cationic or amphoteric yield improvers that have been used in the past, as long as the desired effects of the present invention are not impaired during the paper making of the paper substrate. In addition, various papermaking additives such as freeness improvers can be appropriately selected and used as necessary. Furthermore, internal additives for papermaking such as dyes, fluorescent brighteners, pH adjusters, antifoaming agents, pitch control agents, slime control agents and the like can be added as necessary.
紙基材の抄紙方法については特に限定はなく、例えば抄紙ｐＨが４．５付近で行われる酸性抄紙法、炭酸カルシウム等のアルカリ性填料を主成分として含み、抄紙ｐＨ約６の弱酸性から抄紙ｐＨ約９の弱アルカリ性で行われる中性抄紙法等の全ての抄紙方法を適用することができ、抄紙機も長網抄紙機、ツインワイヤー抄紙機、円網抄紙機、ヤンキー抄紙機等を適宜使用することができる。 The paper making method of the paper base is not particularly limited. For example, an acid paper making method in which the paper making pH is around 4.5, an alkaline filler such as calcium carbonate is contained as a main component, and the paper making pH is from a weak acid having a paper making pH of about 6. All papermaking methods such as neutral papermaking, which is performed with a weak alkalinity of about 9, can be applied, and long paper machines, twin wire paper machines, circular paper machines, Yankee paper machines, etc. are used as appropriate. can do.
以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。実施例において示す「部」および「％」は、特に明示の無い限り、質量部および質量％である。 The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. In the examples, “parts” and “%” are parts by mass and mass% unless otherwise specified.
＜実施例１＞
ＮＢＫＰ（ＣＳＦフリーネス３３０ｍｌ）６０質量部、ＬＢＫＰ（ＣＳＦフリーネス３３０ｍｌ）４０質量部のパルプスラリーに、内添サイズ剤としてロジン系サイズ剤（商品名：サイズパインＮ−１１１−５０、荒川化学工業社製）の５０質量％品を２．０質量部、両性ポリアクリルアミド系紙力増強剤（商品名：ポリストロン１２５０、荒川化学工業社製）の２０質量％品を１．０質量部、カーボンブラック（商品名：ＯＫＨＡ−０２、テルナイト社製）の９．５質量％品７０質量部を添加して、紙基材用の紙料を調製した。この紙料を長網抄紙機に供して抄紙し、得られた湿紙の片面（Ｗ面）にアクリル系樹脂（ポリゾールＡＭ−２９０、ガラス転移温度：−１０℃、中和剤としてアミノアルコール類を使用、昭和電工社製）の１０．０質量％水溶液をサイズプレス装置で乾燥後の塗布量が２．０ｇ／ｍ2となるように塗布し、且つ反対面（Ｆ面）には水を塗布乾燥した後、スーパーカレンダーによる平滑化処理を施して坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 1>
A pulp slurry of 60 parts by mass of NBKP (CSF freeness 330 ml) and 40 parts by mass of LBKP (CSF freeness 330 ml), and a rosin sizing agent (trade name: Size Pine N-111-50, manufactured by Arakawa Chemical Industries, Ltd.) as an internal sizing agent ) Is 2.0 parts by mass, amphoteric polyacrylamide-based paper strength enhancer (trade name: Polystron 1250, manufactured by Arakawa Chemical Industries, Ltd.) is 20 parts by mass, carbon black ( 70 parts by mass of a 9.5% by mass product (trade name: OKHA-02, manufactured by Ternite Co., Ltd.) was added to prepare a paper stock for a paper substrate. This stock is subjected to a long paper machine to produce paper, and acrylic resin (Polysol AM-290, glass transition temperature: −10 ° C., amino alcohols as a neutralizing agent is provided on one side (W side) of the obtained wet paper. , Manufactured by Showa Denko Co., Ltd.) with a size press machine so that the coating amount after drying is 2.0 g / m 2 , and water is applied to the opposite surface (F surface). After coating and drying, a protective sheet for an electrophotographic photosensitive member having a basis weight of 68.0 g / m 2 was obtained by performing a smoothing process using a super calendar.
