CN100381940C - Polyhydroxyalkanoate containing amide group, sulfonic group, and sulfonate ester group, method for producing the same, and charge control agent, toner, image forming method, and image forming apparatu - Google Patents

Abstract

A polyhydroxyalkanoate containing in a molecule at least one unit represented by the chemical formula (1). The polyhydroxyalkanoate is a biodegradable plastic with enhanced melt-processability and exhibits excellent charging stability, high chargeability, and enhanced dispersibility when used as a charge control agent of a toner in an electrophotographic process. (R denotes -A1(-SO2R1)x. R1 is selected from OH, a halogen atom, ONa, OK, and OR1a. R1a and A1 are selected from a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, and a substituted or unsubstituted heterocyclic structure. Further, m and x are integers selected from 1 to 8, and when two or more units exist, each of R, R1, R1a, A1, m, and x is defined as above independently for each of the units.

Description

Polyhydroxyalkanoatefrom, its preparation method and charge adjusting agent, toner, formation method and imaging device

Technical field

The present invention relates to a kind of new polyhydroxyalkanoatefrom (hereinafter referred is " PHA ") that contains sulfonic acid group and preparation method thereof.More particularly, the present invention relates to a kind of sulfonic acid group that contains as polyhydroxyalkanoatefrom of hydrophilic radical or polar group and preparation method thereof.

In addition, the invention still further relates to a kind of charge adjusting agent that is used in the recording process, this recording process for example uses electrofax, static or magnetic recording method, also relates to static charge image developing toner, uses the formation method of this toner and uses the imaging device of this toner.

Background technology

[related background art of relevant resin]

(problem of the resin that uses in the prior art)

Usually, with plastics, for example polyethylene terephthalate (PET) resin, vibrin, vestolit and polyolefin resin are used in the various application, as the moulding article of inserting such as food container, beverage bottle, cosmetics containers and flower and plant jar etc.

Most of these plastic products all are dropped after using.Usually, to this plastic waste material burn, processing such as recovery.But the burning of waste product can produce a large amount of burning energy.Therefore, the burning of waste product has following point: the permanance of incinerator under combustion temperatures, disposal cost, harmful gas that burns that high temperature resistant incinerator needs are installed, the air pollution that produces as carbon monoxide, sulfocompound, chlorine He bioxin etc.In addition, in recycling, waste product will keep to semipermanent and not be decomposed, and is handling on the field as waste deposits.Therefore, this sediment becomes the refuse problem of social concerns.And, when being present in the soil, it still is waste product, therefore also can cause other problem.For example, open up wasteland the soil in zone and can not stablize, and environment and the multiple biology opened up wasteland in zone and the peripheral region thereof also can affect adversely.

In order to address these problems, in recent years, the biodegradable resin in this area has caused people's attention.Herein, term " biodegradable " resin " when referring to as material and general purpose plastics have essentially identical physical property, and the resin that after microbiological treatment, can decompose rapidly under such as soil, compost, active sludge and water environment.In other words, biodegradable resin can decompose well, and some resins can be decomposed into carbon dioxide and water at last.

Usually, in order to satisfy above-mentioned needs, except that specific polyesters biodegradable resin, blended resin composition also is known as biodegradable resin.This class blended resin composition comprises starch-ethylene/vinyl alcohol copolymer resin, ethylene/vinyl alcohol copolymer resin-aliphatic polyester resin, and the blended resin composition of aliphatic polyester resin-polyolefin resin.These resins or resin combination can be applied in this area by the processing mode that is applicable to multiple application.But, a kind of resin of excellence is not also proposed, for example, its physical property, have good balance between the required processibility when handling required biodegradability in back and preparation in multiple necessity.

(polyhydroxyalkanoatefrom (PHA))

In recent years, a kind of method of the environmental pollution that brings as refuses such as solving moulded goods has proposed to use the synthetic biodegradable resin of microorganism as moulding material.For example, as the biodegradable resin that comes from microorganism, known have a polyhydroxyalkanoatefrom (hereinafter it can be abbreviated as PHA), for example, poly--3-hydroxyl n-butyric acie (hereinafter it can be abbreviated as PHB), or the multipolymer of positive valeric acid of 3-hydroxyl (hereinafter it can be abbreviated as 3HV) and 3-hydroxyl n-butyric acie (hereinafter it can be abbreviated as 3HB) (hereinafter, this multipolymer can be abbreviated as PHB/V), polysaccharide, for example, bacteria cellulose and amylopectin, and polyaminoacid, for example poly-gamma-glutamic acid and polylysine.In these materials, with regard to producing conventional plastics, especially can prepare different types of product with PHA by methods such as melt-processed.In addition, because PHA has excellent biocompatibility, so it is also expected as medical flexible material.

Existing up to now report, many microorganisms can both produce PHA, and can build up PHA in cell.People are known, depend on microorganism type used in this preparation, nutrient culture media composition, condition of culture etc., and the PHA that makes can have different The Nomenclature Composition and Structure of Complexes.Up to now, people are mainly from improving the viewpoint of physical property, and the The Nomenclature Composition and Structure of Complexes of how controlling prepared PHA is studied.Especially studied the biological synthesis process that has the monomeric unit acquisition PHA of simpler construction by polymerization, this monomeric unit comprises 3HB, 3HV, 3-hydroxy-n-caproic acid (hereinafter being called 3HHx) and 4-hydroxyl n-butyric acie (hereinafter being called 4HB), and has reported with multiple microorganism and prepare PHA.But the PHA (hereinafter it can be abbreviated as scl-PHA) that contains the long 3-hydroxyl alkane acid of short chain ester units has close fusing point and heat decomposition temperature, and the trend of the thermal decomposition of being easy to is arranged.Therefore, extruding plasticity is then not enough.And PHB has high crystalline, little ductility etc.; Therefore, engineering properties is tending towards descending.

Recently, people have carried out strong research to the polyhydroxyalkanoatefrom (hereinafter can be abbreviated as mcl-PHA) of the middle chain length 3-hydroxyl alkane acid ester units that contains 4-12 the carbon atom of having an appointment.Confirmed to use no cycloaliphatic hydrocarbon, sad, caproic acid, gluconic acid sodium salt etc. to prepare mcl-PHA as carbon source.But these mcl-PHA have low melting point, and then becoming viscosity more than 50 ℃, also can soften.

Simultaneously, above-mentioned PHA is the PHA that contains monomeric unit, this monomeric unit only has alkyl group on side chain (hereinafter can be called routine-PHA), or for similarly other PHA is (for example with it, on side chain, has alkenyl, this alkenyl contains two keys in non-end portion), these two kinds of materials all are the beta oxidations by hydrocarbon etc., or by using microorganism synthetic by sugared synthetic fatty acid.In the present circumstance, when being considered as the plastics widespread use, the physical property of these PHA can't meet the demands.

In order to enlarge the application of PHA, it is very important that broad research is carried out in the improvement of its physical property.Therefore, the PHA that contains the monomeric unit with different structure is developed and studies also be absolutely necessary.On the other hand, having introduced substituent " conventional PHA " on its side chain estimates to bring progress, become " functional polymer " with exceedingly useful function and character, wait according to the physical property of hope and to select the substituting group that is introduced into, the function of " functional polymer " and character derive from the character of the groups such as substituting group of introducing.That is to say, the R and D excellence, to make PHA functional and that biodegradability combines also be important purpose.Substituent example can comprise: the group (phenyl, phenoxy group etc.) with aromatic ring; Ester group; Part has unsaturated group (alkenyl and alkadienyl), the especially allyl of two keys endways; Cyano group; Halogenated hydrocarbons; And epoxide.The preparation of report contains phenyl that phenyl or part replace and comprises as the example of substituent PHA: preparation contains the PHA of 3-hydroxyl-5-phenylpentanoic acid unit as substrate to use the 5-phenylpentanoic acid; Use 5-(4 '-tolyl) valeric acid to prepare the PHA that contains 3-hydroxyl-5-(4 '-tolyl) valeric acid unit as substrate; Prepare the PHA that contains 3-hydroxyl-5-(2 ', 4 '-dinitrophenyl) valeric acid unit and 3-hydroxyl-5-(4 '-nitrobenzophenone) valeric acid unit as substrate with use 5-(2 ', 4 '-dinitrophenyl) valeric acid.The preparation of report contains phenoxy group that phenoxy group or part replace and comprises as the example of substituent PHA: use 11-phenoxy group undecanoic acid to prepare the pha copolymer of 3-hydroxyl-5-phenoxy group valeric acid and 3-hydroxyl-9-phenoxy group n-nonanoic acid as substrate; The PHA that contains 3-hydroxyl-4-phenoxybutyhc unit and 3-hydroxyl-6-phenoxy group caproic acid unit by the preparation of 6-phenoxy group caproic acid; The PHA that contains 3-hydroxyl-4-phenoxybutyhc unit, 3-hydroxyl-6-phenoxy group caproic acid unit and 3-hydroxyl-sad unit of 8-phenoxy group by the sad preparation of 8-phenoxy group; And the PHA that contains 3-hydroxyl-5-phenoxy group valeric acid unit and 3-hydroxyl-7-phenoxy group enanthic acid unit by the preparation of 11-phenoxy group undecanoic acid.In addition, also report the PHA homopolymer that contains 3-hydroxyl-5-(single fluorophenoxy) valerate (3H5 (MFP) P) unit and 3-hydroxyl-5-(two fluorophenoxies) valerate (3H5 (DFP) P) unit and contained 3H5 (MFP) P unit at least or the PHA homopolymer of 3H5 (DFP) P unit.Its effect comprises high-melting-point and gives stereospecicity and water proofing property and keep the ability of good processibility simultaneously.In addition, except the PHA that above-mentioned fluorin radical replaces, also studied the PHA that cyano group or nitro replace.For example, reported and used sad and preparation contains the 3-hydroxyl to cyano-benzene oxygen caproic acid or the 3-hydroxyl p-nitrophenyl oxygen base caproic acid PHA as monomeric unit as substrate to cyano-benzene oxygen caproic acid or p-nitrophenyl oxygen base caproic acid.These PHA of report are different from the PHA that has alkyl on the common side chain, and wherein various PHA have aromatic ring on side chain, therefore the polymkeric substance that helps obtaining to have the physical property that comes from aromatic ring.In addition, as the example of the unconventional-PHA with cyclohexyl, also reported by cyclohexyl butyric acid or cyclohexyl valeric acid to prepare PHA.

Recently,, be not limited to only change physical property, also carried out by having the PHA of suitable functional group and use this functional group to develop the research of new function on the preparation side chain as a new type. Polymer, 41,1703-1709 (2000)In disclose and using the 10-undecenoic acid to contain 3-hydroxyl alkenoic acid as monomeric unit and after the side chain terminal place has the PHA of unsaturated link as substrate preparation, its dissolubility to solvent changes when PHA is converted into corresponding 3-hydroxyl alkane acid, and this 3-hydroxyl alkane acid is to utilize the oxidation reaction of potassium permanganate synthetic, and it also has glycol at the side chain terminal place.Therefore, it dissolves in polar solvent, and for example (80/20, v/v) mixed solvent, and in the dimethyl sulfoxide, but be insoluble to non-polar solvent is for example in chloroform, tetrahydrofuran and the acetone for methyl alcohol, acetone-water. Macromolecular Chemistry, 4,289-293 (2001)In disclose after using the 10-undecenoic acid preparation contains the 3-hydroxyl-PHA of 10-undecenoic acid as monomeric unit as substrate, utilize the potassium permanganate oxidation cracking reaction synthetic, contain 3-hydroxyl-9-carboxyl n-nonanoic acid and be improved as the decomposition rate of the PHA of monomeric unit.

[related background art of toner]

It is up to the present, known that many methods are arranged is the methods that can be used in the electrophotography.Usually, use photoconductive material and adopt distinct methods to go up and form electrostatic latent image in image-bearing member (light activated element), use toner to make this image development become visual picture (toner image) subsequently, according to particular requirement toner image is transferred to offset medium, for example on the paper, pass through then to heat and/or suppress toner image on offset medium, thus the image that acquisition is duplicated.As making electrostatic latent image form the method for visible image, known in the art have cascade methods such as (cascade development), magnetic brush development, pressure develoment of developing.Also known another kind of method, this method use magnetic color tuner and tube core place have the rotation developing cylinder of magnetic pole, and make magnetic color tuner diffuse to light activated element from developing cylinder by magnetic field.

During latent electrostatic image developing can with developing method comprise two component development methods of two component developers that use is made up of toner and carrier and use the single component development method of the monocomponent toner that does not adopt carrier and only form by toner.The coloured fine grained that is commonly referred to as toner is by adhesive resin and colorant as solvent, and compositions such as optional charge adjusting agent, Magnaglo.

(charge adjusting agent)

In order to give toner with charge transfer, can utilize the charging property of adhesive resin itself and needn't use any charge adjusting agent, but adhesive resin charged less stable in time, and moisture-proof is also relatively poor, therefore be difficult to obtain the picture quality of being satisfied with.Therefore, for the electric charge that carries out toner keeps and electric charge control, to add charge adjusting agent usually.

Charge adjusting agent known in the art now comprises, as the metal complex of azo dyes metal complex, aromatic dicarboxylic acid metal complex and the salicyclic acid derivatives of the reagent with negative friction electrical property (negative charge correctives).In addition, known positive charge correctives has aniline black byestuffs, kiton colors, organo-tin compound, for example, and dissimilar dibutyl tin oxide (dibutyltin oxide) quaternary ammonium salt, or the like.But, in some cases, depend on the composition of toner, contain wherein that any toner as charge adjusting agent might not all satisfy the desired quality characteristic of toner, for example charging property and stability in time.

For example, be the toner of the azo dyes metal complex of negative charge correctives for containing known, the size of its quantity of electric charge is on the reasonable levels.But, because the azo dyes metal complex is a crystalline compounds, all have low-molecular-weight, therefore, depend on the type of the adhesive resin that will combine with charge adjusting agent, this complex compound may have relatively poor dispersibility.In this case, the negative charge correctives can not be evenly distributed in the adhesive resin, and then the charge amount distribution of gained toner also lacks acutance greatly, so the gained image may have low shade of gray (gradation), demonstrates relatively poor imaging performance.Therefore and the azo dyes metal complex has specific tone, and under existence conditions, it is in the toner of limited tone at center that this complex compound can only be applied to have with black.Produce serious problem when this complex compound is used for color toner, because this complex compound does not have the sharpness of colorant, and this is that to form the image that is starved of tone necessary.

Example as almost colourless negative charge correctives, can enumerate the aromatic dicarboxylic acid metal complex, but this complex compound is not colourless fully, and because this complex compound is a crystalline compounds, and all have low-molecular-weight, therefore it demonstrates low dispersed in some cases.

For aniline black byestuffs and kiton colors as the positive charge correctives, this dyestuff this as coloured, therefore under existence conditions, it is in the toner of limited tone at center that this dyestuff can only be applied to have with black.When the toner that contains this dyestuff used in the continuous compound rate process, time stability may be relatively poor.Toner by traditional quaternary ammonium salt preparation may demonstrate not enough moisture-proof, and time stability may be relatively poor, can not provide the image with good quality in the repeated use process.

In recent years, from the viewpoint of environmental protection, the security that reduces waste product and raising waste product has become the problem that the whole world is paid close attention to.These problems are present in the electrofax field equally.Along with being extensive use of of imaging device, printer paper, discarded toner and the processing of copy paper are also increased year by year, from the viewpoint of global environmental protection, the security of these waste products also is an important problem.

Consider this point, people study the polymer charge correctives.The example of polymer charge correctives comprises USP 4,480,021, disclosed compound among USP 4,442,189 and the USP 4,925,765.And, use styrene and/or α-Jia Jibenyixi usually and have alkyl (methyl) acrylate of sulfonic acid group or the multipolymer of alkyl (methyl) acrylic acid amides, as used polymer charge correctives in the toner that shows the negative charge charging property.Because these materials are colourless therefore favourable, but then should add in a large number in order to reach the aimed charge amount.

