JP2005194518A - Positive charge controlling resin for electrophotography functional part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive charge controlling resin which is environmentally safe, good in electrostatically charging properties, dispersibility, and coloring properties, and can freely control a charge, and to provide an electrophotography functional part comprising the resin. <P>SOLUTION: The positive charge controlling resin comprises a copolymer obtained by polymerizing a monomer composition consisting of a hydroxy group-containing monomer, an amino group-containing monomer, and according to demand, still another monomer containing a (meth)acrylic ester monomer. The electrophotography functional part comprises the positive charge controlling resin as a polyol which is a raw material of a polyurethane. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a positively chargeable control resin used when a latent electrostatic image is made visible in dry electrophotography, and to an electrophotographic functional component containing the resin. More specifically, the charge can be freely controlled. The present invention relates to a positive charge control resin capable of forming a high-density image without causing toner scattering when used as a charge control agent, having a clear hue, excellent image reproducibility, and an electrophotographic functional component containing the same.

  In order to form an image by attaching the toner to a desired position, it is necessary to control the charge amount of the toner.

  In a typical electrophotographic system, a charge is imparted to the toner by frictional charging. However, the toner triboelectric charge is influenced by many factors such as the toner chemical composition, toner particle size, resistivity, dielectric constant, friction partner, friction strength, etc. is not.

  In recent years, as a method for controlling the charge amount of toner, a means for adding a charge control agent to an electrophotographic functional component in contact with the toner has been taken. For example, a urethane elastomer that forms an elastic layer containing a charge control agent has been proposed. (For example, patent document 1). Further, a developing roller is disclosed in which the outermost layer is formed of a polymer material containing a charge control agent (for example, Patent Document 2).

  However, since it is a charge control agent, there are problems such as poor dispersibility and compatibility with the main binder.

Special registration 3159156 page 2 Special registration 3324383 page 2

  It is an object of the present invention to make a positive charge control resin excellent in dispersibility and compatibility with a main binder capable of making an electrophotographic functional component in contact with a toner chargeable so as to be contrary to the polarity of the toner, and containing the same An electrophotographic functional component is provided.

  The present invention is a positively charged control resin characterized by being a copolymer obtained by polymerizing a monomer composition comprising a hydroxyl group-containing monomer represented by formula (1) and an amino group-containing monomer represented by formula (2) Further, the present invention relates to a functional part for electrophotography, which contains the positively chargeable control resin as a polyol which is a raw material of polyurethane.

（式中、Ｘは水素原子またはメチル基、Ｙは炭素数２〜６のアルキレン基）

(Wherein X is a hydrogen atom or a methyl group, Y is an alkylene group having 2 to 6 carbon atoms)

（式中、Ｘは水素原子またはメチル基、ＹはＯまたはＮＨ、Ｚは炭素数２〜６のアルキレン基、Ｒ¹Ｒ²は各々水素原子、酸基を除く置換基で置換可能な炭素数１乃至２０のアルキル基を示すかまたは、Ｒ¹及びＲ²が化学的に結合して炭素数４乃至２０の複素環基を形成しているか、Ｒ¹及びＲ²炭素原子以外に窒素原子、酸素原子又は／及びイオウ原子を構成原子と、且つ炭素数４乃至１９を有する環状構造を形成していても良い。）

(Wherein X is a hydrogen atom or a methyl group, Y is O or NH, Z is an alkylene group having 2 to 6 carbon atoms, R ¹ R ² is a carbon atom that can be substituted with a substituent other than a hydrogen atom or an acid group, respectively. Represents an alkyl group having 1 to 20 or R ¹ and R ² are chemically bonded to form a heterocyclic group having 4 to 20 carbon atoms, or a nitrogen atom in addition to R ¹ and R ² carbon atoms, (A cyclic structure having 4 to 19 carbon atoms and oxygen atoms and / or sulfur atoms as constituent atoms may be formed.)