＜実施例２＞
実施例１のカーボンブラック添加量を１０５質量部とし、それ以外は実施例１と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 2>
The amount of carbon black added in Example 1 was 105 parts by mass, and other than that was obtained in the same manner as in Example 1 to obtain a protective sheet for an electrophotographic photoreceptor having a basis weight of 68.0 g / m 2 .
＜実施例３＞
実施例１のカーボンブラック添加量を１４０質量部とし、それ以外は実施例１と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 3>
The amount of carbon black added in Example 1 was 140 parts by mass, and other than that was obtained in the same manner as in Example 1 to obtain a protective sheet for an electrophotographic photoreceptor having a basis weight of 68.0 g / m 2 .
＜実施例４＞
実施例１と同様のパルプスラリーに、内添サイズ剤としてロジン系サイズ剤（商品名：サイズパインＮ−１１１−５０、荒川化学工業社製）の５０質量％品を２．０質量部、硫酸バンドの８．０質量％品を１．０質量部（固形分で０．０８質量部）、両性ポリアクリルアミド系紙力増強剤（商品名：ポリストロン１２５０、荒川化学工業社製）の２０質量％品を１．０質量部、カーボンブラック（商品名：ＯＫＨＡ−０２、テルナイト社製）の９．５質量％品を７０質量部添加して、紙基材用の紙料を調製した。この紙料を長網抄紙機に供して抄紙し、得られた湿紙の片面（Ｗ面）に実施例１と同様のアクリル系樹脂水溶液をサイズプレス装置で乾燥後の塗布量が２．０ｇ／ｍ2となるように塗布し、且つ反対面（Ｆ面）には水を塗布乾燥して坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 4>
To the same pulp slurry as in Example 1, 2.0 parts by mass of 50% by mass of a rosin sizing agent (trade name: Size Pine N-111-50, manufactured by Arakawa Chemical Industries) as an internal sizing agent, sulfuric acid 1.0 mass part (0.08 mass parts in solid content) of the 8.0 mass% product of the band, 20 masses of the amphoteric polyacrylamide-based paper strength enhancer (trade name: Polystron 1250, manufactured by Arakawa Chemical Industries, Ltd.) A paper stock for a paper base material was prepared by adding 1.0 part by weight of 70% by weight and 70 parts by weight of 9.5% by weight of carbon black (trade name: OKHA-02, manufactured by Ternite). This stock is subjected to a long paper machine to make paper, and the wet paper obtained is coated on one side (W side) with the same acrylic resin aqueous solution as that used in Example 1 in a size press device with a coating amount of 2.0 g. / m 2 and so as to be applied, the and the opposite side (F side) to obtain an electrophotographic photoreceptor protective sheet having a basis weight of 68.0 g / m 2 by coating and drying the water.
＜実施例５＞
実施例４のカーボンブラック添加量を１０５質量部とし、それ以外は実施例４と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 5>
In the same manner as in Example 4 except that the amount of carbon black added in Example 4 was 105 parts by mass, a protective sheet for an electrophotographic photoreceptor having a basis weight of 68.0 g / m 2 was obtained.
＜実施例６＞
実施例４のカーボンブラック添加量を１４０質量部とし、それ以外は実施例４と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 6>
The amount of carbon black added in Example 4 was 140 parts by mass, and other than that was obtained in the same manner as in Example 4 to obtain a protective sheet for an electrophotographic photoreceptor having a basis weight of 68.0 g / m 2 .
＜実施例７＞
実施例２の硫酸バンド添加量を２．５質量部（固形分で０．２０質量部）とし、それ以外は実施例２と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 7>
For the electrophotographic photosensitive member having a basis weight of 68.0 g / m 2 , the sulfuric acid band addition amount of Example 2 was set to 2.5 parts by mass (0.20 parts by mass in solid content), and otherwise, in the same manner as Example 2. A protective sheet was obtained.