Therefore, these compounds do not have the enough performances as charge adjusting agent, and have problems at aspects such as the quantity of electric charge, charged rising characteristic, time stability, environmental stabilities.Consider charge adjusting agent itself and be used for the compound of synthetic this charge adjusting agent or the function of organic solvent and the influence of human body and environment, be starved of a kind of charge adjusting agent, it can obtain the synthesis technique of safer compound, safer and milder, and uses the organic solvent of less amount.But, yet there are no this aimed charge correctives and synthetic method thereof are reported.Therefore, also have very big space further to improve the function of charge adjusting agent, and to the further influence of environmental protection.

[other prior art document]

Use the microorganism of describing among USP 6,521,429 and the USP 6,586,562 among the present invention.In addition, J.Biol.Chem., 218, the description of relevant nutrient culture media also is bonded to herein among the 97-106 (1956).And, as correlation technique of the present invention, also having other document, it relates to by obtain method (J.Chem.Soc., Perkin.Trans.1,806 (1973) of carboxylic acid with oxygenant oxidation cracking carbon-to-carbon double bond; Org.Synth., 4,698 (1963); J.Org.Chem., 46,19 (1981); And J.Am.Chem.Soc., 81,4273 (1959), and synthetic (Macromolecules, 29, the 1762-1766 (1996)) of 5-(4-aminomethyl phenyl) valeric acid.

Summary of the invention

The research of the new function of exploitation biodegradable resin PHA is attempted, but relevant report seldom.Especially, the 3-hydroxybutyric acid has in natural surroundings the advantage that can be decomposed fully by microorganism; But because its high crystalline and rockiness, therefore melt-processed property is not enough.So just wish to have a kind of PHA that has improved melt-processed property.

The invention provides a kind of PHA and derivant thereof of new introducing hydrophilic radical sulfonic acid group, it is in order to improve melt-processed property, also to provide the method for preparing this new PHA.In addition, PHA of the present invention is owing to its water wettability has excellent biocompatibility; Therefore, can expect that also it is used for medical treatment etc. uses as flexible member.

In addition; a further object of the invention provides a kind of charge adjusting agent that can be electronegative; it is more favourable to environmental protection etc.; and its dispersiveness that has high-performance (time stability and the very high environmental stability of large charge amount, charged rising fast, excellence) and improve, a kind of formation method and imaging device that contains the static charge image developing toner of this charge adjusting agent and use this static charge image developing toner is provided.

The present inventor is devoted to research and develop the PHA of new introducing hydrophilic radical, and this hydrophilic radical is considered to can be used for improving melt-processed property, and the result has obtained following discovery.Just, the present inventor finds that above-mentioned PHA has the excellent properties as charge adjusting agent, and as safe as a house to human body and environment.In addition, when the static charge image developing toner that will contain above-mentioned charge adjusting agent was used for having the imaging device of certain developing system, it had brought into play significant superiority.

The invention provides a kind of polyhydroxyalkanoatefrom, it is characterized in that comprising in its molecule the unit of at least one chemical formula (1) representative.

(R represents-A ₁(SO ₂R ₁) _xR ₁Be selected from OH, halogen atom, ONa, OK and OR _1aR _1aAnd A ₁Be selected from and replace or unsubstituted aliphatic hydrocrbon structure, replacement or unsubstituted aromatic ring structure and replacement or unsubstituted heterocycle structure.In addition, m and x are the integer that is selected from 1-8, and when having two or more unit, the R of each unit, R ₁, R _1a, A ₁, m and x independently of one another as above-mentioned definition.)

In addition, the invention provides a kind of preparation method of polyhydroxyalkanoatefrom, it is characterized in that comprising the steps: to prepare the polyhydroxyalkanoatefrom matrix of the unit that contains chemical formula (22) representative and the amines of at least one chemical formula (23) representative; Obtain containing the polyhydroxyalkanoatefrom of the unit of chemical formula (1) representative with condensation reaction by this polyhydroxyalkanoatefrom matrix and this amines.

(1 for being selected from the integer of 1-8, R ₁₈Be selected from H atom, Na atom and K atom, and when having two or more unit, 1 and R of each unit ₁₈Independently of one another as above-mentioned definition.)

H ₂N-A ₃(-SO ₂R ₁₉) _y (23)

(R ₁₉Be selected from OH, halogen atom, ONa, OK and OR _19aAnd, R _19aAnd A ₃Be selected from and replace or unsubstituted aliphatic hydrocrbon structure, replacement or unsubstituted aromatic ring structure and replacement or unsubstituted heterocycle structure.Y is the integer that is selected from 1-8, and when having two or more unit, the R of each unit ₁₉, R _19a, A ₃With y independently of one another as above-mentioned definition.)

(R represents-A ₁(SO ₂R ₁) _xR ₁Be selected from OH, halogen atom, ONa, OK and OR _1aR _1aAnd A ₁Be selected from and replace or unsubstituted aliphatic hydrocrbon structure, replacement or unsubstituted aromatic ring structure and replacement or unsubstituted heterocycle structure.In addition, m and x are the integer that is selected from 1-8, and when having two or more unit, the R of each unit, R ₁, R _1a, A ₁, m and x independently of one another as above-mentioned definition.)

In addition, the present invention also provides a kind of charge adjusting agent that is used to control the electriferous state of powder, it is characterized in that being included in the polyhydroxyalkanoatefrom of the unit that contains at least one chemical formula (1) representative in the molecule.

(R represents-A ₁(SO ₂R ₁) _xR ₁Be selected from OH, halogen atom, ONa, OK and OR _1aR _1aAnd A ₁Be selected from and replace or unsubstituted aliphatic hydrocrbon structure, replacement or unsubstituted aromatic ring structure and replacement or unsubstituted heterocycle structure.In addition, m and x are the integer that is selected from 1-8, and when having two or more unit, the R of each unit, R ₁, R _1a, A ₁, m and x independently of one another as above-mentioned definition.)

In addition, the present invention also provides a kind of static charge image developing toner, it is characterized in that comprising at least adhesive resin, colorant and charge adjusting agent of the present invention.

In addition, the present invention also provides a kind of formation method, it is characterized in that comprising at least: apply voltage from the outside to charge member, use so that the charged charge step of electrostatic latent image load-carrying unit; On charged electrostatic latent image load-carrying unit, form the sub-image image-forming step of electrostatic image; Make electrostatic image development with static charge image developing toner, thereby form the development step of toner image on the electrostatic latent image load-carrying unit, wherein this static charge image developing toner is a static charge image developing toner of the present invention; Toner image on the electrostatic latent image load-carrying unit is transferred to transfer step on the recording materials; Photographic fixing step with hot this toner image of photographic fixing on recording materials.

In addition, the present invention also provides a kind of imaging device, it is characterized in that comprising at least: apply voltage from the outside to charge member, use so that the charged charging device of electrostatic latent image load-carrying unit; On charged electrostatic latent image load-carrying unit, form the sub-image imaging device of electrostatic image; Make electrostatic image development with static charge image developing toner, thereby form the developing apparatus of toner image on the electrostatic latent image load-carrying unit, wherein this static charge image developing toner is a static charge image developing toner of the present invention; Toner image on the electrostatic latent image load-carrying unit is transferred to transfer device on the recording medium; Fixing device with hot this toner image of photographic fixing on recording medium.

According to the present invention, it provides a kind of new PHA, contains the unit with sulfonic acid group in its molecule, and this sulfonic acid group is water wettability or polar group, and the preparation method of the derivant and this new PHA that contain amido link on its side chain also is provided.This new PHA is owing to its water wettability has excellent melt-processed property and biocompatibility; Therefore, can expect that also it is used for medical treatment etc. uses as flexible member.

In addition, according to the present invention, by in the static charge image developing toner composition, adding the polyhydroxyalkanoatefrom of one or more chemical formulas (1) representative as charge adjusting agent, a kind of static charge image development toner can be provided, this toner charging property excellence, the dispersiveness of compound and consumption character (spent property) are improved in the toner resin, can not form the image fog, have excellent transfer printing when from imaging device, exporting, and highly be applicable to electrophotographic processes.And the charge adjusting agent that uses among the present invention is colourless or light, therefore can require to select arbitrarily colorant according to the tone of color toner.This charge adjusting agent also has this characteristics: it does not hinder the intrinsic tone in dyestuff and the pigment.In addition, therefore static charge image developing toner high safety of the present invention and biodegradable need not burn processing.From environmental protection, for example prevent the viewpoint of air pollution and global warming, toner of the present invention has very valuable industrial effect.

As mentioned above, polyhydroxyalkanoatefrom of the present invention has the basic skeleton structure of biodegradable resin.Therefore, can be according to identical with conventional plastics, but the mode different with the synthetic polymer of petroleum derivation, adopt methods such as melt-processed, prepare multiple product with this polyhydroxyalkanoatefrom, the peculiar property of this polyhydroxyalkanoatefrom is, this polyhydroxyalkanoatefrom can be by biolysis, and can be attached in the natural material cycle.Therefore, because this polyhydroxyalkanoatefrom does not need burning disposal, for the viewpoint that prevents air pollution and global warming, this polyhydroxyalkanoatefrom still is effective material, and this polyhydroxyalkanoatefrom also can be used as environmentally-friendly plastic.

And polyhydroxyalkanoatefrom of the present invention demonstrates as the characteristic of the height excellence of charge adjusting agent with to the tight security of human body and environment.In addition, when the static charge image developing toner that contains this charge adjusting agent is used in the imaging device with certain developing system, also can obtain significant effect.

That is to say, the invention provides a kind of static charge image developing toner that contains the charge adjusting agent of above-mentioned polyhydroxyalkanoatefrom and contain this charge adjusting agent.In addition, the present invention also provides a kind of formation method that uses this static charge image developing toner, comprising: apply voltage from the outside to charge member, make electrostatic latent image load-carrying unit uniform charged, form the charge step and the sub-image image-forming step of sub-image then; On the electrostatic latent image load-carrying unit, form the development step of toner image; By or by the intermediate transfer element, the toner image on the electrostatic latent image load-carrying unit is transferred to transfer step on the recording medium; Heat the hot photographic fixing step of toner image on recording medium with passing through.The present invention also provides a kind of imaging device, and it comprises each device corresponding to above steps, that is, and and charging device, sub-image imaging device, developing apparatus, transfer device and heat-fixing device.

The accompanying drawing summary

Fig. 1 is the synoptic diagram of the imaging device of use in embodiment 25-embodiment 30 and the comparative example 7-comparative example 12.

Fig. 2 is two component developers that use in embodiment 25-embodiment 30 and the comparative example 7-comparative example 12, the cut-open view of the critical piece of developing apparatus.

Have the synoptic diagram that toner utilize the imaging device of mechanism again of Fig. 3 for using in embodiment 31-embodiment 34 and the comparative example 13-comparative example 15.

Fig. 4 is the monocomponent toner that uses in embodiment 31-embodiment 34 and the comparative example 13-comparative example 15, the cut-open view of the critical piece of developing apparatus.

Fig. 5 is the decomposition diagram of the fixing device critical piece that uses in the embodiment of the invention.

Fig. 6 is the amplification view of the critical piece that uses in the embodiment of the invention, and it has shown the not film state of the fixing device of operation.

Fig. 7 has shown the synoptic diagram of the discharging quantity of electric charge measurement mechanism that is used to measure the toner charge amount.

Fig. 8 illustrates the FT-IR spectrum of resulting polymers in the embodiment A-1.

Fig. 9 illustrates the FT-IR spectrum of resulting polymers in the Embodiment B-1.

Preferred forms of the present invention

The target P HA of chemical formula among the present invention (1) representative is made by the sulfamate compounds thing reaction that the PHA of the 3-hydroxyl-ω-carboxyl alkanoate unit that contains chemical formula (22) representative and chemical formula (23) are represented.

(1 for being selected from the integer of 1-8, R ₁₈Be H atom, Na atom or K atom, and when having two or more unit, 1 and R of each unit ₁₈Independently of one another as above-mentioned definition.)

H ₂N-A ₃(-SO ₂R ₁₉) _y (23)

(R ₁₉Be selected from OH, halogen atom, ONa, OK and OR _19aAnd, R _19aAnd A ₃Be selected from and replace or unsubstituted aliphatic hydrocrbon structure, replacement or unsubstituted aromatic ring structure and replacement or unsubstituted heterocycle structure.Y is the integer that is selected from 1-8, and when having two or more unit, the R of each unit ₁₉, R _19a, A ₃With y independently of one another as above-mentioned definition.)

(preparation method who contains the PHA of unit shown in the chemical formula (22))

The PHA of chemical formula (22) representative is that the oxidation by two keys parts of a kind of PHA makes, and this PHA contains 3-hydroxyl-ω-chain acid ester unit that chemical formula (24) is represented.

(p is the integer that is selected from 0-7, and when having two or more unit, the p of each unit is independently as above-mentioned definition.)

Use oxygenant to comprise by the example that above-mentioned this carbon-to-carbon double bond obtains the known method of carboxylic acid: the method (J.Chem.Soc. that uses permanganate by oxidative cracking reaction, Perkin.Trans.1,806 (1973)), use the method (Org.Synth. of dichromate, 4,698 (1963)), use the method (J.Org.Chem. of periodate, 46,19 (1981)), use the method (Japanese Unexamined Patent Publication No No.S59-190945) of nitric acid and the method (J.Am.Chem.Soc. of use ozone, 81,4273 (1959)).In addition, for PHA, above-mentioned Macromolecular chemistry, 4, a kind of method that obtains carboxylic acid is disclosed among the 289-293 (2001): use potassium permanganate as oxygenant, the carbon-to-carbon double bond on the PHA side chain terminal is reacted.Similarly method can be used among the present invention equally.

As the permanganate as oxygenant, commonly used is potassium permanganate.Because oxidative cracking reaction is stoichiometric reaction, therefore with respect to the unit of 1 mole of chemical formula (24) representative, the use amount of permanganate is generally 1 molar equivalent or more, preferred 2-10 molar equivalent.

For reaction system is under the acid condition, use multiple mineral acid and organic acid usually, for example, sulfuric acid, hydrochloric acid, acetate and nitric acid.But when using such as sulfuric acid, nitric acid and hydrochloric acid sour, the ester bond on the PHA main chain is cleaved, and therefore the danger that molecular weight is reduced arranged.Therefore, preferably use acetate.With respect to the unit of 1 mole of chemical formula (24) representative, the use amount of acid is generally 0.2-2,000 molar equivalent, preferred 0.4-1,000 molar equivalent.If should amount less than 0.2 molar equivalent, productive rate step-down then, and if should amount surpass 2,000 molar equivalents, be accessory substance then by sour analytical product.Therefore, both of these case is not preferred.In addition, crown ether can be used for accelerated reaction.In this case, crown ether and permanganate form complex compound, thereby produce the effect of intensified response activity.Normally used crown ether comprises dibenzo-18-hat-6-ether, two ring-18-hat-6-ethers and 18-hat-6-ether.With respect to 1 mole of permanganate, the use amount of wishing crown ether usually is the 0.005-2.0 molar equivalent, preferred 0.01-1.5 molar equivalent.

In addition, be not particularly limited, as long as it is the solvent of non-activity in reaction for the solvent in the oxidation reaction.The example of spendable solvent can comprise: water; Acetone; Ether, for example tetrahydrofuran is with diox; Aromatic hydrocarbons, for example benzene; Aliphatic hydrocrbon, for example hexane and heptane; And halogenated hydrocarbons, for example methyl chloride, methylene chloride and chloroform.In these solvents, halogenated hydrocarbons, for example methyl chloride, methylene chloride and chloroform and acetone are the solvents of the preferred PHA that considers.

In above-mentioned oxidation reaction, the pha copolymer, permanganate and the acid that contain the unit of chemical formula (24) representative can add with reaction dissolvent at the beginning of reaction simultaneously, and maybe wherein various materials are continuously or add in the reaction system intermittence.In addition, reaction also can be carried out like this: be dissolved or suspended in permanganate in the solvent separately in advance, then PHA and acid continuously or intermittently in the adding system, perhaps are dissolved or suspended in PHA separately in the solvent in advance, then with permanganate and acid continuously or intermittently in the adding system.In addition, reaction also can be carried out like this: add PHA and acid in advance, then permanganate continuously or intermittently in the adding system, is perhaps added potassium permanganate and acid in advance, then with PHA continuously or intermittently in the adding system.