  Furthermore, the present invention is a copolymer obtained by adding a monomer composition comprising a (meth) acrylic acid ester monomer represented by the formula (3) to the positive charge control resin as a copolymerization component. The present invention relates to a positive charge control resin and a functional part for electrophotography characterized by containing the positive charge control resin as a polyol which is a raw material of polyurethane.

（式中、Ｒ³は炭素数４以上のアルキル基、Ｒ⁴は水素原子またはメチル基を表わす。）

(Wherein R ³ represents an alkyl group having 4 or more carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.)

  The positively chargeable control resin of the present invention is excellent in dispersibility and compatibility with the main binder, and by evaluating the charge amount by measuring the inclined charge amount, the electrophotographic functional component in contact with the toner is contrary to the toner polarity. It was found that the charging property can be improved, and good charging property can be obtained. Also, good images could be obtained when applied to electrophotographic apparatus members.

  According to the study of the present inventor, in order to obtain a sufficient image density even in a high temperature and high humidity environment, the toner has a stable triboelectric chargeability as a method for controlling the charge amount of the toner in order to obtain a sufficient image density even in a high temperature and high humidity environment. In order to form an image by attaching the toner to a desired position, attention was paid to positively or negatively charging the electrophotographic functional component in contact with the toner in accordance with the polarity of the toner so as to be opposite to the toner polarity. .

  The present invention relates to a main binder that can positively charge a friction charging member by adding a charge control resin to an electrophotographic functional component that comes into contact with a negative toner, and can impart a stable triboelectric chargeability to the toner. The present invention provides a positively charged control resin excellent in dispersibility and compatibility and an electrophotographic functional component containing the same.

  According to the study of the present inventors, at least a hydroxyl group-containing monomer represented by the formula (1), an amino group-containing monomer represented by the formula (2), and (meth) acrylic acid represented by the formula (3) as necessary. It has been found that the use of a positively chargeable control resin characterized by being a copolymer obtained by polymerizing a monomer composition containing an ester monomer has a remarkable effect on chargeability.

（式中、Ｘは水素原子またはメチル基、Ｙは炭素数２〜６のアルキレン基）

(Wherein X is a hydrogen atom or a methyl group, Y is an alkylene group having 2 to 6 carbon atoms)

（式中、Ｘは水素原子またはメチル基、ＹはＯまたはＮＨ、Ｚは炭素数２〜６のアルキレン基、Ｒ¹Ｒ²は各々水素原子、酸基を除く置換基で置換可能な炭素数１乃至２０のアルキル基を示すかまたは、Ｒ¹及びＲ²が化学的に結合して炭素数４乃至２０の複素環基を形成しているか、Ｒ¹及びＲ²炭素原子以外に窒素原子、酸素原子又は／及びイオウ原子を構成原子と、且つ炭素数４乃至１９を有する環状構造を形成していても良い。）

(Wherein X is a hydrogen atom or a methyl group, Y is O or NH, Z is an alkylene group having 2 to 6 carbon atoms, R ¹ R ² is a carbon atom that can be substituted with a substituent other than a hydrogen atom or an acid group, respectively. Represents an alkyl group having 1 to 20 or R ¹ and R ² are chemically bonded to form a heterocyclic group having 4 to 20 carbon atoms, or a nitrogen atom in addition to R ¹ and R ² carbon atoms, (A cyclic structure having 4 to 19 carbon atoms and oxygen atoms and / or sulfur atoms as constituent atoms may be formed.)

（式中、Ｒ³は炭素数４以上のアルキル基、Ｒ⁴は水素原子またはメチル基を表す。）

(Wherein R ³ represents an alkyl group having 4 or more carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.)

  In the positive charge control resin of the present invention, representative examples of the hydroxyl group-containing monomer represented by the formula (1) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. Examples include (meth) acrylate, 3-hydroxypentyl (meth) acrylate, 3-hydroxyphenyl (meth) acrylate and the like. Two or more monomers can also be copolymerized. "(Meth) acrylate" means methacrylate or acrylate (hereinafter the same).