＜実施例８＞
実施例２の硫酸バンド添加量を３．０質量部（固形分で０．２４質量部）とし、それ以外は実施例２と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 8>
For the electrophotographic photosensitive member having a basis weight of 68.0 g / m 2 , the sulfuric acid band addition amount of Example 2 was set to 3.0 parts by mass (solid content: 0.24 parts by mass), and other than that, the basis weight was 68.0 g / m 2. A protective sheet was obtained.
＜実施例９＞
実施例２の硫酸バンド添加量を３．９質量部（固形分で０．３１質量部）とし、それ以外は実施例２と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 9>
The amount of sulfuric acid band added in Example 2 was 3.9 parts by mass (0.31 parts by mass in solid content), and other than that, in the same manner as in Example 2, for an electrophotographic photoreceptor having a basis weight of 68.0 g / m 2. A protective sheet was obtained.
＜実施例１０＞
実施例１と同様のパルプスラリーに、内添サイズ剤としてロジン系サイズ剤（商品名：サイズパインＮ−１１１−５０、荒川化学工業社製）の５０質量％品を２．０質量部、硫酸バンドの８．０質量％品を３．９質量部（固形分で０．３１質量部）、両性ポリアクリルアミド系紙力増強剤（商品名：ポリストロン１２５０、荒川化学工業社製）の２０質量％品を１．０質量部、カーボンブラック（商品名：ＯＫＨＡ−０２、テルナイト社製）の９．５質量％品を７０質量部添加して、紙基材用の紙料を調製した。この紙料を長網抄紙機に供して抄紙し、得られた湿紙の両面に実施例１と同様のアクリル系樹脂水溶液をサイズプレス装置で乾燥後の塗布量が両面で４．０ｇ／ｍ2となるように塗布乾燥して坪量７０．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 10>
To the same pulp slurry as in Example 1, 2.0 parts by mass of 50% by mass of a rosin sizing agent (trade name: Size Pine N-111-50, manufactured by Arakawa Chemical Industries) as an internal sizing agent, sulfuric acid 3.9 parts by mass (8.01 parts by mass in solid content) of 8.0% by mass of band, 20 parts by mass of amphoteric polyacrylamide paper strength enhancer (trade name: Polystron 1250, manufactured by Arakawa Chemical Industries, Ltd.) A paper stock for a paper base material was prepared by adding 1.0 part by weight of 70% by weight and 70 parts by weight of 9.5% by weight of carbon black (trade name: OKHA-02, manufactured by Ternite). The stock was subjected to a paper web machine to make a paper, and an acrylic resin aqueous solution similar to that of Example 1 was applied to both sides of the obtained wet paper with a size press machine, and the coating amount on both sides was 4.0 g / m. 2 was applied and dried to obtain a protective sheet for an electrophotographic photoreceptor having a basis weight of 70.0 g / m 2 .
＜実施例１１＞
実施例１で得られた電子写真感光体用保護シートをさらにスーパーカレンダーによる平滑化処理を施して、高平滑とした以外は実施例１と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 11>
An electrophotographic photogram having a basis weight of 68.0 g / m 2 was obtained in the same manner as in Example 1 except that the electrophotographic photosensitive member protective sheet obtained in Example 1 was further smoothed by supercalendering to obtain a high smoothness. A protective sheet for a photoreceptor was obtained.
＜実施例１２＞
実施例１０において、サイズプレス装置で塗布するアクリル系樹脂として「ＸＰ８８０７」（商品名）（ガラス転移温度：−２３℃、中和剤としてアンモニアを使用、星光ＰＭＣ社製）の１０．０質量％水溶液を、サイズプレス装置で乾燥後の塗布量が４．０ｇ／ｍ2となるように塗布した以外は実施例１０と同様にして坪量７０．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Example 12>
In Example 10, 10.0% by mass of “XP8807” (trade name) (glass transition temperature: −23 ° C., using ammonia as a neutralizing agent, manufactured by Seiko PMC Co., Ltd.) as an acrylic resin to be applied with a size press apparatus. A protective sheet for an electrophotographic photosensitive member having a basis weight of 70.0 g / m 2 in the same manner as in Example 10 except that the aqueous solution was coated with a size press so that the coating amount after drying was 4.0 g / m 2. Got.