Temperature of reaction is generally-40-40 ℃, and preferred-10-30 ℃.Reaction time is depended on the ω-chain acid ester unit of chemical formula (24) representative and the stoichiometric proportion of permanganate, and temperature of reaction, but is generally 2-48 hour.

In addition, except that the 3-hydroxyl-ω-chain acid ester unit of chemical formula (24) representative, when use contained the PHA of the 3-hydroxyl-replacement alkanoate unit of chemical formula (9) representative or the 3-hydroxy-cyclohexyl alkanoate unit that chemical formula (10) is represented, reaction can be carried out under similarity condition.

(n is the integer that is selected from 1-8, R ₉Expression contains the substituting group of the residue with phenyl structure or thienyl structure, and when having two or more unit, the n of each unit and R ₉Independently of one another as above-mentioned definition.)

(R ₁₀The substituting group of representative ring hexyl, it is selected from H atom, CN group, NO ₂Group, halogen atom, CH ₃Group, C ₂H ₅Group, C ₃H ₇Group, CF ₃Group, C ₂F ₅Group and C ₃F ₇Group, k are the integer that is selected from 0-8.When having two or more unit, the R of each unit ₁₀Independently as above-mentioned definition.)

(preparation method who contains the polyhydroxyalkanoatefrom of unit shown in the chemical formula (24))

As mentioned above, the PHA of unit that contains chemical formula (22) representative is by the PHA preparation of the 3-hydroxyl-ω-chain acid ester unit that contains chemical formula (24) representative, and wherein this chain acid ester contains carbon-to-carbon double bond at its side chain terminal place.

The PHA that contains unit shown in the above-mentioned chemical formula (24) is had no particular limits, and can use following method preparation: use the preparation method of micro-organisms technology, the preparation method who uses the genetically engineered plants system, chemical polymerization preparation method etc.Herein, when comprising the step of using micro-organisms in the method for preparing above-claimed cpd, this polyhydroxyalkanoatefrom is the isotachyte of only being made up of the R type.But this compound is not particularly limited and is can also use atactic polymer by isotachyte, as long as can both realize purpose of the present invention with these compounds aspect physical property and the function two.And, also can use the method that comprises the chemosynthesis step, utilize the ring-opening polymerization of lactone compound etc. to obtain this polyhydroxyalkanoatefrom.

For the PHA of the 3-hydroxyl-ω-chain acid ester unit that contains chemical formula (24) representative, its multiple preparation method is all existing to be described.

In the culture medium of the ω-alkenoic acid that contains chemical formula (25) representative, cultivate mentioned microorganism, thereby make the PHA that contains unit shown in the chemical formula (24).

(wherein, q is the integer that is selected from 1-8).

Be used for preparing the microorganism that contains the PHA of unit shown in the chemical formula (24) and can be any microorganism, as long as this microorganism has the ability that produces PHA, that is to say, by cultivating in the nutrient culture media that contains ω-alkenoic acid shown in the chemical formula (25), it can produce the PHA-type polyester of the 3-hydroxyl-ω-chain acid ester unit that contains general formula (24) representative.Suitable example with the available microorganism that produces the PHA ability is the microorganism that belongs to pseudomonas (Pseudomonas).In these microorganisms, more preferably such bacterial strain: it does not have the enzyme reaction of the vinyl that replaces on oxidation or the epoxidation phenyl, but has the ability that produces PHA.

More particularly, hope is Pseudomonas cichorii (Pseudomonas cichorii), pseudomonas putida (Pseudomonas putida), Pseudomonas fluorescens (Pseudomonasfluorecence), Pseudomonas oleovorans (Pseudomonas oleovorans), pseudomonas aeruginosa (Pseudomonas aeruginosa), Pseudomonas stutzeri (Pseudoraonas stutzeri), Zhan Shi pseudomonad (Pseudomonas jessenii) etc.The microorganism example comprises more specifically, Pseudomonas cichorii strain YN2 (FERM BP-7375), Pseudomonas cichorii strain H45 (FERMBP-7374), Zhan Shi pseudomonad strain P161 (FERM BP-7376) and pseudomonas putida strain P91 (FERM BP-7373).These four kinds of microorganisms are deposited in International Patent Organism Depositary (IPOD) National Instituteof Advanced Industrial Science and Technology (AIST), TsukubaCentral 6 on November 20th, 2000, among 1-1, Higashi 1-chome, Tsukuba-shi, the Ibaraki-ken 305-8566 (Japan), and in Japanese Unexamined Patent Publication No No.2001-288256 and 2002-080571, be described.

Also can use any nutrient culture media as the nutrient culture media that in cultivating the step of microorganism, uses,, get final product as the minimal medium of ammonium salt or nitrate as long as this nutrient culture media is for containing phosphate and nitrogenous source.In addition, in the step that makes microorganisms PHA, can improve the productive capacity of PHA by the concentration of regulating nitrogenous source in the nutrient culture media.

And, also can in nutrient culture media, add nutrient, for example yeast extract, poly-peptone or meat extract are as the substrate that promotes microbial growth.In other words, can also with nutrient for example the form of yeast extract, poly-peptone or meat extract add peptide, as the energy or carbon source.

Selectively, for nutrient culture media, with the energy or carbon source that carbohydrate consumes as microbial growth, it comprises: aldose class, for example glyceraldehyde, erythrose, arabinose, wood sugar, glucose, galactose, mannose and fructose; Glycitols, for example, glycerine, antierythrite and xylitol; Aldonic acid, for example, gluconic acid; Uronic acid, for example, glucuronic acid and galacturonic acid; And disaccharides, for example, maltose, sucrose and lactose.

Also available organic acid or its salt replace carbohydrate, more particularly, with the relevant organic acid of TCA circulation, by the organic acid that comprises that the biochemical reaction that is less than one or two step of TCA round-robin makes, or this organic acid water soluble salt.The used organic acid or the example of its salt comprise: hydroxycarboxylic acid, for example, pyruvic acid, oxaloacetic acid, citric acid, isocitric acid, ketoglutaric acid, succinic acid, fumaric acid, malic acid and lactic acid; Oxo carboxylic acid; And water soluble salt.Selectively, also can use amino acid, for example, aspartic acid and glutamic acid, or its salt.When adding organic acid or its salt, more preferably from group down, select one or both or multiple compound: pyruvic acid, oxaloacetic acid, citric acid, isocitric acid, ketoglutaric acid, succinic acid, fumaric acid, malic acid, lactic acid; And salt, then selected compounds (multiple compound) is joined in the nutrient culture media and dissolving.Selectively, when adding amino acid or its salt, more preferably from aspartic acid, glutamic acid and salt thereof, select one or more amino acid or its salt, join in the nutrient culture media selected amino acid or salt and dissolving then.In this case, if desired, this compound of all or part can be added with the form of water soluble salt, and solve homogeneously in the nutrient culture media, thereby can not influence the pH of nutrient culture media.

To be generally per unit nutrient culture media 0.1-5% (w/v) with the concentration that the energy that produces PHA joins the cosubstrate in the nutrient culture media as the carbon source of microbial growth, be preferably 0.2-2% (w/v).Just, can add one or more peptides, yeast extract, organic acid or its salt, amino acid or its salt and carbohydrate, every kind of material wherein all can be used as cosubstrate.At this moment, it is desirable for these compounds of adding and make its total concentration within above-mentioned concentration range.

It is desirable to, the used substrate of preparation target P HA, i.e. the content of the ω-alkenoic acid of general formula (25) representative is chosen as per unit nutrient culture media 0.01-1% (w/v), more preferably 0.02-0.2% (w/v).

Cultivation temperature should make the microorganism used therefor bacterial strain breed well.Usually, suitable is that the selection cultivation temperature is 15-37 ℃, more preferably 20-30 ℃.

Can adopt any cultural method to carry out this cultivation, for example Liquid Culture or solid culture need only microorganism used therefor and can breed and produce PHA therein.In addition, also can use the training method of any kind, comprise batch culture, fed-batch culture, semicontinuous cultivation or Continuous Cultivation.For example, the liquid batch culture can be designed to the cultural method that shaken cultivation base limit, limit infeeds oxygen, perhaps for using the stirring ventilation type oxygen supply method of jar fermenter.

As the method for using micro-organisms and accumulation PHA, except single phase of in the inorganic medium that contains the phosphate that adds with predetermined concentration and nitrogenous source such as ammonium salt or nitrate, cultivating microorganism the cultivation, also can adopt incubation is divided into two stages carries out two stage cultivations of microbe culture.In this two stages cultivation, cultivate as the phase one, microorganism is fully bred in inorganic medium, this inorganic medium contains phosphate and the nitrogenous source that adds with predetermined concentration, and for example ammonium salt or nitrate are then in subordinate phase is cultivated, to cultivate the bacterial cell that is obtained the phase one is transferred in another nutrient culture media, this nutrient culture media contains limited nitrogenous source in the substrate cultivation process that adds predetermined concentration, for example ammonium chloride, and further cultivation in this nutrient culture media.This subordinate phase is cultivated and is made micro-organisms and accumulate PHA.Adopt this two stages cultivation can improve the throughput rate of target P HA.

Usually, the PHA type polyester that makes has hydrophobic atomic group on side chain, for example derived from the vinyl alkyl group of 3-hydroxyl-ω-chain acid ester unit.Therefore, this PHA type polyester poorly water-soluble, and in the bacterial cell of microorganism, accumulating, and this microorganism each all have the ability that produces PHA.Therefore, by propagation in incubation and collection bacterial cell, can easily the microbial cell of producing and accumulate target P HA type polyester be separated from nutrient culture media.Washing and the dry culture of bacteria cell of collecting, recyclable then target P HA polyester.

In addition, PHA is accumulated in usually and has in the microbial bacterial cell that produces the PHA ability.As the method that from microbial cell, reclaims target P HA, can use any method commonly used in this area.For example, the simplest method is to use organic solvent, and for example chloroform, methylene chloride, acetone or ethyl acetate extract.Except those solvents, also can use diox, tetrahydrofuran or acetonitrile.Under the working environment of not wishing with an organic solvent, can adopt the method for following recovery PHA to replace solvent extraction, promptly carry out removing again after the following step bacterial cell component the removal target P HA.That is to say that this step comprises: use surfactant, for example SDS handles; Use enzyme, for example lysozyme is handled; Use such as the reagent of hypochlorite, ammonia or EDTA and handle; With with following a kind of method physics disruption of microorganisms cell: ultrasonication, homogenate, pressure breaking, ball collide, mill, smash to pieces and freeze thawing.

As the example of inorganic medium available in the production method of the present invention, shown in composed as follows of the inorganic medium that uses among the following embodiment (M9 nutrient culture media).

(composition of M9 nutrient culture media)

Na ₂HPO ₄： 6.3

KH ₂PO ₄： 3.0

NH ₄Cl： 1.0

NaCl： 0.5

(g/L，pH＝7.0)

In addition, for the PHA productive capacity that good bacterial cell is bred and improved and propagation accompanies, need for example add an amount of essential trace element, for example essential trace metal element in the M9 nutrient culture media to inorganic medium.The trace components solution with following composition that adds about 0.3% (v/v) in nutrient culture media is very effective.Add this trace components solution and then supplied trace metal element used in the microbial growth process etc.

(composition of trace components solution)

Nitrilotriacetic acid(NTA): 1.5

MgSO ₄： 3.0

MnSO ₄： 0.5

NaCl： 1.0

FeSO ₄： 0.1

CaCl ₂： 0.1

CoCl ₂： 0.1

ZnSO ₄： 0.1

CuSO ₄： 0.1

AlK(SO ₄) ₂： 0.1

H ₃BO ₃： 0.1

Na ₂MoO ₄： 0.1

NiCl ₂： 0.1

(g/L)

And, by in incubation, existing simultaneously with the substrate for preparing target P HA, promptly, ω-alkenoic acid that chemical formula (25) representative is not only arranged, also have the replacement alkanoate compound of chemical formula (26) representative or the cyclohexyl alkanoate compound of chemical formula (27) representative, then can prepare the PHA of the unit of the unit of the 3-hydroxyl-ω-chain acid ester unit that contains chemical formula (24) representative and other chemical formula (9) representative or chemical formula (10) representative.In this case, the content of the cyclohexyl alkanoate compound of the replacement alkanoate compound of the ω-alkenoic acid of chemical formula (25) representative, chemical formula (26) representative and chemical formula (27) representative is than wishing to be chosen as per unit nutrient culture media 0.01-1% (w/v), more preferably 0.02-0.2% (w/v).

(r is the integer that is selected from 1-8.R ₂₀Expression contains the substituting group of residue, and this residue has the ring structure of phenyl or thienyl, and it is the group of one of chemical formula (11), (12), (13), (14), (15), (16), (17), (18), (19), (20) and (21) representative.When having two or more unit, the R of each unit ₂₀Independently as above-mentioned definition.)

(R ₂₁Substituting group on the representative ring hexyl, it is selected from H atom, CN group, NO ₂Group, halogen atom, CH ₃Group, C ₂H ₅Group, C ₃H ₇Group, CF ₃Group, C ₂F ₅Group and C ₃F ₇Group, s are the integer that is selected from 1-8.)

(R _11aSubstituting group on the expression aromatic ring, and R _11aBe selected from H atom, halogen atom, CN group, NO ₂Group, CH ₃Group, C ₂H ₅Group, C ₃H ₇Group, CH=CH ₂Group, COOR _11b(R _11bBe selected from H atom, Na atom and K atom), CF ₃Group, C ₂F ₅Group and C ₃F ₇Group, and when having two or more unit, the R of each unit ₁₁Independently as above-mentioned definition.)

(R ₁₂Substituting group on the expression aromatic ring, and R ₁₂Be selected from H atom, halogen atom, CN group, NO ₂Group, CH ₃Group, C ₂H ₅Group, C ₃H ₇Group, SCH ₃Group, CF ₃Group, C ₂F ₅Group and C ₃F ₇Group, and when having two or more unit, the R of each unit ₁₂Independently as above-mentioned definition.)

(R ₁₃Substituting group on the expression aromatic ring, and R ₁₃Be selected from H atom, halogen atom, CN group, NO ₂Group, CH ₃Group, C ₂H ₅Group, C ₃H ₇Group, CF ₃Group, C ₂F ₅Group and C ₃F ₇Group, and when having two or more unit, the R of each unit ₁₃Independently as above-mentioned definition.)

(R _14aSubstituting group on the expression aromatic ring, and R _14aBe selected from H atom, halogen atom, CN group, NO ₂Group, COOR _14b, SO ₂R _14c(R _14bBe selected from H, Na, K, CH ₃And C ₂H ₅, R _14cBe selected from OH, ONa, OK, halogen atom, OCH ₃And OC ₂H ₅), CH ₃Group, C ₂H ₅Group, C ₃H ₇Group, (CH ₃) ₂-CH group and (CH ₃) ₃-C group, and when having two or more unit, the R of each unit _14a, R _14bAnd R _14cIndependently of one another as above-mentioned definition.)

(R _15aSubstituting group on the expression aromatic ring, and R _15aBe selected from H atom, halogen atom, CN group, NO ₂Group, COOR _15b, SO ₂R _15c(R _15bBe selected from H, Na, K, CH ₃And C ₂H ₅, R _15cBe selected from OH, ONa, OK, halogen atom, OCH ₃And OC ₂H ₅), CH ₃Group, C ₂H ₅Group, C ₃H ₇Group, (CH ₃) ₂-CH group and (CH ₃) ₃-C group, and when having two or more unit, the R of each unit _15a, R _15bAnd R _15cIndependently of one another as above-mentioned definition.)

(R _16aSubstituting group on the expression aromatic ring, and R _16aBe selected from H atom, halogen atom, CN group, NO ₂Group, COOR _16b, SO ₂R _16c(R _16bBe selected from H, Na, K, CH ₃And C ₂H ₅, R _16cBe selected from OH, ONa, OK, halogen atom, OCH ₃And OC ₂H ₅), CH ₃Group, C ₂H ₅Group, C ₃H ₇Group, (CH ₃) ₂-CH group and (CH ₃) ₃-C group, and when having two or more unit, the R of each unit _16a, R _16bAnd R _16cIndependently of one another as above-mentioned definition.)