  In the positively chargeable control resin of the present invention, typical examples of the monomer having an amino group represented by the formula (2) include N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meta ) Acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, pN, N-dimethylaminophenyl (meth) acrylate, pN, N-diethylaminophenyl (meth) acrylate, pN, N-dipropylaminophenyl (meth) acrylate, pN, N-dibutylamino Phenyl (meth) acrylate, pN-laurylaminophenyl (meth Acrylate, pN-stearylaminophenyl (meth) acrylate, pN, N-dimethylaminobenzyl (meth) acrylate, pN, N-diethylaminobenzyl (meth) acrylate, pN, N-dipropylamino Benzyl (meth) acrylate, pN, N-dibutylaminobenzyl (meth) acrylate, pN-laurylaminobenzyl (meth) acrylate, pN-stearylaminobenzyl (meth) acrylate, acryloyloxymethylmorpholine, Examples include acryloyloxyethylmorpholine.

  Further, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, p- N, N-dimethylaminophenyl (meth) acrylamide, pN, N-diethylaminophenyl (meth) acrylamide, pN, N-dipropylaminophenyl (meth) acrylamide, pN, N-dibutylaminophenyl ( (Meth) acrylamide, pN-laurylaminophenyl (meth) acrylamide, pN-stearylaminophenyl (meth) acrylamide, pN, N-dimethylaminobenzyl (meth) acrylamide, pN, N-diethylaminobenzyl (Meta) a Rilamide, pN, N-dipropylaminobenzyl (meth) acrylamide, pN, N-dibutylaminobenzyl (meth) acrylamide, pN-laurylaminobenzyl (meth) acrylamide, pN-stearylaminobenzyl Examples include (meth) acrylamide. “(Meth) acrylamide” means methacrylamide or acrylamide (hereinafter the same). Two or more monomers can also be copolymerized.

  In the positively chargeable control resin of the present invention, the (meth) acrylic acid ester monomer represented by the formula (3) includes n-butyl (meth) acrylate, tert-butyl (meth) acrylate, and iso-butyl (meth) acrylate. , N-amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-nonyl Examples include (meth) acrylate, n-lauryl (meth) acrylate, n-tridecyl (meth) acrylate, n-stearyl (meth) acrylate, isobornyl (meth) acrylate and the like.

  The vinyl copolymer obtained by copolymerizing the hydroxyl group-containing monomer represented by the formula (1) contained in the positively chargeable control resin of the present invention is a vinyl monomer represented by the formula (1) with respect to all monomers constituting the copolymer. In an amount of 0.5 to 99.5% by mass. When the content is less than 0.5% by mass, the ratio of the hydroxyl group to the main binder decreases, so the effect of the positive charge control resin obtained by copolymerizing the hydroxyl group-containing monomer may be obtained depending on the binder. There are cases where it is not preferable. If it exceeds 99.5% by mass, the dispersion state of the positively chargeable control resin in the main binder may not be uniform, which is not preferable.

  The vinyl copolymer obtained by copolymerizing a vinyl monomer having an amino group of formula (2) contained in the positively chargeable control resin of the present invention is a vinyl of formula (2) with respect to all monomers constituting the copolymer. It contains 0.5 to 99.5% by mass of monomer. When the content is less than 0.5% by weight, the charge amount may be insufficient, which is not preferable. When the content exceeds 99.5% by weight, the dispersion state of the positive charge control resin in the main binder is not preferable. It is not preferable because it may be uneven.

  The copolymer obtained by copolymerizing the (meth) acrylic acid ester monomer of the formula (3) contained in the positively chargeable control resin of the present invention contains the monomer of the formula (3) with respect to all the monomers constituting the copolymer. 99.5 mass% or less is contained. When the content exceeds 99.5% by mass, the triboelectric charge amount may be insufficient, which is not preferable.