＜比較例１＞
実施例４の硫酸バンド添加量を５．０質量部（固形分で０．４０質量部）とし、それ以外は実施例４と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Comparative Example 1>
The amount of sulfuric acid band added in Example 4 was 5.0 parts by mass (0.40 parts by mass in solid content), and other than that, in the same manner as in Example 4, for an electrophotographic photoreceptor having a basis weight of 68.0 g / m 2. A protective sheet was obtained.
＜比較例２＞
実施例１０の硫酸バンド添加量を５．０質量部（固形分で０．４０質量部）とし、それ以外は実施例１０と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Comparative example 2>
The amount of sulfuric acid band added in Example 10 was 5.0 parts by mass (0.40 parts by mass in solid content), and other than that, in the same manner as in Example 10, for an electrophotographic photoreceptor having a basis weight of 68.0 g / m 2. A protective sheet was obtained.
＜比較例３＞
実施例１と同様のパルプスラリーに、内添サイズ剤としてロジン系サイズ剤（商品名：サイズパインＮ−１１１−５０、荒川化学工業社製）の５０質量％品を２．０質量部、硫酸バンドの８．０質量％品を３．０質量部（固形分で０．２４質量部）、両性ポリアクリルアミド系紙力増強剤（商品名：ポリストロン１２５０、荒川化学工業社製）の２０質量％品を１．０質量部、カーボンブラック（商品名：ＯＫＨＡ−０２、テルナイト社製）の９．５質量％品を７０質量部添加して、紙基材用の紙料を調製した。この紙料を長網抄紙機に供して抄紙し、得られた湿紙を乾燥させ坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Comparative Example 3>
To the same pulp slurry as in Example 1, 2.0 parts by mass of 50% by mass of a rosin sizing agent (trade name: Size Pine N-111-50, manufactured by Arakawa Chemical Industries) as an internal sizing agent, sulfuric acid 8.0 parts by mass of 8.0% by mass of a band (0.24 parts by mass in solid content), 20 parts by mass of an amphoteric polyacrylamide paper strength enhancer (trade name: Polystron 1250, manufactured by Arakawa Chemical Industries, Ltd.) A paper stock for a paper base material was prepared by adding 1.0 part by weight of 70% by weight and 70 parts by weight of 9.5% by weight of carbon black (trade name: OKHA-02, manufactured by Ternite). The stock was subjected to a paper web machine to make paper, and the obtained wet paper was dried to obtain a protective sheet for an electrophotographic photoreceptor having a basis weight of 68.0 g / m 2 .
＜比較例４＞
比較例３の硫酸バンド添加量を５．０質量部（固形分で０．４０質量部）とし、それ以外は比較例３と同様にして坪量６８．０ｇ／ｍ2の電子写真感光体用保護シートを得た。
<Comparative example 4>
For the electrophotographic photosensitive member having a basis weight of 68.0 g / m 2 , the sulfuric acid band addition amount of Comparative Example 3 was 5.0 parts by mass (0.40 parts by mass in terms of solid content), and other than that, as in Comparative Example 3. A protective sheet was obtained.
実施例及び比較例で得られた電子写真感光体用保護シートの、アルミニウムイオンおよびアンモニウムイオンの熱水抽出量、表面平滑度、黒色の分光濃度、波長３００〜８５０ｎｍでの光透過率の最大値、製造工程での粕発生の有無、感光体と擦り合わせた際の傷つき度合い、保護シートを接触させて高温高湿処理を行った感光体による出力画像の画質、表面電気抵抗を以下の方法で評価した。その結果を表１に示す。 Maximum amount of aluminum ion and ammonium ion hot water extraction, surface smoothness, black spectral density, and light transmittance at a wavelength of 300 to 850 nm of the protective sheets for electrophotographic photoreceptors obtained in Examples and Comparative Examples. The following methods are used to determine the presence or absence of wrinkles in the manufacturing process, the degree of scratching when rubbing with the photoreceptor, the image quality of the output image by the photoreceptor subjected to high-temperature and high-humidity treatment by contacting the protective sheet, and the surface electrical resistance by the following methods: evaluated. The results are shown in Table 1.