(R _17aSubstituting group on the expression aromatic ring, and R _17aBe selected from H atom, halogen atom, CN group, NO ₂Group, COOR _17b, SO ₂R _17c(R _17bBe selected from H, Na, K, CH ₃And C ₂H ₅, R _17cBe selected from OH, ONa, OK, halogen atom, OCH ₃And OC ₂H ₅), CH ₃Group, C ₂H ₅Group, C ₃H ₇Group, (CH ₃) ₂-CH group and (CH ₃) ₃-C group, and when having two or more unit, the R of each unit _17a, R _17bAnd R _17cIndependently of one another as above-mentioned definition.)

In addition, the PHA that contains the 3-hydroxyl-ω-carboxyl alkanoate unit of at least one chemical formula (22) representative in the molecule can prepare by Hydrolyze method in the presence of acid or alkali, or by the preparation of hydrogenolysis method, this hydrogenolysis method comprises catalytic reduction reaction, and the pha copolymer that wherein uses the 3-hydroxyl-ω-alkoxy carbonyl alkanoate unit that contains at least one chemical formula (28) representative is as starting material.

(wherein, n is the integer that is selected from 1-8, R ₂₂Be one of residue of following general formula representative,

And when having two or more unit, the n of each unit and R ₂₂Independently of one another as above-mentioned definition.)

(wherein, l is the integer that is selected from 1-8, R ₁₈Be selected from H atom, Na atom and K atom, and when having two or more unit, 1 and R of each unit ₁₈Independently of one another as above-mentioned definition.)

And, by in incubation, existing simultaneously with the substrate for preparing target P HA, promptly, ω-alkenoic acid that chemical formula (25) representative is not only arranged, also have the replacement alkanoate compound of chemical formula (26) representative or the cyclohexyl alkanoate compound of chemical formula (27) representative, then can prepare the multipolymer with a kind of PHA, this PHA contains 3-hydroxyl-ω-chain acid ester unit and the unit of other chemical formula (9) representative or the unit of chemical formula (10) representative of chemical formula (24) representative.

As mentioned above, when comprising the step of using micro-organisms in the method for preparing above-claimed cpd, this PHA is for only containing the isotachyte of R type.But this compound is not particularly limited and is can also use atactic polymer by isotachyte, as long as can both realize purpose of the present invention with these polymkeric substance aspect physical property and the function two.And, also can use the method that comprises the chemosynthesis step to obtain this PHA, and use the ring-opening polymerization of lactone compound etc. in this synthesis step.

(example of the sulfamate compounds thing of chemical formula (23) representative)

H ₂N-A ₃(-SO ₂R ₁₉) _y (23)

(R ₁₉Be selected from OH, halogen atom, ONa, OK and OR _19aAnd, R _19aAnd A ₃Be selected from and replace or unsubstituted aliphatic hydrocrbon structure, replacement or unsubstituted aromatic ring structure and replacement or unsubstituted heterocycle structure.Y is the integer that is selected from 1-8, and when having two or more unit, the R of each unit ₁₉, R _19a, A ₃With y independently of one another as above-mentioned definition.)

R ₁₉Be preferably selected from the straight or branched alkyl and replacement or the unsubstituted phenyl that contain 1-8 carbon atom.A ₃Represent straight or branched to replace or unsubstituted C ₁-C ₈Alkylidene, replacement or unsubstituted phenylene, replacement or unsubstituted naphthyl and contain the replacement or the unsubstituting heterocycle structure of at least one atom that is selected from N, S and O.If A ₃Has ring structure, the also further condensation of then unsubstituted ring.In addition, when having two or more unit, the R of each unit ₁₉, R _19a, A ₃With y independently of one another as above-mentioned definition.

If A ₃For straight chain replaces or unsubstituted alkylidene, the compound of then following chemical formula (29) representative can be used as an example.

H ₂N-A ₄(-SO ₂R ₂₀) _z (29)

(R ₂₀Be selected from OH, halogen atom, ONa, OK and OR _20aAnd, R _20aBe selected from the straight or branched alkyl and replacement or the unsubstituted phenyl that contain 1-8 carbon atom.A ₄Be straight or branched, replacement or unsubstituted C ₁-C ₈Alkylidene, and can be contained the replacement such as alkyl, alkoxy of 1-20 carbon atom.Z is the integer that is selected from 1-8, and when having two or more unit, the R of each unit ₂₀, R _20a, A ₄With z independently of one another as above-mentioned definition.)

The example of the compound of chemical formula (29) representative can comprise 2-tarine (taurine), 3-aminopropanesulfonic acid, 4-aminobutanesulfonic acid, 2-amino-2-methyl propane sulfonic acid, its alkali metal salt and ester thereof.

If A ₃For replacing or unsubstituted phenylene, the compound of then following chemical formula (30) representative can be used as an example.

(R _3a, R _3b, R _3c, R _3dAnd R _3eIn at least one group be selected from SO ₂R _3f(R _3fBe selected from OH, halogen atom, ONa, OK and OR _3f1R _3f1Be selected from the straight or branched alkyl and replacement or the unsubstituted phenyl that contain 1-8 carbon atom).In addition, R _3a, R _3b, R _3c, R _3dAnd R _3eBe selected from hydrogen atom, halogen atom, contain the alkyl of 1-20 carbon atom, the alkoxy that contains 1-20 carbon atom, OH base, NH ₂Base, NO ₂Base, COOR _3g(R _3gOne of expression H atom, Na atom and K atom), acetamide group, OPh group, NHPh group, CF ₃Group, C ₂F ₅Group and C ₃H ₇Group.When having two or more unit, the R of each unit _3a, R _3b, R _3c, R _3d, R _3e, R _3f, R _3f1And R _3gIndependently of one another as above-mentioned definition.)

The example of the compound of chemical formula (30) representative can comprise: multiple amino phenyl sulfonyl acid derivative and salt thereof, for example, sulfanilic acid (sulfanilic acid), metanilic acid, orthanilic acid, between-toluidine-4-sulfonic acid, neighbour-toluidine-4-sodium sulfonate, right-toluidine-2-sulfonic acid, 4-aminoanisole-2-sulfonic acid, neighbour-anisidine-5-sulfonic acid, right-anisidine-3-sulfonic acid, right-anisidine-2-sulfonic acid, 3-nitroaniline-4-sulfonic acid, 2-nitroaniline-4-sodium sulfonate, 4-nitroaniline-2-sodium sulfonate, 1,5-dinitroaniline-4-sulfonic acid, 2-amino-phenol-4-hydroxyl-5-nitrobenzene-sulfonic acid, 2,4-xylidin-5-sodium sulfonate, 2,4-xylidin-6-sulfonic acid, 3,4-xylidin-5-sulfonic acid, 4-isopropyl aniline-6-sulfonic acid, 4-5-trifluoromethylaniline-6-sulfonic acid, 3-carboxyl-4-hydroxyanilines-5-sulfonic acid, 4-carboxyl aniline-6-sulfonic acid and aniline 2, the 4-disulfonic acid; With the ester class, for example, the methyl esters and the phenyl ester of multiple amino phenyl sulfonyl acid derivative and salt thereof, for example 2-aminobenzenesulfonic acid methyl esters, 4-aminobenzenesulfonic acid methyl esters, 2-amino phenyl sulfonyl acid phenenyl ester, 4-amino phenyl sulfonyl acid phenenyl ester and alkali metal salt thereof etc.

If A ₃For replacing or unsubstituted naphthyl, then following chemical formula (31A) or the compound of (31B) representing can be used as example.

(R in the general formula (31A) _4a, R _4b, R _4c, R _4d, R _4e, R _4fAnd R _4gIn at least one group, or general formula (31B) in R _4h, R _4i, R _4j, R _4k, R _4l, R _4mAnd R _4nIn at least one group be selected from SO ₂R _4o(R _4oBe selected from OH, halogen atom, ONa, OK and OR _4olR _4olBe selected from the straight or branched alkyl and replacement or the unsubstituted phenyl that contain 1-8 carbon atom).In addition, R _4a, R _4b, R _4c, R _4d, R _4e, R _4f, R _4g, R _4h, R _4i, R _4j, R _4k, R _4l, R _4mAnd R _4nBe selected from hydrogen atom, halogen atom, contain the alkyl of 1-20 carbon atom, the alkoxy that contains 1-20 carbon atom, OH base, NH ₂Base, NO ₂Base, COOR _4p(R _4pOne of expression H atom, Na atom and K atom), acetamide group, OPh group, NHPh group, CF ₃Group, C ₂F ₅Group and C ₃H ₇Group.When having two or more unit, the R of each unit _4a, R _4b, R _4c, R _4d, R _4e, R _4f, R _4g, R _4h, R _4i, R _4j, R _4k, R _4l, R _4m, R _4n, R _4o, R _4ol, R _4pWith m independently of one another as above-mentioned definition.)

Chemical formula (31A) or (31B) example of compound of representative can comprise: multiple naphthylamine sulfonic acid derivant and salt thereof, for example, 1-naphthylamine-5-sulfonic acid, naphthalidine-4-sulfonic acid, naphthalidine-8-sulfonic acid, 2-naphthylamines-1-sulfonic acid, 2-naphthylamines-5-sulfonic acid, naphthalidine-6-sulfonic acid, naphthalidine-7-sulfonic acid, naphthalidine-2-ethoxy-6-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 6-amino-1-naphthols-3-sulfonic acid, 1-amino-8-naphthol-2,4-sodium sulfonate and 1-amino-8-naphthol-3, the 6-sodium sulfonate; Also have the ester class in addition, the methyl esters and the phenyl ester of for example multiple naphthylamine sulfonic acid derivant and salt thereof, for example, naphthalidine-8-methylmesylate, 2-naphthylamines-1-methylmesylate, naphthalidine-8-phenyl sulfonate and 2-naphthylamines-1-phenyl sulfonate, and alkali metal salt etc.

If A ₃Be the replacement or the unsubstituted heterocycle structure that contain at least a atom among N, S and the O, then this heterocycle structure can be any ring of pyridine ring, piperazine ring, furan nucleus, mercaptan ring etc.

The example of compound can comprise: sulfonic acid, for example, 2-aminopyridine-6-sulfonic acid, 2-aminopiperazine-6-sulfonic acid; Its alkali metal salt; And ester.The example of sulphonic acid ester can comprise and replacing or unsubstituted aliphatic hydrocrbon structure, replacement or unsubstituted aromatic ring structure and replacement or unsubstituted heterocycle structure.Especially preferred is straight or branched alkyl and replacement or the unsubstituted phenyl that contains 1-8 carbon atom.With regard to carrying out reaction such as esterification easily, more preferably OCH ₃, OC ₂H ₅, OC ₆H ₅, OC ₃H ₇, OC ₄H ₉, OCH (CH ₃) ₂, OCH ₂(CH ₃) ₃, OC (CH ₃) ₃Deng.

(preparation method of the PHA of chemical formula (1) representative)

Reaction between the sulfamate compounds thing that the PHA of the unit that contains chemical formula (22) representative and chemical formula (23) are represented is described in detail.

With respect to the consumption of the unit of representing as the chemical formula (22) of raw material, the use amount of the compound of chemical formula (23) representative is a doubly mole of 0.1-50.0, preferred 1.0-20.0 times of mole.

The method that forms amido link by carboxylic acid and amine among the present invention comprises the condensation reaction of being undertaken by thermal dehydration.Especially, for making ester bond on the main polymer chain that the purpose of cracking does not take place under mild reaction conditions, then following method is effective:, and then react with amine forming the active acyl intermediate with activator activating carboxy acid part.The example of active acyl intermediate comprises acid halide, acid anhydrides and active ester.Especially, in order to simplify production technology, preferably use condensation agent in same conversion zone, to form the method for amido link.

If desired, can after being separated into acid halide, carry out once again with the condensation reaction of amine.

According to the combination of compounds of chemical formula (23) and (22), used condensation agent can suitably be selected from the phosphate condensation agent that is used in the aromatic polyamide polycondensation reaction, be used for the synthetic carbodiimide condensation agent of peptide, acid chloride condensation agent etc.

The example of phosphate condensation agent can comprise phosphite ester condensation agent, phosphorus pentachloride condensation agent, phosphoric anhydride condensation agent, phosphate condensation agent and phosphoamide condensation agent.In reaction of the present invention, can use the phosphite ester condensation agent.Used phosphite ester condensation agent can comprise benzene methyl between triphenyl phosphite, phosphorous acid diphenyl ester, tricresyl phosphite o-toluene ester, phosphorous acid two o-toluene esters, tricresyl phosphite, two benzene methyls of phosphorous acid, tricresyl phosphite to benzene methyl, two pairs of benzene methyls of phosphorous acid, phosphorous acid two adjacent chlorobenzene esters, tricresyl phosphite to chlorobenzene ester, phosphorous acid two pairs of chlorobenzene esters, Trimethyl phosphite and triethyl phosphites.The preferred triphenyl phosphite that uses in these compounds.In addition, also can add slaine, for example, lithium chloride and lime chloride are in order to improve the dissolubility and the reactivity of polymkeric substance.

The example of carbodiimide condensation agent can comprise dicyclohexylcarbodiimide (DCC), DIC (DIPC) and N-ethyl-N '-3-dimethylaminopropyl carbodiimide (EDC=WSCI) and hydrochloride (WSCIHCl) thereof.DCC or WSCI can with N-hydroxy-succinamide (HONSu), I-hydroxybenzotriazole (HOBt), 3-hydroxyl-4-oxygen-3,4-dihydro-1,2,3-phentriazine (HOObt) etc. is used in combination.With respect to the consumption of the unit of chemical formula (22) representative, the condensation agent consumption is a doubly mole of 0.1-50, and preferred 1-30 is mole doubly.In addition, condensation agent itself also can be used as reaction dissolvent.

Can as requested solvent be used for reaction of the present invention.The example of available solvent comprises: hydro carbons, for example hexane, cyclohexane and heptane; Ketone, for example acetone and MEK; Ethers, for example dimethyl ether, diethyl ether and tetrahydrofuran; Halogenated hydrocarbons, for example methylene chloride, chloroform, phenixin, ethylene dichloride and trichloroethanes; Aromatic hydrocarbons, for example benzene and toluene; Aprotic polar solvent, N for example, dinethylformamide, dimethyl sulfoxide, dimethyl acetamide and hexamethyl phosphoramide; Pyridine derivate, for example pyridine and picoline; And N-Methyl pyrrolidone.Especially preferably use pyridine, N-Methyl pyrrolidone etc.Can correspondingly wait to determine used quantity of solvent according to raw material, matrix type, reaction conditions.The method according to this invention, temperature of reaction is not particularly limited, but is generally the fusing point of-20 ℃-solvent.But wish under the optimum temperature of used condensation agent, to react.

The method according to this invention, the reaction time is generally 1-48 hour.According to the present invention, can adopt classic method, for example distillation, that purifying forms as mentioned above, as to contain the PHA of chemical formula (1) representative reaction liquid.Selectively, can reclaim the target P HA of chemical formula (1) representative in the following manner: will contain the reactant liquor of PHA and the insoluble therein solvent of target P HA of chemical formula (1) representative, for example water, alcohol (methyl alcohol, ethanol etc.) and ether (dimethyl ether, diethyl ether, tetrahydrofuran etc.) evenly mix; Precipitate the target P HA of chemical formula (1) representative again.Can separate and purifying PHA gained, chemical formula (1) representative as required.Separate and purification process is not particularly limited, the example of its method can comprise that use do not dissolve the reprecipitation method of the solvent of the PHA that chemical formula (1) represents, and chromatography and dialysis.

For another preparation method of the present invention, partly be-A at the R of chemical formula (1) ₁-SO ₃Under the situation of H, can be after carrying out condensation reaction with amine, use esterification agent is partly carried out esterification to the R of chemical formula (1), with formation-A ₁-SO ₃CH ₃With regard to the esterification agent, can use the methyl esterification of fatty acid method in the gas chromatographic analysis.