  The weight average molecular weight (Mw) of the positively chargeable control resin of the present invention is preferably 2000 to 500,000. If the weight average molecular weight (Mw) is less than 2000, it may bleed out over time, which is not preferable. When it exceeds 500,000, the dispersion state of the positively chargeable control resin in the main binder tends to be uneven, which is not preferable.

  The glass transition temperature (Tg) of the positive charge control resin of the present invention is preferably -100 to 180 ° C. If the glass transition temperature (Tg) is less than −100 ° C., it is not preferable because the adhesiveness is large and the friction coefficient may be large. When it exceeds 180 ° C., the dispersion state of the positively chargeable control resin in the main binder may not be uniform, which is not preferable.

  The amine value of the positively chargeable control resin of the present invention is preferably 5 to 450 mgKOH / g. If the amine value of the positive charge control resin is less than 5 mgKOH / g, the charge amount may be insufficient. If it exceeds 450 mgKOH / g, the charge control resin of the main binder The dispersion state is likely to be uneven, and the charge amount may be insufficient, which is not preferable.

  Examples of the copolymer component of the hydroxyl group-containing monomer represented by the formula (1) and the amino group-containing monomer represented by the formula (2) and the (meth) acrylate monomer represented by the formula (3) of the present invention include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn- Styrene derivatives such as hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl methyl ketone and vinyl Examples thereof include vinyl ketones such as ruhexyl ketone and vinyl isopropyl ketone. One of these may be used, or two or more may be used in combination.

  The polymerization method for obtaining the positively chargeable control resin of the present invention is not particularly limited, and examples thereof include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method. A solution polymerization method is preferable from the viewpoint that the reaction can be easily controlled, and the solvent is not particularly limited, but xylene, toluene, ethyl acetate, isobutyl acetate, isopropyl alcohol, methanol, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, dimethylformamide, or the like is used, and the ratio of the solvent to the monomer is not particularly limited, but it is preferably performed at 30 to 400 parts by mass of the monomer with respect to 100 parts by mass of the solvent.

  The polymerization initiator used for polymerizing the positively chargeable control resin of the present invention is not particularly limited, but includes t-butylperoxy-2-ethylhexanoate, cumyl perpivalate, t- Butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) ), Dimethyl 2,2′-azobis (2-methylpropionate), etc., and these may be used alone or in combination. It can be used Te.

  The polymerization initiator is used at a concentration of 0.05 to 30 parts by mass (preferably 0.1 to 15 parts by mass) with respect to 100 parts by mass of the monomer, and the reaction temperature is not particularly limited, and the solvent used Although it can set according to an initiator and a monomer, it is preferable to carry out at 40 to 150 degreeC.

  The electrophotographic functional member of the present invention contains polyurethane as a component. Polyurethane is a polymer having a urethane bond (—NH—COO—), and obtained by reaction of an isocyanate component (compound having an isocyanate group (—NCO)) and a polyol component (compound having a hydroxyl group (—OH)). It is what The functional member for electrophotography of the present invention contains the positively chargeable control resin of the present invention as a polyol component.

  The isocyanate component constituting the polyurethane of the present invention is not particularly limited, and not only general-purpose TDI, MDI, crude-MDI (polymeric MDI), and modified MDI, but also a special isocyanate may be used. Examples of the special isocyanate include 1,5-naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, transcyclohexane 1,4 diisocyanate, xylylene diisocyanate (XDI), hydrogenated-XDI, Hydrogenated-MDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4 -Isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate Sulfonates, include trimethyl hexamethylene diisocyanate, and they can be used also suitable. Moreover, the block type isocyanate of the structure which masked the isocyanate with the blocking agent can also be used. Block type isocyanate does not react at room temperature, and when heated to a temperature at which the blocking agent dissociates, the isocyanate group is regenerated.