（アルミニウムイオン熱水抽出量の測定）
電子写真感光体用保護シートを、「ＪＩＳ Ｐ ８１３３：１９９８ 紙、板紙及びパルプ −水抽出液ｐＨの試験方法 ６．試料の採取及び試験片の調製」に準拠して試料調製した。調製した試料を「ＪＩＳ Ｐ ８１４４：１９９８ 紙、板紙及びパルプ −水溶性塩化物の分析方法 ９．ａ抽出操作」に準拠して熱水抽出を行った。抽出液中のアルミニウムイオン濃度を、ＩＣＰ−ＯＥＳ（誘導結合プラズマ発光分光）によって測定した。
(Measurement of aluminum ion hot water extraction)
A protective sheet for an electrophotographic photosensitive member was prepared in accordance with “JIS P 8133: 1998 Paper, paperboard and pulp—Test method for water extract pH 6. Sample collection and test piece preparation”. The prepared sample was subjected to hot water extraction in accordance with “JIS P 8144: 1998 paper, paperboard and pulp-analytical method of water-soluble chloride 9.a extraction operation”. The aluminum ion concentration in the extract was measured by ICP-OES (inductively coupled plasma emission spectroscopy).
（アンモニウムイオン熱水抽出量の測定）
電子写真感光体用保護シートを、「ＪＩＳ Ｐ ８１３３：１９９８ 紙、板紙及びパルプ −水抽出液ｐＨの試験方法 ６．試料の採取及び試験片の調製」に準拠して試料調製した。調製した試料を「ＪＩＳ Ｐ ８１４４：１９９８ 紙、板紙及びパルプ −水溶性塩化物の分析方法 ９．ａ抽出操作」に準拠して熱水抽出を行った。抽出液中のアンモニウムイオン濃度を、イオンクロマトグラフィーによって測定した。
(Measurement of ammonium ion hot water extraction)
A protective sheet for an electrophotographic photosensitive member was prepared in accordance with “JIS P 8133: 1998 Paper, paperboard and pulp—Test method for water extract pH 6. Sample collection and test piece preparation”. The prepared sample was subjected to hot water extraction in accordance with “JIS P 8144: 1998 paper, paperboard and pulp-analytical method of water-soluble chloride 9.a extraction operation”. The ammonium ion concentration in the extract was measured by ion chromatography.
（表面平滑度の測定）
王研式平滑度計（ＪＡＰＡＮ ＴＡＰＰＩ Ｎｏ．５−２：２０００に準拠）を用いて保護シートの表面平滑度を測定した。
(Measurement of surface smoothness)
The surface smoothness of the protective sheet was measured using a Oken type smoothness meter (based on JAPAN TAPPI No. 5-2: 2000).
（こわさの測定）
ガーレー剛軟度測定器（ＪＡＰＡＮ ＴＡＰＰＩ Ｎｏ．４０に準拠）を用いて保護シートの抄紙方向に対して平行（縦）方向と直角（横）方向のこわさを測定した。
(Measure stiffness)
The stiffness of the protective sheet in the parallel (longitudinal) direction and the right angle (transverse) direction was measured using a Gurley stiffness measuring instrument (based on JAPAN TAPPI No. 40).
（粕発生の有無）
サイズプレス装置を用い、抄速１００ｍ／分の速度で、紙基材を、塗料溜りのある２つのロール間（サイズプレスロール）を通過させて、紙基材にアクリル樹脂を塗布した。１時間操業し、サイズプレスロールに粕付着が見られた場合「有」、見られなかった場合を「無」とした。
(Presence or absence of wrinkles)
Using a size press apparatus, an acrylic resin was applied to the paper base material by passing the paper base material between two rolls (size press rolls) having a paint reservoir at a papermaking speed of 100 m / min. The operation was carried out for 1 hour, and when there was wrinkle adhesion on the size press roll, it was judged as “Yes”, and when it was not seen as “No”.