The example of acid catalyzed process comprises the method for use hydrochloric acid-methyl alcohol, boron trifluoride-methanol and sulfuric acid-methyl alcohol, and the example of base catalysis method comprises the method for using sodium methoxide, tetramethyl guanidine and trimethyl silyl diazomethane.In these methods, the method for using the trimethyl silyl diazomethane is preferred, because this methylation reaction can carry out under temperate condition.

With respect to-A ₁-SO ₃The amount of H (it is the represented group of R in the chemical formula (1)), the consumption of trimethyl silyl diazomethane are doubly mole of 0.1-50, and preferred 1-20 is mole doubly.Temperature of reaction is not particularly limited, but is generally-20 ℃-30 ℃.According to the present invention, though the reaction time can not determine uniquely, be generally 1-48 hour.

The example of solvent for use can comprise in the present invention's reaction: hydrocarbon, for example hexane, cyclohexane and heptane; Alcohol, for example methyl alcohol and ethanol; Halogenated hydrocarbons, for example methylene chloride, chloroform, phenixin, ethylene dichloride and trichloroethanes; Aromatic hydrocarbons, for example benzene and toluene; Aprotic polar solvent, N for example, dinethylformamide and dimethyl sulfoxide; And pyridine derivate.Especially preferably use halogenated hydrocarbons and alcohol.Can correspondingly wait and suitably determine used quantity of solvent according to raw material, reaction conditions.

The method according to this invention, temperature of reaction is not particularly limited, but is generally-20 ℃-30 ℃.But wish under the optimum temperature of used condensation agent and reagent, to react.

According to reaction of the present invention, reaction dissolvent, temperature of reaction, reaction time and purification process are not limited to said method.

The molecular weight of PHA can be determined as relative molecular weight and absolute molecular weight among the present invention.For example, can use determining molecular weight simply such as gel permeation chromatography (GPC).The concrete grammar of measuring with GPC comprises, above-mentioned PHA is dissolved in to be easy to dissolve in the solvent of PHA in advance, and uses similar mobile phase to measure.According to the PHA that will measure, can use differential refractometer (RI) or UV-detector (UV) as detecting device.By with reference material (polystyrene, polymethylmethacrylate etc.) relatively obtain molecular weight.The solvent of dissolve polymer can be selected from dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), chloroform, tetrahydrofuran (THF), toluene and hexafluoroisopropanol (HFIP).For polar solvent, can add salt and measure.

In addition, according to the present invention, preferably uses the above-mentioned PHA of the ratio (Mw/Mn) of the weight-average molecular weight (Mw) measured as mentioned above and number-average molecular weight (Mn) as 1-10.The number-average molecular weight (Mn) that it is desirable for PHA of the present invention is 1,000-1, and 000,000, preferred 1,000-500,000.

[application of toner]

The formation method that comprises static charge image developing toner and this toner of use according to the application of polyhydroxyalkanoatefrom of the present invention.Specifically, this polyhydroxyalkanoatefrom can be used as internally or the outside charge adjusting agent that joins in the toner.

That is to say, the invention provides a kind of charge adjusting agent that contains polyhydroxyalkanoatefrom, the static charge image developing toner that contains this charge adjusting agent is provided in addition.And the present invention also provides a kind of formation method, and it comprises: charging/sub-image image-forming step promptly applies voltage so that this electrostatic latent image load-carrying unit uniform charged from the outside to charge member, and forms electrostatic latent image continuously; On the electrostatic latent image load-carrying unit, form the development step of toner image; Via or not via the intermediate transfer element, the toner image on the electrostatic latent image load-carrying unit is transferred to transfer step on the recording medium; Hot photographic fixing step with toner image on the heat fixer transfer materials.The present invention also provides a kind of imaging device, and it comprises the corresponding device of each step with said method, that is, and and charging device, sub-image imaging device, developing apparatus, transfer device and heat-fixing device.

＜as the purposes of charge adjusting agent 〉

For the structure of the polyhydroxyalkanoatefrom that uses among the present invention, importantly, this polyhydroxyalkanoatefrom has the structure that side chain is replaced by the sulfonic acid or derivatives thereof, as the monomeric unit of chemical formula (1) representative.Those unit with negative ion or electrophilic functional group are preferred for improving electronegative property, and in fact, charge adjusting agent of the present invention has excellent electronegative property.

Polyhydroxyalkanoatefrom that uses among the present invention and adhesive resin have good compatibility, especially, have good compatibility with the polyester binder resin.The toner that contains polyhydroxyalkanoatefrom of the present invention has very high specific charge and good time stability, so this toner even also can continue to provide distinct image in the imaging process of electrostatic recording after standing storage.In addition because this toner is colourless or light, and has electronegative property, so its can be prepared into can electronegative black toner and color toner.

And, form the kind and the ratio of the monomeric unit of polyhydroxyalkanoatefrom of the present invention by suitable selection, also can in wide region, adjust compatibility.

If the resin composition is selected, make charge adjusting agent in toner binder, can adopt the structure of microphase-separated, then in toner, do not produce electric continuity, so this toner can stably keep electric charge.Because polyhydroxyalkanoatefrom of the present invention does not contain heavy metal, therefore different with observed situation in containing the charge adjusting agent of metal, when using suspension polymerization or emulsion polymerization to prepare toner, the polymerization inhibiting effect that does not have heavy metal, result just can stably make this toner.

The adding of＜PHA in toner 〉

The method that above-claimed cpd is sneaked in the toner comprises inner addition method and outside addition method.When compound is added fashionablely by inside, with regard to the mass ratio of charge adjusting agent and toner binder, the use amount of compound is generally 0.1-50 quality %, is preferably 0.2-20 quality %.If it is not consumption is then worthless less than 0.1 quality %, remarkable to the improvement degree of toner charging property.On the other hand, consider that it is not preferred that consumption surpasses 50 quality % from economic angle.When compound of the present invention is added fashionablely by the outside, the mass ratio of preferred charge adjusting agent and toner binder is 0.01-5 quality %.Especially preferred its is fixed on the toner surface by the mechanochemistry mode.In addition, polyhydroxyalkanoatefrom of the present invention also can be used in combination with known charge adjusting agent.

The number-average molecular weight of polyhydroxyalkanoatefrom of the present invention is generally 1,000-1, and 000,000, be preferably 1,000-300,000.If less than 1,000, then polyhydroxyalkanoatefrom and toner binder are compatible fully, thereby are difficult to form discontinuous zone, cause quantity of electric charge deficiency, and the flowability of toner is had a negative impact.If surpass 500,000, then be difficult to polyhydroxyalkanoatefrom is dispersed in the toner.

Use gel permeation chromatography (GPC) to measure the molecular weight of polyhydroxyalkanoatefrom of the present invention.The concrete grammar of measuring with GPC comprises, above-mentioned polyhydroxyalkanoatefrom is dissolved in to be easy to dissolve in the solvent of this polyhydroxyalkanoatefrom in advance, and uses similar mobile phase to measure.The detecting device of use such as differential refractometer (RI) or UV-detector (UV) obtains molecular weight distribution from the calibration curve of polystyrene standard resin.The solvent of dissolve polymer is optional from the dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), chloroform, tetrahydrofuran (THF), toluene and the hexafluoroisopropanol (HFIP) that contain the LiBr of 0.1 quality %.

In addition, in the present invention, preferably use the polyhydroxyalkanoatefrom of the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) as 1-10.

In the present invention, the fusing point of preferred used polyhydroxyalkanoatefrom is 20-150 ℃, especially is 40-150 ℃, or does not have fusing point, but have 10-150 ℃, more preferably 20-150 ℃ vitrifying point.When the fusing point of polyhydroxyalkanoatefrom is lower than 20 ℃, or do not have fusing point but vitrifying point when being lower than 20 ℃, the flowability of toner or bin stability have the trend that affects adversely.If the fusing point of this polyhydroxyalkanoatefrom surpasses 150 ℃, or do not have fusing point but vitrifying point when surpassing 150 ℃, this charge adjusting agent is difficult to rub up in toner, thereby makes CHARGE DISTRIBUTION be tending towards extensive.

In this case, can use hot differential scanning calorimeter in the high-precision input offset type, for example, the DSC-7 that PerkinElmer Inc. makes measures fusing point Tm and vitrifying point Tg.

In toner binder according to the present invention and static charge image developing toner, the mass ratio of charge adjusting agent and toner binder is generally 0.1-50 quality %, is preferably 0.2-20 quality %.With regard to proportion of composing, static charge image developing toner of the present invention contains the charge adjusting agent of 0.1-50 quality %, the correctives bonding agent of 20-95 quality % and the colorant of 0-15 quality % usually.When if desired, its function is shown as when being combined with the colorant function, and toner can contain 60 quality % or Magnaglo still less (ferromagnetic metal powder, for example iron, cobalt and nickel, or such as magnetic iron ore, haematite and ferritic compound).In addition, static charge image developing toner of the present invention also can contain multiple additives (lubricant (teflon, low-molecular-weight polyolefin, fatty acid, its slaine or acid amides etc.), other charge adjusting agent (containing the azo dyes of metal, salicylic slaine etc.), or the like), in addition, in order to improve the flowability of toner, also can use hydrophobic colloid silicon particle etc.Based on the quality of toner, the amount of adjuvant is generally 10 quality % or still less.

In toner of the present invention, preferred at least a portion toner binder forms external phase, and at least a portion charge adjusting agent forms discontinuous zone.Charge adjusting agent and toner binder are compatible fully in toner, and do not form discontinuous zone therein, compare with this toner, the charge adjusting agent of adding is tending towards being exposed on the toner surface, therefore adds a little charge correctives and then demonstrates sufficient effect.This regional fineness of dispersion is preferably 0.01-4 μ m, more preferably 0.05-2 μ m.If surpass 4 μ m, the problem of toner transparency reduction is widened and produced to then dispersibility deficiency, so CHARGE DISTRIBUTION.If fineness of dispersion is less than 0.01 μ m, then situation and charge adjusting agent are compatible to the correctives bonding agent and do not form the situation in discontinuous zone therein basic identical fully, in this case, need to add a large amount of charge adjusting agents.In fact, at least a portion charge adjusting agent forms discontinuous zone, and can determine fineness of dispersion by observing section with transmission electron microscope(TEM).In order clearly to observe the interface, with this toner sections of dyeing such as ruthenium tetroxide, osmium tetroxides, it also is effective observing with electron microscope then.

For the granularity in the discontinuous zone that reduces to form by polyhydroxyalkanoatefrom of the present invention, can adding and toner binder and polyhydroxyalkanoatefrom compatible polymers of the present invention, as compatibilizing agent.This compatibilizing agent comprises following polymkeric substance: this polymkeric substance comprises a kind of essentially identical polymer of monomers chain of monomeric unit structure that contains in 50 moles of % or the polyhydroxyalkanoatefrom more and of the present invention, with a kind of essentially identical polymer of monomers chain of monomer structure that contains in 50 moles of % or more and the toner binder, and these polymer chains are connected to graft type or block type.With respect to the quality of polyhydroxyalkanoatefrom of the present invention, the consumption of compatibilizing agent is generally 30 quality % or still less, is preferably 1-10 quality %.

＜other composition material 〉

Other contained in the static charge image developing toner of the present invention composition material hereinafter will be described.

(adhesive resin)

At first, adhesive resin is not particularly limited, can uses any adhesive resin commonly used in the toner preparation.Can before the preparation toner charge adjusting agent of the present invention and adhesive resin be pre-mixed, this potpourri can be used as according to toner binder composition of the present invention, that have the electric charge regulating power.The example of adhesive resin comprises styrene polymer, polyester polymers, epoxy polymer, polyolefin polymer and polyether polyols with reduced unsaturation.These materials can use separately, perhaps use as potpourri.

The example of styrene polymer comprises the multipolymer, these monomers of styrene and (methyl) acrylate and the multipolymer of other monomer of copolymerization with it, with the multipolymer of styrene and diene monomers (butadiene, isoprene etc.), and the multipolymer of these monomers and other monomer of copolymerization with it etc.The example of polyester polymers comprises the polycondensation product of the alkylene oxide adduct of aromatic dicarboxylic acid and aromatic diol.The example of epoxy polymer comprises the reaction product of aromatic diol and epichlorokydrin, and modified outcome.The example of polyolefin polymer comprises tygon, polypropylene, and these monomers and the copolymer chain of other monomer of copolymerization with it.The example of polyether polyols with reduced unsaturation comprises the addition polymerization product of the alkylene oxide adduct of aromatic diisocyanate and aromatic diol.

The object lesson that is used for adhesive resin of the present invention comprises the polymkeric substance of following polymerisable monomer, their potpourri, or the copolymerization product that uses two or more following polymerisable monomers to obtain.Specifically, this polymkeric substance comprises, for example, and styrene polymer, as styrene/acrylic acid co-polymer or styrene/methacrylic acid multipolymer, polyester polymers, epoxy polymer, polyolefin polymer and polyether polyols with reduced unsaturation, and preferably use these polymkeric substance.

The object lesson of polymerisable monomer comprises: styrene and derivant thereof, for example o-methyl styrene, p-methylstyrene, to methoxy styrene, to styryl phenyl, to chlorostyrene, 3, the 4-dichlorostyrene, to ethyl styrene, 2, the 4-dimethyl styrene, align butylstyrene, to t-butyl styrene, to positive hexyl phenenyl ethene, to n-octyl styrene, align nonyl benzene ethene, align decyl styrene and align dodecyl styrene; The unsaturated mono-olefin of ethylenic, for example ethene, propylene, butylene and isobutylene; Unsaturated polyenoid, for example butadiene; Vinyl halide, for example vinyl chloride, vinylidene chloride, bromine ethene and fluorothene; Vinyl esters, for example vinyl acetate, propionate and vinyl benzoate; Alpha-methylene aliphatic monocarboxylic acid ester, for example methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, isobutyl methacrylate, n octyl methacrylate, methacrylic acid dodecane ester, methacrylic acid 2-Octyl Nitrite, methacrylic acid stearoyl ester, phenyl methacrylate, dimethylaminoethyl methacrylate and diethyl aminoethyl methacrylate; Acrylate, for example methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic acid n-octyl, acrylic acid dodecane ester, 2-EHA, stearyl acrylate acyl ester, acrylic acid 2-chloroethene ester and phenyl acrylate; Vinyl ether, for example vinyl methyl ether, EVE and vinyl isobutyl ether; Vinyl ketone, for example ethenyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; The N-vinyl compound, for example, N-vinyl pyrrole, N-vinylcarbazole, N-vinyl indoles and N-vinyl pyrrolidone; Vinyl naphthalene; The acrylic or methacrylic acid derivative, for example, vinyl cyanide, methacrylonitrile and acrylamide; Above-mentioned α, the ester of beta-unsaturated acid and the diester of dibasic acid; Dicarboxylic acid, for example maleic acid, maleic acid methyl esters, maleic acid butyl ester, dimethyl maleate, phthalic acid, succinic acid and terephthalic acid (TPA); Polyol compound, for example ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butylene glycol, 1,6-hexanediol, bisphenol-A, hydrogenated bisphenol A and polyoxyethylene bisphenol-A; Isocyanates for example, supports diisocyanate and 1 to phenylene diisocyanate, terephthaldehyde, the 4-tetramethylene diisocyanate; Amine, for example, ethamine, butylamine, ethylenediamine, 1,4-diaminobenzene, 1,4-diaminobutane and monoethanolamine; And epoxy compound, for example, diglycidyl ether, ethylene glycol diglycidylether, bisphenol-A glycidol ether and quinhydrones diglycidyl ether.

(crosslinking chemical)

In the preparation process of adhesive therefor resin of the present invention, can use following crosslinking chemical if desired.The example of bi-functional cross-linking agent can comprise divinylbenzene, two (4-acryloxy polyethoxy phenyl) propane, glycol diacrylate, 1, the 3-butanediol diacrylate, 1, the 4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1, the 6-hexanediyl ester, neopentylglycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, the Macrogol 200 diacrylate, the PEG400 diacrylate, the Macrogol 600 diacrylate, propylene glycol diacrylate, polypropyleneglycol diacrylate, polyester-type diacrylate (Nippon Kayaku Co., MANDA) and the above-mentioned diacrylate that replaced by methacrylate of acrylate part Ltd..