  As the isocyanate component constituting the polyurethane of the present invention, a general polyol component as a polyurethane material can be used together with the positive charge control resin of the present invention. As a general polyol component as a material of polyurethane, for example, polyether polyol (PPG), polytetramethylene ether glycol (PTMG), THF-alkylene oxide copolymer polyol, polyester polyol, acrylic polyol, polyolefin polyol, ethylene -Partially saponified products of vinyl acetate copolymers, phosphate-based polyols, halogen-containing polyols, adipate-based polyols, polycarbonate-based polyols, polycaprolactone-based polyols, polybutadiene polyols, and the like can be suitably used.

  In the polyurethane reaction, a catalyst may be used to promote or control the reactivity.

  The choice of catalyst and the use of the appropriate amount and the reaction temperature at that time are extremely important and affect the reactivity. Typical catalysts include triethylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, triethylenediamine, dimethylaminoethanol, bis (2 -Dimethylaminoethyl) ether and the like, but not particularly limited.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by an Example. The structural formulas of the hydroxyl group-containing monomers A1 and A2 described in the examples are (4) and (5), and the structural formulas of the monomers B1, B2 and B3 having an amino group are (6), (7) and (8). (9), (10), (11), and (12) show structural formulas of (meth) acrylic acid ester monomers C1, C2, C3, and C4.

[Example 1]
Production of CCR1 :
2-hydroxyethyl methacrylate (A1) as a hydroxyl group-containing monomer and N, N-dimethylaminoethyl as a vinyl monomer having an amino group in a four-necked separable flask equipped with a stirrer, a cooler, a thermometer and a nitrogen introduction tube Acrylate (B1), methyl methacrylate (C4) as a (meth) acrylic acid ester monomer is charged in the amounts shown in Table 1, and as a solvent, 60 g of toluene, 20 g of methanol and 2,2′-azobis (2-methylbutyro) 4.0 g of nitrile) was added, stirred and subjected to solution polymerization for 8 hours under reflux with introduction of nitrogen. Then, CCR1 was obtained by drying under reduced pressure. The amine value, weight average molecular weight (Mw), and Tg of the obtained CCR1 were respectively determined by a fully automatic titration device (manufactured by Kyoto Electronics Co., Ltd.), GPC measurement (device: manufactured by Tosoh Corp., column: Showa Denko Co., Ltd.) And DSC measurement (Seiko Instruments Inc.).

Inclined charge measurement 5 g of CCR1 obtained and MDI (adjusted so that OH / NCO = 1) are further added to MEK to prepare a sample solution. The sample solution is uniformly coated on a SUS plate for measuring the inclined charge amount and heated to prepare a measurement sample plate. The charge amount was measured with a cascade type surface charge amount measuring device (manufactured by Toshiba Chemical Corporation) (FIG. 1). In a N / N (22 ° C., 55% RH) environment, a measurement sample plate is fixed to a fluororesin table with a gradient of 60 degrees, and a reference powder is poured from the inlet for 20 seconds to charge the measurement sample plate. The amount is measured (three points are taken for one measurement point, and the average value is the charge amount). In FIG. 1, 1 is a reference powder inlet, 2 is an inclined plate (sample stage), 4 is a tray, 5 is an insulating plate, 6 is an electrometer, and 7 is a meter connection terminal.

[Examples 2-3]
Production of CCR2, 3 :
CCRs 2 and 3 were obtained in the same manner as in Example 1 except that the charged amounts of A1, B1 and C4 were changed as shown in Table 1. The amine value, Mw, and Tg of the obtained CCR2 and 3 were measured in the same manner as in Example 1. The results are shown in Table 2. In the same manner as in Example 1, the charge amounts of CCRs 2 and 3 were measured. The results are shown in Table 3.

Example 4
Production of CCR4 :
CCR4 was prepared in the same manner as in Example 1 except that A1 was 2-hydroxyethyl acrylate (A2) as the hydroxyl monomer, B1 was N, N-dimethylaminopropylacrylamide (B2) as the vinyl monomer having an amino group. Got. The amine value, Mw, and Tg of the obtained CCR4 were measured in the same manner as in Example 1. The results are shown in Table 2. In the measurement of the inclined charge amount, the charge amount was measured in the same manner as in Example 1 except that MDI was changed to TDI. The results are shown in Table 3.