（傷付き度合いの評価方法）
電子写真感光体用保護シートを２００ｍｍ×１００ｍｍにカットし、東洋精機製作所製の「サウザランド・ラブテスタ」のサンプル台にＷ面が上になるように固定した。リコー社製の「感光体ユニット２５００」より２００ｍｍ×５０ｍｍの感光体フィルムを採集し、質量が１９１６ｇの摺動子に巻きつけた。この摺動子をサウザランド・ラブテスタにセットし、円弧軌道上を一定速度で２０往復させ、電子写真感光体用保護シートのＷ面と感光体フィルムを擦り、下記基準で、感光体の傷付き度合いを目視で評価した。○、△が実用的である。
○： 傷がつかなかった
△： 若干傷がみられた
×： 傷がついた
(Evaluation method of degree of scratch)
The protective sheet for an electrophotographic photosensitive member was cut into 200 mm × 100 mm, and fixed to a sample table of “Sautherland Love Tester” manufactured by Toyo Seiki Seisakusho with the W surface facing up. A photoconductor film of 200 mm × 50 mm was collected from “Photoconductor unit 2500” manufactured by Ricoh Co., Ltd., and was wound around a slider having a mass of 1916 g. This slider is set on the Sauzaland Love Tester, reciprocated 20 times on the circular arc track at a constant speed, rubbing the W surface of the electrophotographic photosensitive member protective sheet and the photosensitive film, and the degree of damage to the photosensitive member based on the following criteria. Was visually evaluated. ○ and Δ are practical.
○: Scratch not found △: Slightly scratched ×: Scratched
（出力画像の画質評価）
電子写真感光体用保護シートをリコー社製電子写真プリンター「イプシオ ＳＰ Ｃ８１０」の感光ドラムに巻き付け、４５℃８０％ＲＨ環境下に２４時間放置し、その後、２３℃５０％ＲＨ環境下に２４時間放置した後にプリンターに装填して、画像を出力して、出力画像への影響を評価した。○、△が実用的である。
○：出力画像への影響が見られなかった
△：出力画像への影響が若干見られた
×：出力画像が大きく乱れた
(Quality evaluation of output image)
The protective sheet for the electrophotographic photosensitive member is wound around the photosensitive drum of the Ricoh electrophotographic printer “Ipsio SP C810” and left in an environment of 45 ° C. and 80% RH for 24 hours, and then in an environment of 23 ° C. and 50% RH for 24 hours. After leaving it to stand, it was loaded into a printer and an image was output to evaluate the influence on the output image. ○ and Δ are practical.
○: No effect on the output image was observed △: Some effect on the output image was observed ×: The output image was greatly disturbed
（黒色の分光濃度測定）
Ｘ−Ｒｉｔｅ ９３９ ０°／４５°ポータブル分光測色計（エックスライト社製）を用いて黒色の分光濃度を測定した。
(Black spectral density measurement)
The spectral density of black was measured using an X-Rite 939 0 ° / 45 ° portable spectrocolorimeter (manufactured by X-Rite).
（保護シートの光透過率測定）
分光光度計Ｖ−６７０ＳＴ、日本分光社製を用いて、波長が３００〜８５０ｎｍでの光透過率の最大値を測定した。
(Measurement of light transmittance of protective sheet)
Using a spectrophotometer V-670ST, manufactured by JASCO Corporation, the maximum light transmittance at a wavelength of 300 to 850 nm was measured.
（表面電気抵抗）
アドバンテスト社製 ロレスタ−ＧＰを用いて２３℃・５０％ＲＨの環境下で、四探針法により電子写真感光体用保護シートのＷ面側の表面電気抵抗を測定した。
(Surface electrical resistance)
The surface electrical resistance on the W surface side of the protective sheet for electrophotographic photosensitive member was measured by a four-probe method in an environment of 23 ° C. and 50% RH using a Loresta-GP manufactured by Advantest Corporation.