More more than difunctional, promptly, polyfunctional crosslinking agent can comprise pentaerythritol triacrylate, trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, low-polyacrylate and methacrylate thereof, also have 2, two (the 4-methacryloxy polyethoxy phenyl) propane of 2-, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, trimellitic acid triallyl and chlorine mattress diallyl phthalate.

(polymerization initiator)

In the preparation process of adhesive therefor resin of the present invention, can use following polymerization initiator if desired.Polymerization initiator can comprise, for example, peroxide-2 ethyl hexanoic acid the tert-butyl ester, cross hot valeric acid benzylamino isopropyl ester, the peroxide lauric acid tert-butyl ester, benzoyl peroxide, lauroyl peroxide, the peroxidating decoyl, di-tert-butyl peroxide, tert butyl isopropyl benzene peroxide, the diisopropylbenzyl superoxide, 2,2 '-azoisobutyronitrile, 2,2, '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2, two (the 4-methoxyls-2 of 2 '-azo, the 4-methyl pentane nitrile), 1, two (t-butyl peroxy)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 1, two (t-butyl peroxy) cyclohexanes of 1-, 1, two (t-butyl peroxy carbonyl) cyclohexanes of 4-, 2, two (t-butyl peroxy) octanes of 2-, normal-butyl-4, two (t-butyl peroxy) valerates of 4-, 2, two (t-butyl peroxy) butane of 2-, 1, two (t-butyl peroxy isopropyl) benzene of 3-, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, 2,5-dimethyl-2,5-two (benzoyl peroxide) hexane, di-t-butyl diperoxy isophthalate, 2,2-two (4,4-di-t-butyl peroxide cyclohexyl) propane, di-t-butyl peroxide-Alpha-Methyl succinate, di-t-butyl peroxide dimethylated pentanedioic acid ester, di-t-butyl peroxide six hydrogen terephthalates, di-t-butyl peroxide azelate, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, diglycol two (t-butyl peroxy carbonic ester), di-t-butyl peroxide trimethyladipic acid ester, three (t-butyl peroxy) triazines and vinyl three (t-butyl peroxy) silane.These compounds can separately or be used in combination.With regard to its consumption, with respect to the monomer of 100 mass parts, its working concentration can be 0.05 mass parts or more (being preferably the 0.1-15 mass parts).

(other biodegradable plastics)

In addition, in the present invention, preferably use with the binder combination of forming by other biodegradable plastics.This biodegradable plastics can comprise " Ecostar " and " Ecostar Plus " (Hagiwara Kogyo Co., Ltd.), " Biopol " (Monsanto Company), " Ajicoat " (Ajinomoto Co., Inc.), " Celgreen " (Daicel ChemicalIndustries, Ltd.), " Bionolle " (Showa Kobunshi K.K.), " Eco Plastic " (Toyota Motor Corporation), " LACEA " (Mitsui Chemical Inc.), " Biogreen " (Mitsubishi Gas Chemical Company, Inc.), " Nature Works " (Cargill Dow LLC) and " Biomax " (Du Pont).

Preferably adhesive resin and charge adjusting agent of the present invention are combined, thereby make the polymer architecture of adhesive resin similar as far as possible each other to the polymer chain structure of charge adjusting agent.If the polymer architecture of adhesive resin is different to a great extent each other with the polymer chain structure of charge adjusting agent, then the dispersion of charge adjusting agent in adhesive resin is tending towards insufficient.

Charge adjusting agent of the present invention joins in the resin binder internally, and its mass ratio is generally 0.1-50 quality %, is preferably 0.2-20 quality %.If the mass ratio of the inner charge adjusting agent that adds is less than 0.1 quality %, then the quantity of electric charge of toner is too little, and if it surpasses 50 quality %, the then charged stability decreases of toner.

The charge adjusting agent of＜non-PHA 〉

Except that charge adjusting agent of the present invention, also can use traditional charge adjusting agent, it is different from charge adjusting agent of the present invention.The object lesson of other charge adjusting agent can comprise aniline black byestuffs, quaternary ammonium salt and Monoazo metal complex salt dyestuff.The amount of the charge adjusting agent that adds can determine that for example, the charging property of adhesive resin, preparation method comprise colorant addition and process for dispersing, and the charging property of other adjuvant according to various conditions.With respect to the adhesive resin of 100 mass parts, the addition of used charge adjusting agent can be the 0.1-20 mass parts, is preferably the 0.5-10 mass parts.Selectively, can be with the metal oxide inorganic particle etc., or the inorganic material that the surface was handled by above-mentioned organic material is used as charge adjusting agent.Can be by with its adding or be mixed to and use wherein various charge adjusting agents in the adhesive resin, or use with the form that sticks on the correctives particle surface.

＜colorant 〉

With regard to the colorant of forming static charge image developing toner of the present invention, can use normally used any colorant in the toner preparation process, be not particularly limited.For example, can use carbon black, titanium white and other any pigment and/or dyestuff.

For example, when static charge image developing toner of the present invention when the magnetic color toner, the example of available colorant comprises that C.I. is directly red 1, C.I. is directly red 4, C.I. azogeramine, C.I. alkali red 1:1, C.I. mordant dyeing (Mordant) are red 30, C.I. is directly blue 1, C.I. is directly blue 2, C.I. acid blue 9, C.I. Blue VRS 5, C.I. alkali blue 3, C.I. alkali blue 5, C.I. mordant dyeing indigo plant 7, C.I. direct green 6, C.I. Viride Nitens 4 and C.I. Viride Nitens 6.The example of available pigment comprises chrome yellow, cadmium yellow, the mineral fast yellow, navel Huang (navel yellow), naphthol yellow S, hansa yellow G, permanent yellow NCG, tartrazine lake, chrome orange, molybdate orange, permanent orange GTR, pyrazolone orange, Benzidine orange G, cadmium red, permanent red 4R, the red calcium salt of watching, eosine lake, brilliant fuchsin 3B, manganese violet, Fast violet B, the methyl violet color lake, Prussian blue, cobalt blue, alkali blue lake, the Victoria blue color lake, phthalocyanine blue, fast sky blue, indanthrene blue BC, chrome green, chromium oxide, the green B of pigment, peacock green color lake and whole (final) yellowish green G.

In addition, when static charge image developing toner of the present invention was used as two component full-color toners, the example that following material can be used as colorant. is used for the coloring pigment of magenta toner comprises C.I. paratonere 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,21,22,23,30,31,32,37,38,39,40,41,48,49,50,51,52,53,54,55,57,58,60,63,64,68,81,83,87,88,89,90,112,114,122,123,163,202,206,207 and 209 and C.I. pigment violet 19, C.I. urn red 1,2,10,13,15,23,29 and 35.

In the present invention, above-named pigment can use separately.But, more preferably be used in combination pigment and dyestuff, thereby for the picture quality of full-colour image, improve the sharpness of pigment.The spendable in this case example that is used for pinkish red dyestuff comprises: oil-soluble dyes, for example, C.I. solvent red 1,3,8,23,24,25,27,30,49,81,82,83,84,100,109 and 121, C.I. disperse red 9, C.I. solvent purple 8,13,14,21 and 27 and C.I. disperse violet 1; And basic-dyeable fibre, C.I. alkali red 1:1,2,9,12,13,14,15,17,18,22,23,24,27,29,32,34,35,36,37,38,39,40 and C.I. alkaline purple 1,3,7,10,14,15,21,25,26,27 and 28 for example.

Other coloring pigment comprises the blue-green coloring pigment, and for example the C.I. alizarol saphirol 2,3,15,16 and 17, C.I. father-in-law's indigo plant 6, C.I. acid blue 45 and have the copper phthalocyanine of the phthalocyanine frame that is replaced by 1-5 phthalimidomethyl.

The example of yellow coloring pigment comprises C.I. pigment yellow 1,2,3,4,5,6,7,10,11,12,13,14,15,16,17,23,65,73 and 83 and C.I. father-in-law's Huang 1,3 and 20.

Above-mentioned dyestuff and pigment can use separately, or use as optional potpourri, to obtain to wish the toner of tone.Under taking environmental conservation into consideration, situation, suitably can use multiple food dye to security of human body etc.The coloring effect or the other factors that depend on hope, the content of above-mentioned colorant in toner can change on a large scale.Usually, in order to obtain best toner characteristic, promptly, under the situation of the diffusion of consider printing colorability, toner shape stability, toner etc., with respect to the adhesive resin of 100 mass parts, used colorant is generally the 0.1-60 mass parts, is preferably the 0.5-20 mass parts.

Other component of＜toner 〉

Static charge image developing toner of the present invention is except that containing above mentioned adhesive resin and colorant set exceptionally, also can contain following compound, this compound in certain content range, thereby bring adverse effect (its ratio is less than the content of binder resin component) can not for effect of the present invention.The example of this compound comprises: aliphatic hydrocrbon or alicyclic hydrocarbon resin and aromatic petroleum resin, for example, silicones, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenolic resin, low molecular weight polyethylene and low-molecular-weight polypropylene; Chlorinated paraffin; And paraffin.Wherein preferred available paraffin comprises low-molecular-weight polypropylene and accessory substance, low molecular weight polyester and ester type waxes, and aliphatic derivatives.And, use distinct methods to carry out the prepared paraffin of fractionation according to the molecular weight of these paraffin and preferably use in the present invention.In addition, after the fractionation, can carry out oxidation, block copolymerization or graft modification.

Especially, the static charge image developing toner of the present invention that contains above-mentioned paraffinic components demonstrates excellent characteristic, when carrying out the tomography observation with transmission electron microscope (TEM), show that these paraffinic components are dispersed in the adhesive resin with the island shape that is essentially sphere and/or fusiformis.

＜toner preparation processes 〉

Specific preparation method as the static charge figure charge image developing toner of the present invention with above-mentioned composition can use any known method.Static charge image developing toner of the present invention can prepare by the so-called breaking method that obtains toner, for example, adopts following method.Promptly, particularly, use mixer, for example Henschel mixer or bowl mill are to polyhydroxyalkanoatefrom, resin, for example adhesive resin, the paraffin of Jia Ruing fully mixes on demand, and use hot kneading machine, for example hot-rolling, kneader carry out fusion-kneading, or use extruder to make resin compatible with each other.Then, will be as pigment, dyestuff or the magnetic material of colorant and the adjuvant that adds on demand, for example metallic compound is dispersed or dissolved in the resin of kneading, and cooling and curing.This solid product is with for example airslide disintegrating mill or bowl mill pulverizing and sorting of comminutor, to obtain to have the static charge image developing toner of the present invention of wishing granularity then.Should note in sorting step, preferably using the more piece separator, to enhance productivity.

The also available following method of static charge image development toner of the present invention makes.That is, use solvent (aromatic hydrocarbons, for example toluene and dimethylbenzene, halogenide, for example chloroform and dichloroethylene, ketone, for example acetone and MEK, acid amides, dimethyl formamide etc. for example), with the solution form adhesive resin and polyhydroxyalkanoatefrom are mixed, and stir.Afterwards, with causing precipitation again in the mixed solution impouring water, filter solid product, drying, and use comminutor for example airslide disintegrating mill or bowl mill pulverizing, sorting afterwards obtains to have the static charge image developing toner of the present invention of wishing granularity.Should note in sorting step, preferably using the more piece separator, to enhance productivity.

In addition, static charge image development toner of the present invention also can use following so-called polymerization preparation.Promptly, in this case, mix and disperse polyhydroxyalkanoatefrom, polymerisable monomer and as pigment, dyestuff or the magnetic material of colorant, and optional crosslinking chemical, polymerization initiator, paraffin and other adjuvant, and in the presence of surfactant etc., in aqueous dispersion medium, carry out suspension polymerization, with synthetic polymerisable colored resin particle.Then, make the gained particle carry out solid-liquid separate, dry and carry out sorting as required afterwards, to obtain static charge image development toner of the present invention.

In addition, also can prepare the coloured particulate that does not contain charge adjusting agent according to the method described above, polyhydroxyalkanoatefrom can be added separately or with external additive such as colloid silicon then, and be fixed on the particle surface by mechanochemistry method etc.

(silicon dioxide external additive)

In the present invention, preferably join the toner that makes as stated above, to improve charge stability, development capability, flowability and permanance from the outside with fine silica.In this case, use by the BET method and measure through the nitrogen suction-operated, specific surface area is 20m ²/ g or bigger (especially be 30-400m ²/ g) fine silica can be brought good result.In this case, with respect to the toner-particle of 100 mass parts, the use amount of preferred fine silica is about 8 mass parts of about 0.01-, is preferably about 0.1-5 mass parts.With regard to used fine silica, for the charging property that gives the toner hydrophobicity or regulate toner, preferred use the processed dose of fine silica of handling, this treating agent is silicon varnish, multiple modified silicone resin varnish, silicone oil, multiple modified silicon oil, silane coupling agent for example, have the silane coupling agent of functional group and other organo-silicon compound of needs.These treating agents can be used as potpourri and use.

(inorganic powder)

Development capability and permanance in order to improve toner preferably add inorganic powder, for example: and metal oxide, as the oxide of magnesium, zinc, aluminium, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin and antimony; Composite metal oxide, for example calcium titanate, magnesium titanate and strontium titanates; Slaine, for example lime carbonate, magnesium carbonate and aluminium carbonate; Clay pit, for example porcelain earth; Phosphate compounds, for example apatite; Silicon compound, for example silit and silicon nitride; With the charcoal end, for example carbon black and graphite.In these materials, preferably use zinc paste, aluminium oxide, cobalt oxide, manganese dioxide, strontium titanates and magnesium titanate fine powder.

(lubricant)

In addition, also following lubricant powder can be added in the toner.The particle of lubricant powder comprises, fluororesin, for example teflon, polyvinylidene fluoride; Fluorine compounds, for example fluorocarbons; Fatty acid metal salts, for example zinc stearate; Fatty acid and derivative of fatty acid, for example fatty acid ester; And molybdenum sulfide.

＜carrier 〉

Static charge image development toner of the present invention with above-mentioned composition can be applicable in the multiple known toner; For example, it can be used as nonmagnetic toner, and it uses as the non-magnetic mono-component developer separately, or is used as magnetic two component developers with magnetic carrier, perhaps is used alone as magnetic single component developer as magnetic color tuner.In two component development methods, any traditional known carrier all can be used as carrier.Specifically, by metal, for example iron, nickel, cobalt, manganese, chromium and rare earth element, its alloy or oxide form, and particle mean size is that the surface oxidation of 20-300 μ m or non-oxide particle can be used as carrier granular.Preferred carrier used in this invention comprises above-mentioned carrier granular, and its surface-coated has the material such as styrene resin, acryl resin, silicones, fluororesin or vibrin, or these materials are sticked to wherein.

＜magnetic color tuner 〉

Static charge image developing toner of the present invention can contain magnetisable material in toner-particle, to form magnetic color tuner.In this case, magnetic material also can be used as colorant.The magnetic material that can use under this occasion comprises iron oxide, for example magnetic iron ore, haematite and ferrite; And metal, for example iron, cobalt and nickel, or the alloys and mixts that forms of these metals and other metal, other metal for example is aluminium, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium.Preferably, the magnetic material particle mean size of using among the present invention is 2 μ m or littler, more preferably from about the about 0.5 μ m of 0.1-.With respect to the adhesive resin of 100 mass parts, preferably its content in toner is the 20-200 mass parts, especially is preferably the 40-150 mass parts.

In addition, in order to obtain very high picture quality, need and truly to develop to meticulousr latent image dots., for example, preferably static charge image development correctives particle of the present invention is regulated, be 4 μ m-9 μ m thereby make its average particle size for this reason.That is to say, the toner-particle average particle size is undesirable less than 4 μ m, because use this toner can make the image transfer efficiency be tending towards descending, and the toner in many not transfer printings after the transfer printing is easy to be retained on the light activated element, and this will cause the inhomogeneous of image because of forming fog/transfer printing failure.If the average particle size of toner-particle surpasses 9 μ m, the trend that character or line chart dispersion take place is arranged then.