Example 5
Production of CCR5 :
CCR5 was obtained in the same manner as in Example 1 except that the charged amounts of A2, B2, and C4 were changed as shown in Table 1. The amine value, Mw, and Tg of the obtained CCR5 were measured in the same manner as in Example 1. The results are shown in Table 2. In the measurement of the inclined charge amount, the charge amount was measured in the same manner as in Example 1 except that CCR 5g was changed to CCR 3g and PPG 2g. The results are shown in Table 3.

Example 6
Production of CCR6 :
CCR6 was obtained in the same manner as in Example 1 except that B1 was changed to acryloyloxyethylmorpholine (B3) as a vinyl monomer having an amino group. The amine value, Mw, and Tg of the obtained CCR6 were measured in the same manner as in Example 1. The results are shown in Table 3.

Example 7
Production of CCR7 :
CCR7 was obtained in the same manner as in Example 1 except that the amounts of A1, B3, and C4 were changed as shown in Table 1. The amine value, Mw, and Tg of the obtained CCR7 were measured in the same manner as in Example 1. The results are shown in Table 2. In the measurement of the inclined charge amount, the charge amount was measured in the same manner as in Example 1 except that MDI was changed to TDI. The results are shown in Table 3.

Example 8
CCR8 was obtained in the same manner as in Example 1 except that the charged amounts of A1, B1, and C1 were changed as shown in Table 1. The amine value, Mw, and Tg of the obtained CCR8 were measured in the same manner as in Example 1. The results are shown in Table 2. The charge amount was measured in the same manner as in Example 1. The results are shown in Table 3.

Example 9
Production of CCR9 :
CCR9 was obtained in the same manner as in Example 1 except that the charged amounts of A1, B1, and C1 were changed as shown in Table 1. The amine value, Mw, and Tg of the obtained CCR9 were measured in the same manner as in Example 1. The results are shown in Table 2. The charge amount was measured in the same manner as in Example 1. The results are shown in Table 3.

Example 10
CCR10 was obtained in the same manner as in Example 1 except that the charged amounts of A1, B1, and C2 were changed as shown in Table 1. The amine value, Mw, and Tg of the obtained CCR10 were measured in the same manner as in Example 1. The results are shown in Table 2. The charge amount was measured in the same manner as in Example 1. The results are shown in Table 3.

Example 11
CCR11 was obtained in the same manner as in Example 1 except that the charged amounts of A2, B2, and C2 were changed as shown in Table 1. The amine value, Mw, and Tg of the obtained CCR11 were measured in the same manner as in Example 1. The results are shown in Table 2. In the measurement of the inclined charge amount, the charge amount was measured in the same manner as in Example 1 except that MDI was changed to TDI. The results are shown in Table 3.

Example 12
CCR12 was obtained in the same manner as in Example 1 except that the charged amounts of A2, B2, and C3 were changed as shown in Table 1. The amine value, Mw, and Tg of the obtained CCR12 were measured in the same manner as in Example 1. The results are shown in Table 2. In the measurement of the inclined charge amount, the charge amount was measured in the same manner as in Example 1 except that CCR 5g was changed to CCR 3g and PPG 2g. The results are shown in Table 3.

Example 13
CCR13 was obtained in the same manner as in Example 1 except that the charged amounts of A1, B3, and C1 were changed as shown in Table 1. The amine value, Mw, and Tg of the obtained CCR13 were measured in the same manner as in Example 1. The results are shown in Table 2. The charge amount was measured in the same manner as in Example 1. The results are shown in Table 3.

Example 14
CCR14 was obtained in the same manner as in Example 1 except that the amounts of A1, B3, and C3 were changed as shown in Table 1. The amine value, Mw, and Tg of the obtained CCR14 were measured in the same manner as in Example 1. The results are shown in Table 2.