表１からわかるように、パルプ固形分１００質量部に対し、硫酸バンドの固形分が０．３３質量以下の紙基材を用い、且つアクリル系樹脂を紙基材の少なくとも一方の面に有する実施例１〜１２は、保護シートから抽出されるアルミニウムイオンは１５質量ｐｐｍ以下と抑制され、粕発生は見られず、感光体と擦り合わせた際も傷がつかなかった。
また、実施例１〜６および１１と、実施例７〜１０および１２とを比較すると、硫酸バンドの固形分が、パルプ固形分１００質量部に対し０．１９〜０．３１質量部である実施例７〜１０および１２は、１．２０以上の分光濃度を有し、好ましい遮光性が得られていることがわかる。更には、表面抵抗値が１×１０8Ω／□以下であり、好ましい表面電気抵抗値が得られていることがわかる。特に、硫酸バンドの固形分が、パルプ固形分１００質量部に対し０．２１〜０．３１質量部である実施例８〜１０および１２は、１．３０以上の分光濃度を有し、表面抵抗値が１×１０4Ω／□以下であった。
また、実施例１〜１０、１２と、実施例１１とを比較すると、表面平滑度が２００秒以下とすることにより感光体の傷つきを効果的に抑制出来た。
また、実施例１〜１１と、実施例１２とを比較すると、保護シートから抽出されるアンモニウムイオンを３００質量ｐｐｍ以下とすることにより、保護シートと接触させた状態で高温高湿処理を行った後の感光体を用いて印刷しても、出力画像に乱れはなく良好であった。
一方、比較例１、２は、アルミニウムイオンが３５質量ｐｐｍと多く抽出されていた。また、アクリル系樹脂が凝集した粕が発生し、粕が保護シートにも混入した。粕が混入した保護シートと感光体とが擦り合うことにより傷がついた。
また、比較例３，４はアクリル系樹脂を有していないため、感光体と擦り合わせると傷がついた。
As can be seen from Table 1, with respect to 100 parts by mass of pulp solids, a paper base material having a solid content of sulfuric acid band of 0.33 mass or less and having an acrylic resin on at least one surface of the paper base material In Examples 1 to 12, aluminum ions extracted from the protective sheet were suppressed to 15 ppm by mass or less, no generation of wrinkles was observed, and no scratches were observed even when rubbed with the photoreceptor.
Moreover, when Examples 1-6 and 11 are compared with Examples 7-10 and 12, solid content of a sulfuric acid band is 0.19-0.31 mass part with respect to 100 mass parts of pulp solid content. It can be seen that Examples 7 to 10 and 12 have a spectral density of 1.20 or more, and preferable light-shielding properties are obtained. Furthermore, the surface resistance value is 1 × 10 8 Ω / □ or less, which indicates that a preferable surface electric resistance value is obtained. In particular, Examples 8 to 10 and 12 in which the solid content of the sulfuric acid band is 0.21 to 0.31 parts by mass with respect to 100 parts by mass of the pulp solids have a spectral density of 1.30 or more, and the surface resistance The value was 1 × 10 4 Ω / □ or less.
Further, when Examples 1 to 10 and 12 were compared with Example 11, it was possible to effectively suppress the damage of the photoreceptor by setting the surface smoothness to 200 seconds or less.
Moreover, when Examples 1-11 were compared with Example 12, the high-temperature, high-humidity process was performed in the state made to contact with a protective sheet by making ammonium ion extracted from a protective sheet into 300 mass ppm or less. Even when printing was performed using a later photoconductor, the output image was good without any disturbance.
On the other hand, in Comparative Examples 1 and 2, the aluminum ion was extracted as much as 35 mass ppm. Moreover, the wrinkles which acrylic resin aggregated generate | occur | produced and the wrinkles mixed also in the protective sheet. The protective sheet mixed with wrinkles and the photoconductor rubbed each other and scratched.
Moreover, since Comparative Examples 3 and 4 did not have an acrylic resin, they were scratched when rubbed with the photoreceptor.
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