In the present invention, use Coulter Counter TA-II or Coulter Multisizer (by Beckman Coulter, Inc. manufacturing) particle mean size and the size-grade distribution of measurement toner, above-mentioned instrument and interfacing equipment (Nikkaki Bios Co., Ltd) be connected with PC, be used for exporting digital distribution and volume distributed median.Electrolyte as using in measuring adopts the 1%NaCl aqueous solution by grade sodium chloride preparation.As electrolyte, also can use, for example, the ISOTON R-II of commercially available acquisition (making) by Coulter Scientific Japan Co..Specifically,, 0.1-5ml is joined in the 100-150ml electrolytic solution as the surfactant (preferred alkyl benzene sulfonate) of spreading agent and other 2-20mg measurement sample, measure sample with preparation in order to measure.In measuring process, with ultrasonic decollator the suspending liquid that the measurement sample is dissolved in gained in the electrolytic solution was carried out the about 1-3 of dispersion treatment minute, using the aperture then is volume and the quantity that the above-mentioned Coulter Counter TA-II of 100 μ m measures the toner-particle that is equal to or greater than 2 μ m, distributes and distributed number in order to volume calculated.Then, draw equal granularity of volume-basic weight of the present invention (D4) and the long equal granularity (D1) of quantity-Ji respectively from volume distributed median and distributed number.

＜the quantity of electric charge 〉

Improve transfer efficiency in the printing transferring method for the transferring member that applies voltage in use, preferred static charge image development toner of the present invention has the quantity of electric charge (two component method) of per unit mass-10--80 μ C/g, more preferably-and 15--70 μ C/g.

Utilize the method for the two component methods mensuration quantities of electric charge (two component triboelectric charge amounts) that use among the present invention as described below.Use quantity of electric charge measurement mechanism shown in Figure 7 in the measurement.At first, under certain environment, with EFV 200/300 (the Powdertech Co. of 9.5g as carrier, Ltd. preparation) and the potpourri of the toner that will measure of 0.5g join in the polyethylene bottle of 50-100ml capacity, then this volumetric flask is placed on predetermined a period of time of vibration on the oscillator, the oscillating condition of this oscillator is set at fixed ampllitude 100mm, oscillation rate be impact for 100 times/minute.Then the 1.0-1.2g potpourri is added in the metal measuring vessel 42 (by the metal manufacturing), this canister has 500 eye mesh screens 43 that are positioned at quantity of electric charge measurement mechanism bottom as shown in Figure 7, and this container is covered by crown cap 44.Gross mass to measuring vessel 42 is measured, and represents with W1 (g).Operate air exhauster (not shown) (being insulator with measuring vessel 42 contacted parts at least in this air exhauster) then, aspirate, by regulating control damper the pressure of vacuum meter 45 is adjusted to 2,450Pa (250mmAq) simultaneously by inlet hole 47.In this state, continue to aspirate 1 minute to remove toner.This moment, the voltage number of voltage table 49 was represented with V (volt).Herein, reference number 48 refers to have the capacitor of capacitor C (μ F).The suction back is measured the gross mass of measurement mechanism, and represents with W2 (g).Calculate the triboelectric charge amount (μ C/g) of toner according to following formula:

Triboelectric charge amount (μ C/g)=C * V/ (W1-W2).

The molecular weight distribution of＜adhesive resin 〉

Preferably, the adhesive resin that is used as static charge image developing toner composition material of the present invention shows 3 in the GPC molecular weight distribution, 000-15, and 000 peak, low-molecular-weight zone is especially when utilizing comminuting method to prepare.That is to say that if the GPC peak in the low-molecular-weight zone surpasses 15,000, then transfer efficiency improves insufficient in some cases.On the other hand, the adhesive resin that has the GPC peak in less than 3,000 low-molecular-weight zone is not preferred yet, because it is tending towards merging when surface treatment.

In the present invention, use GPC (gel permeation chromatography) to measure the molecular weight of adhesive resin.Use the concrete grammar of GPC determining molecular weight to comprise the following steps: to use the Soxhlet extractor, extracted toner in advance 20 hours with THF (tetrahydrofuran) solvent, and the gained sample is used to measure molecular weight, use A-801,802,803,804,805,806 and 807 posts (making) of polyphone in the molecular weight measurement, and use the calibration curve of polystyrene standard resin by Showa Denko K.K..In the present invention, preferably use the adhesive resin of the ratio (Mw/Mn) of institute's check weighing average molecular weight (Mw) and number-average molecular weight (Mn) as 2-100.

The vitrifying point of＜toner 〉

Preferably, consider photographic fixing character and shelf-life, use suitable material preparation toner of the present invention, making its vitrifying point Tg is 40-75 ℃, more preferably 52-70 ℃.In this case, use hot differential scanning calorimeter in the high precision input offset type, for example, the DSC-7 that PerkinElmer Inc. makes measures the vitrifying point Tg of toner according to ASTM D 3418-82.In the present invention, when measuring vitrifying point Tg, the temperature of sample to be tested is once raise, to write down all thermal hysteresis, and cooling rapidly then.With 10 ℃/minute heating rate specimen temperature is increased to 0-200 ℃ again.Can suitably use the DSC curve that obtains according to the measurement result under these conditions.

＜formation method and device 〉

Static charge image developing toner of the present invention with above-mentioned composition particularly preferably is used in a kind of formation method, and this formation method comprises the steps: to make the charged charge step of electrostatic latent image load-carrying unit by applying voltage from the outside to charge member at least; On charged electrostatic latent image load-carrying unit, form the step of electrostatic image; Use toner on the electrostatic latent image load-carrying unit, to form toner image, thereby make the development step of electrostatic image development; Toner image on the electrostatic latent image load-carrying unit is transferred to transfer step on the recording materials; Hot photographic fixing step with hot this toner image of photographic fixing on recording medium.Selectable, toner of the present invention particularly preferably can be used in a kind of formation method, in this formation method, transfer step comprises the toner image on the electrostatic latent image load-carrying unit is transferred to first transfer step of intermediate transfer element and the toner image on the intermediate transfer element is transferred to second transfer step on the recording medium.

Embodiment

Hereinafter reference example is explained in more detail the present invention, but the present invention should not be understood that only for therewith.

Reference example A

Prepare 20 and shake bottle (capacity 500mL), poly-peptone (Wako PureChemical Industries with 0.5wt%, Ltd.), the 5-phenylpentanoic acid of 6mmol/L and the 10-undecenoic acid of 2mmol/L be dissolved in the above-mentioned M9 nutrient culture media of 200mL, then potpourri is placed on each 500-mL and shakes in the bottle.Shake bottle and in autoclave, sterilize, and be cooled to room temperature.(2mL) joins in the gained nutrient culture media with nutrient solution, and in this nutrient solution, and Pseudomonas cichorii strain YN2 is shaken cultivation 8 hours in advance in the M9 nutrient culture media that contains 0.5% poly-peptone, adds the back and cultivates 64 hours down at 30 ℃.After cultivate finishing, with each culture solution centrifugal collecting cell of putting together.With methanol wash cell and dry.After measuring the weight of dried cellular, to wherein adding chloroform.Then, under 35 ℃, stirred the mixture 72 hours, in order to the extraction polymkeric substance.Use membrane filter (0.45 μ m) to filter out the chloroform that has extracted polymkeric substance, use the evaporator concentrating filtrate then, in cold methanol, precipitate again afterwards, thereby reclaim this polymkeric substance.This polymkeric substance of drying under reduced pressure is to obtain subject polymer then.

Measure the weight of the weight (dry cell weight) of freeze drying cell as resulting polymers.In this embodiment, obtain 2,708mg PHA (dry weight).

Use gel permeation chromatography (GPC device; Tosoh HLC-8220, post; TosohTSK-GEL Super HM-H, solvent; Chloroform is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 124,000, and weight-average molecular weight (Mw) is 242,000.

In addition, for the structure of clear and definite gained PHA, under following condition, carried out the NMR analysis.

＜measurement mechanism 〉

FT-NMR：Bruker?DPX400

Resonant frequency: ¹H=400MHz

＜measuring condition 〉

Measure nucleic: ¹H

Solvent for use: TMS/CDCl ₃

Measure temperature: room temperature

According to the result, find that gained PHA is a pha copolymer, its 3-hydroxyl-5-phenylpentanoic acid (A unit), 3-hydroxyl-10-undecenoic acid (B unit), 3-hydroxyl-8-nonenoic acid (C unit) and 3-hydroxyl-6-heptenoic acid (D unit) that contains following chemical formula (32) representative is as monomeric unit.

In addition, by ¹The H-NMR spectrum is determined the number percent of each unit.According to this result, find that hydroxyl-5-phenylpentanoic acid (A unit) is 81mol% to 3-, the summation of 3-hydroxyl-10-undecenoic acid, 3-hydroxyl-8-nonenoic acid and 3-hydroxyl-6-heptenoic acid Unit three (B unit+C unit+D unit) is 15mol%, and other compound (the straight chain 3-hydroxyl alkane acid and the 3-hydroxyl chain-5-olefin(e) acid that contains 10 or 12 carbon atoms that contain 4-12 carbon atom) is 4mol%.

According to this result, find that this PHA contains the 3-hydroxyl-ω-chain acid ester unit of chemical formula (24) representative.

The polyhydroxyalkanoatefrom of gained is used in the following reaction among this embodiment.

With 1,000mg PHA joins in the 500mL eggplant type flask, adds the 65mL methylene chloride then with dissolving PHA.This flask is placed in the ice bath, is preced with-6 ethers to wherein adding 11mL acetate and 680mg 18-, and stirs the gained potpourri.Subsequently, 540mg potassium permanganate is slowly joined in the flask in the ice bath, and at room temperature stirred the mixture 20 hours.Reaction adds to 50mL water and sodium bisulfite in this flask after finishing.Then, use 1.0mol/L (1.0N) hydrochloric acid with potpourri pH regulator to 1.Distill out methylene chloride in the mixture solution with evaporator, reclaim the polymkeric substance in the solution afterwards.With 150mL ethanol washing copolymer, further wash three times with the 150mL pure water again, reclaim polymkeric substance afterwards.The drying under reduced pressure polymkeric substance, thus 920mg target P HA obtained.

Use gel permeation chromatography (GPC device; Tosoh HLC-8220, post; TosohTSK-GEL Super HM-H, solvent; Chloroform is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 81,000, and weight-average molecular weight (Mw) is 92,000.

For the structure of clear and definite gained PHA, carry out NMR under these conditions and analyze.

According to the result, find that this PHA is a kind of pha copolymer, its 3-hydroxyl-5-carboxyl valeric acid that contains the 3-hydroxyl-7-carboxyl enanthic acid of 3-hydroxyl-9-carboxyl n-nonanoic acid, chemical formula (35) representative of 3-hydroxyl-5-phenylpentanoic acid, chemical formula (34) representative of following chemical formula (33) representative and chemical formula (36) representative is as monomeric unit.

And, with trimethyl silyl (TMS) diazomethane the carboxyl at PHA side chain terminal place is carried out the esterification effect, to determine the number percent of each unit among the gained PHA.

50mg target P HA is added in the 100-mL eggplant type flask, add the 3.5mL chloroform afterwards and 0.7mL methyl alcohol dissolves this PHA.Then, (0.63mol/L, Tokyo Kasei Kogyo Co. Ltd.) adds in this flask, and at room temperature stirs the mixture 30 minutes with 2mL TMS diazomethane-hexane solution.Reaction is used the evaporator distilling off solvent after finishing, and reclaims polymkeric substance then.With 50mL methanol wash resulting polymers, reclaim polymkeric substance afterwards.This polymkeric substance of drying under reduced pressure is to obtain 49mg PHA.

Carry out NMR according to the mode that is similar to said method and analyze, to determine the number percent of each unit.According to this result, find that hydroxyl-the 5-phenylpentanoic acid is 92mol% to 3-, the total amount of 3-hydroxyl-9-carboxyl n-nonanoic acid, 3-hydroxyl-7-carboxyl enanthic acid and 3-hydroxyl-5-carboxyl valeric acid Unit three is 7mol%, and other compound (the straight chain 3-hydroxyl alkane acid and the 3-hydroxyl chain-5-olefin(e) acid that contains 10 or 12 carbon atoms that contain 4-12 carbon atom) is 1mol%.

Embodiment A-1

Under blanket of nitrogen, the polymkeric substance that contains 7mol%3-hydroxyl-ω-carboxyl alkanoate unit and the 22.9mg para-totuidine-2-sulfonic acid that obtains among the 200mg reference example A is placed in the 50-mL two-neck bottle, and adds the 10mL pyridine, stir afterwards.Subsequently, to wherein adding the 0.22mL triphenyl phosphite, and 100 ℃ of following heating blends 6 hours.Reaction precipitates with EtOH after finishing again, and this sediment of centrifugal recovery.Resulting polymers is stirred 3 days to wash in water, washed again 1 day with 1N hydrochloric acid, and under vacuum dry 1 day.

Use gel permeation chromatography (GPC; Tosoh HLC-8020, post; Polymkeric substance laboratory Mixed-C, solvent; The DMF that contains 0.1%LiBr is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 28,000.

With Fourier transform-infrared absorption (FT-IR) spectrum and ¹H-NMR analyzes the structure of resulting polymers.

According to the analysis result of Fourier transform-infrared absorption (FT-IR) spectrum (Nicolet AVATAR 360FT-IR), find that ownership is 1 of carboxylic acid, 693cm ^-1The peak reduces, and is 1 of amide group, 668cm and ownership occurred ^-1New peak.Fig. 8 has shown the FT-IR spectrum of resulting polymers.

And, according to resulting polymers ¹(FT-NMR:BrukerDPX 400 for the H-NMR analysis result; Resonant frequency: 400MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature), find that ownership for the peak of the methyl of para-totuidine-2-sulfonic acid migration has taken place, and be higher than the peak of ownership for the methyl of para-totuidine-2-sulfonic acid in the raw material.As a result, find that gained PHA contains the unit of chemical formula (7B) representative.

In addition, use Dia Instruments Co., the sulphur content analysis apparatus " TS-100 " that Ltd. makes is by the amount of " oxidation destruction-Ultraluminescence analytic approach " mensuration sulphur.As a result, find that gained PHA is a kind of pha copolymer, it contains 4.9mol% para-totuidine-2-sulfonic acid group.

Adopt large-scale producing method to obtain the 50g pha copolymer, and with this compound as example compound A-1, carry out the preparation and the assessment thereof of toner.

Embodiment A-2

Repeat the step of embodiment A-1, just replace the 22.9mg para-totuidine-2-sulfonic acid in the embodiment A-1, thereby obtain the 84mg polymkeric substance with 27.3mg 2-amino-1-naphthalene sulfonic aicd.

As shown in Figure 8,, be the new peak of amide group and ownership occurred owing to the peak of ownership for carboxylic acid reduces, so FT-IR demonstration formation amido link.Find that gained PHA contains the unit of chemical formula (8A) representative.

Analyze the mean molecular weight of gained PHA according to the mode that is similar to embodiment A-1.The number-average molecular weight of PHA (Mn) is 27,500.And, according to the measurement result of sulfur content, find that gained PHA is the pha copolymer that contains 4.7mol% 2-amino-1-naphthalene sulfonic aicd group.

Adopt large-scale producing method to obtain the 50g pha copolymer, and with this compound as example compound A-2, carry out the preparation and the assessment thereof of toner.

Embodiment A-3

Repeat the step of embodiment A-1,, thereby obtain the 76mg polymkeric substance just with the 22.9mg para-totuidine-2-sulfonic acid in the 21.2mg 4-amino phenyl sulfonyl acid substitution embodiment A-1.

As shown in Figure 8,, be the new peak of amide group and ownership occurred owing to the peak of ownership for carboxylic acid reduces, so FT-IR demonstration formation amido link.Find that gained PHA contains the unit of chemical formula (7A) representative.

Analyze the mean molecular weight of gained PHA according to the mode that is similar to embodiment A-1.The number-average molecular weight of PHA (Mn) is 29,300.And, according to the measurement result of sulfur content, find that gained PHA is the pha copolymer that contains 4.5mol%4-amino phenyl sulfonyl acid groups.

Adopt large-scale producing method to obtain the 50g pha copolymer, and with this compound as example compound A-3, carry out the preparation and the assessment thereof of toner.