  In the measurement of the inclined charge amount, the charge amount was measured in the same manner as in Example 1 except that MDI was changed to TDI. The results are shown in Table 3.

[Comparative Example 1]
In the gradient charge measurement, the charge charge was measured in the same manner as in Example 1 except that CCR1 was changed to polyether polyol (PPG). The results are shown in Table 3.

  When the positive charge control resin of the present invention is used, the proper charge amount is evaluated by comparison with the main binder for the sake of convenience by measuring the charge amount of inclination in FIG.

[Example 15; other embodiments]
When the positive charge control resin of the present invention is actually contained in an electrophotographic functional part and used, it is necessary to adjust an appropriate charge amount each time in correspondence with the actual machine.

  An example in which the conductive roller according to the present invention is used in an image forming apparatus will be described. Here, the description is made on the developing roller, but the present invention can also be applied to other roller type parts such as a charging roller or a transfer roller, a developing blade, and a cleaning blade. The image forming apparatus here is a laser printer using an electrophotographic process cartridge, and is equipped with a developing device having a developing roller.

  FIG. 2 shows an outline of one embodiment of the developing roller of the present invention. FIG. 2A is a schematic sectional view along the axis of the developing roller, and FIG. 2B is a view of the developing roller viewed from the axial direction. The developing roller shown in this figure has an elastic layer 114b formed on a cored bar 114a and an outermost layer 114c provided on the outer periphery thereof. The outermost layer 114C contains carbon black and a positively charged resin.

[Manufacture of developing roller 1]
A developing roller 1 containing a positive charge control resin in the surface layer of the present invention was produced in the following manner.

An 8 mm outer diameter metal core (manufactured by SUM) is placed concentrically in a cylindrical mold with an inner diameter of 16 mm, and a liquid conductive silicone rubber (manufactured by Toray Dow Silicone, Asker C hardness 35 degrees, volume resistivity 10 × 10 ⁹ Ωcm) is cast, placed in an oven at 130 ° C. and heat-molded for 20 minutes. After demolding, secondary vulcanization is performed in an oven at 200 ° C. for 4 hours, and an elastic layer having a thickness of 4 mm is placed around the core metal. Formed.

  Next, urethane paint (trade name: Nipponporan N5033, manufactured by Nippon Polyurethane Co., Ltd.) is diluted with methyl ethyl ketone so that the solid content concentration becomes 10% by mass, and the positive charge control resin CCR1 is added to 100 parts by mass of the solid content of the urethane paint. 10 parts by mass, carbon black (trade name: # 7360SB, manufactured by Tokai Carbon Co., Ltd.) as a resistance adjusting material, and urethane particles (trade name: Art Pearl C400, manufactured by Negami Kogyo Co., Ltd.) having an average particle size of 14 μm as a surface roughening material. 6 parts by mass) was added. It is obtained by adding 10 parts by mass of a curing agent (modified TDI, trade name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) to 100 parts by mass of the solid content of the urethane paint, and stirring the mixture in which each component is sufficiently dispersed. The coating layer is formed by dipping the coated paint on the previously molded elastic layer to a dry film thickness of 20 μm, drying in an oven at 80 ° C. for 15 minutes, and curing in an oven at 140 ° C. for 4 hours. A development roller 1 was obtained.

[Evaluation of developing roller 1]
The developing roller 1 obtained above is attached to an evaluation laser beam printer (having the same configuration as that shown in FIG. 3) using a one-component developer composed of a negatively chargeable non-magnetic toner, 32.5 ° C. × 80% After continuously printing 10,000 predetermined images (character pattern images) in an RH (HH) environment, the charge amount, image density, and fog of the toner adhering to the developing roller were evaluated. The results are shown in Table 4.

[Examples 16 and 17]
Development rollers 2 and 3 were produced and evaluated in the same manner as in Example 15 except that CCR3 and CCR9 produced in Examples 3 and 9 were used instead of CCR1. The results are shown in Table 4.

[Comparative Example 2]
A developing roller 4 was produced and evaluated in the same manner as in Example 15 except that CCR1 was not used. The results are shown in Table 4.

１）帯電量指数
現像ローラーに担持されたトナーを、所定形状を有する容器内に吸引し、この容器の電荷量の変化を容器に接続したクーロンメータで読み取り、且つ、吸引したトナーを測定した。吸引されたトナーの電荷量を吸引したトナー質量で除算することでトナーの帯電量を得た。比較例２で使用した現像ローラー４の帯電量を１００として、それぞれの現像ローラーの帯電量を帯電量指数として表した。
２）かぶり指数
白ベタ画像出力中にプリンターを停止し、感光体上に付着したトナーをテープではがしとり、反射濃度計（マクベス社製スペクトロアイ）にて基準に対する反射率の低下量（％）を測定し、かぶり量とした。比較例２のかぶり量を１００として、実施例１５〜１７のかぶり量をかぶり指数とした。

1) Charge amount index The toner carried on the developing roller was sucked into a container having a predetermined shape, the change in the charge amount of the container was read with a coulomb meter connected to the container, and the sucked toner was measured. The charge amount of the toner was obtained by dividing the charge amount of the sucked toner by the sucked toner mass. The charge amount of the developing roller 4 used in Comparative Example 2 was defined as 100, and the charge amount of each developing roller was expressed as a charge amount index.
2) Fog index The printer is stopped while the white solid image is output, the toner adhering to the photoconductor is peeled off with tape, and the reflectivity reduction amount (%) with respect to the reference with a reflection densitometer (Macbeth Spectroeye) Was measured as the fogging amount. The fog amount of Examples 15 to 17 was defined as the fog index, with the fog amount of Comparative Example 2 being 100.

It is the schematic of the apparatus utilized for the inclination charge amount measurement. It is a figure which shows the basic composition of the developing roller of this invention. It is a schematic block diagram which shows the laser beam printer provided with the developing roller of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photosensitive drum 10 Developing apparatus 11 Developer (one-component developer consisting of negatively chargeable non-magnetic toner)
DESCRIPTION OF SYMBOLS 11a Developer thin film 12 Developer container 13 Development area 16 Blade 18 Constant voltage power supply 19 Charging roller 24 Development roller 24a Core metal 24b Elastic layer 24c Surface layer 25 Supply roller 25a Core metal 25b Elastic layer 25c Surface layer 114 Development roller 114a Core Gold 114b Elastic layer 114c Surface layer L Laser beam

Claims (3)

A positively charged control resin characterized by being a copolymer obtained by polymerizing a monomer composition comprising a hydroxyl group-containing monomer represented by the formula (1) and an amino group-containing monomer represented by the formula (2) .

(Wherein X is a hydrogen atom or a methyl group, Y is an alkylene group having 2 to 6 carbon atoms)

(Wherein X is a hydrogen atom or a methyl group, Y is O or NH, Z is an alkylene group having 2 to 6 carbon atoms, R ¹ R ² is a carbon atom that can be substituted with a substituent other than a hydrogen atom or an acid group, respectively. Represents an alkyl group having 1 to 20 or R ¹ and R ² are chemically bonded to form a heterocyclic group having 4 to 20 carbon atoms, or a nitrogen atom in addition to R ¹ and R ² carbon atoms, (A cyclic structure having 4 to 19 carbon atoms and oxygen atoms and / or sulfur atoms as constituent atoms may be formed.) The positively chargeable control resin according to claim 1, which is a copolymer obtained by polymerizing a monomer composition comprising a (meth) acrylic acid ester monomer represented by formula (3).

(Wherein R ³ represents an alkyl group having 4 or more carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.)   A functional member for electrophotography containing a polyurethane as a component, comprising the positive charge control resin according to claim 1 or 2 as a polyol which is a raw material of polyurethane.

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