Embodiment A-4

The PHA that obtains in the 100mg embodiment A-2 is joined in the 200-mL eggplant type flask, add the 7mL chloroform afterwards and 1.4mL methyl alcohol dissolves this PHA.Then, (0.63mol/L, Tokyo Kasei Kogyo Co. Ltd.) adds in this flask, and at room temperature stirs the mixture 30 minutes with 2mL TMS diazomethane-hexane solution.Reaction is used the evaporator distilling off solvent after finishing, and reclaims polymkeric substance then.With 50mL methanol wash resulting polymers, reclaim polymkeric substance afterwards.This polymkeric substance of drying under reduced pressure obtains 70mg PHA.

For the structure of clear and definite gained PHA, analyze with FT-IR.

As a result, because ownership is for sulfonic 1,190cm ^-1With 1,059cm ^-1The peak migrates to ownership and is 1 of methylmesylate, 370cm ^-1With 1,176cm ^-1Therefore the peak judges that gained PHA is the PHA of esterification.

And, show that also sulfonic acid has become methylmesylate, because use potentiometric titrimeter (AT-510, by Kyoto Electronics Manufacturing, Co., Ltd makes) not find to belong to peak when carrying out acid number titration for sulfonic acid.

Adopt large-scale producing method to obtain the 50g pha copolymer, and with this compound as example compound A-4, carry out the preparation and the assessment thereof of toner.

Embodiment A-5

Repeat the step of embodiment A-1,, thereby obtain the 80mg polymkeric substance just with the 22.9mg para-totuidine-2-sulfonic acid in the 30.7mg 2-amino phenyl sulfonyl acid phenenyl ester replacement embodiment A-1.

As shown in Figure 8,, be the new peak of amide group and ownership occurred owing to the peak of ownership for carboxylic acid reduces, so FT-IR demonstration formation amido link.Simultaneously, found that ownership is 1 of phenyl sulfonate, 375cm ^-1With 1,193cm ^-1The peak.As a result, find that gained PHA contains the unit of chemical formula (7B) representative.

Analyze the mean molecular weight of gained PHA according to the mode that is similar to embodiment A-1.The number-average molecular weight of PHA (Mn) is 31,400.And, according to the measurement result of sulfur content, find that gained PHA is the pha copolymer that contains 4.5mol% 2-aminobenzenesulfonic acid phenyl ester group.

Adopt large-scale producing method to obtain the 50g pha copolymer, and with this compound as example compound A-5, carry out the preparation and the assessment thereof of toner.

Embodiment A-6

Repeat the step of embodiment A-1,, thereby obtain the 71mg polymkeric substance just with the 22.9mg para-totuidine-2-sulfonic acid in the 30.7mg 2-amino-2-methyl propane sulfonic acid replacement embodiment A-1.

By ¹H-NMR (FT-NMR:Bruker DPX 400; Resonant frequency: 400MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature) and Fourier transform-infrared absorption (FT-IR) compose (Nicolet AVATAR 360 FT-IR) resulting polymers analyzed, with clear and definite its structure.

As shown in Figure 8,, be the new peak of amide group and ownership occurred owing to the peak of ownership for carboxylic acid reduces, so FT-IR demonstration formation amido link.Determine that gained PHA contains the unit of chemical formula (7B) representative.

In addition, according to resulting polymers ¹H-NMR result finds that gained PHA is the polyhydroxy alkanoate copolymer that contains 2-amino-2-methyl propane sulfonic acid group, because ownership because of the introducing of 2-amino-2-methyl propane sulfonic acid migration has taken place for the 1.5ppm peak of methyl.

And, according to the measurement result of sulfur content, find that gained PHA is the pha copolymer that contains 5mol% 2-amino-2-methyl propane sulfonic acid group.

Use gel permeation chromatography (GPC device; Tosoh HLC-8020, post; Polymkeric substance laboratory Plgel 5 μ MIXED-C, solvent; DMF/LiBr 0.1% (w/v) is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 27,600, and weight-average molecular weight (Mw) is 31,000.

Embodiment A-7

The PHA that obtains in the 30mg embodiment A-6 is joined in the 100-mL eggplant type flask, add the 3mL chloroform afterwards and 0.6mL methyl alcohol dissolves this PHA, and potpourri is cooled to 0 ℃.Then, (2mol/L, by Aldrich Co., Ltd. prepares) adds in this flask with 0.8mL trimethyl silyl diazomethane-hexane solution, and stirs the mixture 4 hours.Reaction is used the evaporator distilling off solvent after finishing, and reclaims polymkeric substance.

And, chloroform and methyl alcohol are added in the flask, with dissolve polymer once more.Use the evaporator distilling off solvent then.This step is repeated 3 times.

The polymkeric substance that drying under reduced pressure reclaims herein, thus 24mgPHA obtained.

By ¹H-NMR (FT-NMR:Bruker DPX 400; Resonant frequency: 400 MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature) resulting polymers is analyzed, with clear and definite its structure.According to ¹H-NMR result is owing to found that at the 3-4ppm place ownership is the peak of methylmesylate, therefore judges that gained PHA is the polyhydroxy alkanoate copolymer that contains 5mol% 2-amino-2-methyl propane sulfonic acid ester group.

And, show that also sulfonic acid has become methylmesylate, because use potentiometric titrimeter (AT-510, by Kyoto Electronics Manufacturing, Co., Ltd makes) not find to belong to peak when carrying out acid number titration for sulfonic acid.

Use gel permeation chromatography (GPC device; Tosoh HLC-8020, post; Polymkeric substance laboratory PLgel 5 μ MIXED-C, solvent; DMF/LiBr 0.1% (w/v) is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 24,000, and weight-average molecular weight (Mw) is 30,000.

Embodiment A-8

Repeat the step of embodiment A-1,, thereby obtain the 78mg polymkeric substance just with the 22.9mg para-totuidine-2-sulfonic acid in the 21.1mg 2-amino phenyl sulfonyl acid substitution embodiment A-1.

By ¹H-NMR (FT-NMR:Bruker DPX 400; Resonant frequency: 400MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature) and Fourier transform-infrared absorption (FT-IR) compose (Nicolet AVATAR 360 FT-IR) resulting polymers analyzed, with clear and definite its structure.

According to ¹H-NMR result has found that at about 7.7 and 8.5 places ownership is the peak of aromatic ring, therefore judges that gained PHA is the polyhydroxy alkanoate copolymer that contains 2-amino phenyl sulfonyl acid groups owing to the introducing of 2-aminobenzenesulfonic acid.As shown in Figure 8,, and ownership occurred and be the new peak of amide group, so FT-IR shows the PHA of gained PHA for the unit that contains chemical formula (7B) and represent, and formed amido link in this unit because ownership reduces for the peak of carboxylic acid.For mean molecular weight, the number-average molecular weight of PHA (Mn) is 27,700.And, according to the measurement result of sulfur content, find that gained PHA is the pha copolymer that contains 4.7mol% 2-amino phenyl sulfonyl acid groups.

Adopt large-scale producing method to obtain the 50g pha copolymer, and with this compound as example compound A-8, carry out the preparation and the assessment thereof of toner.

Embodiment A-9

The PHA that obtains in the 1.00g embodiment A-8 is joined in the 300-mL eggplant type flask, add the 70mL chloroform afterwards and 17mL methyl alcohol dissolves this PHA, and potpourri is cooled to 0 ℃.Then, (2mol/L, by Aldrich Co., Ltd. prepares) adds in this flask with 27mL trimethyl silyl diazomethane-hexane solution, and stirs the mixture 4 hours.Reaction is used the evaporator distilling off solvent after finishing, and reclaims polymkeric substance.

And, chloroform and methyl alcohol are added in the flask, with dissolve polymer once more.Use the evaporator distilling off solvent then.This step is repeated 3 times.

The polymkeric substance that drying under reduced pressure reclaims herein, thus 0.88g PHA obtained.

By ¹H-NMR (FT-NMR:Bruker DPX 400; Resonant frequency: 400 MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature) resulting polymers is analyzed, with clear and definite its structure.According to ¹H-NMR result judges that gained PHA is the polyhydroxy alkanoate copolymer that contains 4mol% 2-aminobenzenesulfonic acid methyl esters group.

And, show that also sulfonic acid has become methylmesylate, because use potentiometric titrimeter (AT-510, by Kyoto Electronics Manufacturing, Co., Ltd makes) not find to belong to peak when carrying out acid number titration for sulfonic acid.

Use gel permeation chromatography (GPC device; Tosoh HLC-8020, post; Polymkeric substance laboratory PLgel 5 μ MIXED-C, solvent; DMF/LiBr 0.1% (w/v) is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 24,000, and weight-average molecular weight (Mw) is 31,000.

Embodiment A-10

Under blanket of nitrogen, polymkeric substance and the 594mg 4-aminoanisole-2-sulfonic acid that obtains among the 1.5g reference example A is placed in the 100-mL three-neck flask, and the 57mL pyridine is joined in the flask.After stirring the mixture, the 1.5mL triphenyl phosphite is joined in the flask, and 100 ℃ of following heating blends 6 hours.Reaction precipitates with ethanol again, and reclaims this sediment after finishing.Resulting polymers is stirred 5.5 hours washing in pure water, and this polymkeric substance of filtered and recycled.Drying under reduced pressure is dissolved in desciccate among the 150mlTHF after this leaches thing.Then, with potpourri and 150ml 1N mixed in hydrochloric acid and stirring.After 13 hours, distill out THF in the mixed solution, reclaim the polymkeric substance in the solution then with evaporator.

By ¹H-NMR (FT-NMR:Bruker DPX 400; Resonant frequency: 400MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature) and Fourier transform-infrared absorption (FT-IR) compose (Nicolet AVATAR 360 FT-IR) resulting polymers analyzed, with clear and definite its structure.

According to ¹H-NMR result has found that at the 8.4ppm place ownership is the peak of aromatic ring, therefore judges that gained PHA is the polyhydroxy alkanoate copolymer that contains 5mol%4-aminoanisole-2-sulfonic acid group owing to the introducing of 4-aminoanisole-2-sulfonic acid group.The IR measurement result shows, belongs to the peak 1 for carboxylic acid, 693cm ^-1Reduce, be the new peak 1 of amide group, 669cm and ownership occurred ^-1Find that gained PHA is the PHA that contains the unit of chemical formula (7B) representative.

Use gel permeation chromatography (GPC; Tosoh HLC-8020, post; Polymkeric substance laboratory PLgel 5 μ MIXED-C, solvent; DMF/LiBr 0.1% (w/v) is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 36,000, and weight-average molecular weight (Mw) is 49,000.

Embodiment A-11

The PHA that obtains in the 0.90g embodiment A-10 is joined in the 300-mL eggplant type flask, add the 70mL chloroform afterwards and 17.5mL methyl alcohol dissolves this PHA, and potpourri is cooled to 0 ℃.Then, (2mol/L, by Aldrich Co., Ltd. prepares) adds in this flask with 28mL trimethyl silyl diazomethane-hexane solution, and stirs the mixture 4 hours.Reaction is used the evaporator distilling off solvent after finishing, and reclaims polymkeric substance.

And, chloroform and methyl alcohol are added in the flask, with dissolve polymer once more.Use the evaporator distilling off solvent then.This step is repeated 3 times.

The polymkeric substance that drying under reduced pressure reclaims herein, thus 0.83g PHA obtained.

By ¹H-NMR (FT-NMR:Bruker DPX 400; Resonant frequency: 400 MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature) resulting polymers is analyzed, with clear and definite its structure.According to ¹H-NMR result is owing to find that at the 3-4ppm place ownership is the peak of methylmesylate, therefore judges that gained PHA is the polyhydroxy alkanoate copolymer that contains 5mol% 4-aminoanisole-2-methylmesylate group.

And, show that also sulfonic acid has become methylmesylate, because use potentiometric titrimeter (AT-510, by Kyoto Electronics Manufacturing, Co., Ltd makes) not find to belong to peak when carrying out acid number titration for sulfonic acid.

Use gel permeation chromatography (GPC device; Tosoh HLC-8020, post; Polymkeric substance laboratory Plgel 5 μ MIXED-C, solvent; DMF/LiBr 0.1% (w/v) is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 33,000, and weight-average molecular weight (Mw) is 43,000.

Embodiment A-12

Under blanket of nitrogen, polymkeric substance and the 650mg naphthalidine-8-sulfonic acid that obtains among the 1.5g reference example A is placed in the 100-mL three-neck flask, and the 56.5mL pyridine is joined in the flask.After stirring the mixture, the 1.5mL triphenyl phosphite is joined in the flask, and 100 ℃ of following heating blends 6 hours.Reaction precipitates with ethanol again, and reclaims this sediment after finishing.Resulting polymers is stirred 5.5 hours washing in pure water, and this polymkeric substance of filtered and recycled.Drying under reduced pressure is dissolved in desciccate among the 150mlTHF after this leaches thing.Then, with potpourri and 150ml 1N mixed in hydrochloric acid and stirring.Behind the aforesaid operations 14 hours, distill out THF in the mixed solution, reclaim the polymkeric substance in the solution then with evaporator.

By ¹H-NMR (FT-NMR:Bruker DPX 400; Resonant frequency: 400MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature) and Fourier transform-infrared absorption (FT-IR) compose (Nicolet AVATAR 360 FT-IR) resulting polymers analyzed, with clear and definite its structure.

The IR measurement result shows, belongs to peak 1,693 cm for carboxylic acid ^-1Reduce, and ownership occurred and be the new peak 1 of amide group, 670cm ^-1Find that gained PHA contains the unit of chemical formula (7B) representative.

According to ¹H-NMR result is because therefore ownership judges that gained PHA is the polyhydroxy alkanoate copolymer that contains naphthalidine-8-sulfonic acid group for moving at the peak of naphthyl.

Find that gained PHA contains the unit of chemical formula (8B) representative.Use gel permeation chromatography (GPC; Tosoh HLC-8020, post; Polymkeric substance laboratory PLgel 5 μ MIXED-C, solvent; DMF/LiBr 0.1% (w/v) is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 29,000, and weight-average molecular weight (Mw) is 40,000.

Embodiment A-13

The PHA that obtains in the 1.00g embodiment A-12 is joined in the 300-mL eggplant type flask, add the 70mL chloroform afterwards and 17mL methyl alcohol dissolves this PHA, and potpourri is cooled to 0 ℃.Then, (2mol/L, by Aldrich Co., Ltd. prepares) adds in this flask with 27mL trimethyl silyl diazomethane-hexane solution, and stirs the mixture 4 hours.Reaction is used the evaporator distilling off solvent after finishing, and reclaims polymkeric substance.

And, chloroform and methyl alcohol are added in the flask, with dissolve polymer once more.Use the evaporator distilling off solvent then.This step is repeated 3 times.

The polymkeric substance that drying under reduced pressure reclaims herein, thus 0.87g PHA obtained.

By ¹H-NMR (FT-NMR:Bruker DPX 400; Resonant frequency: 400 MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature) resulting polymers is analyzed, with clear and definite its structure.According to ¹H-NMR result is owing to find that at the 3-4ppm place ownership is the peak of methylmesylate, therefore judges that gained PHA is the polyhydroxy alkanoate copolymer that contains naphthalidine-8-methylmesylate group.

And, show that also sulfonic acid has become methylmesylate, because use potentiometric titrimeter (AT-510, by Kyoto Electronics Manufacturing, Co., Ltd makes) not find to belong to peak when carrying out acid number titration for sulfonic acid.

Use gel permeation chromatography (GPC device; Tosoh HLC-8020, post; Polymkeric substance laboratory PLgel 5 μ MIXED-C, solvent; DMF/LiBr 0.1% (w/v) is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 29,000, and weight-average molecular weight (Mw) is 43,000.

Embodiment A-14

At first, 10.0g 2-amino-1-naphthalene sulfonic aicd (by Tokyo Kasei Kogyo Co., the Ltd. preparation) is joined in the 2L eggplant type flask.Add 1 then, 400mL chloroform and 460mL methyl alcohol dissolve this compound, and potpourri is cooled to 0 ℃.Subsequently, (2mol/L, by Aldrich Co., Ltd. prepares) adds in this flask with 113mL trimethyl silyl diazomethane-hexane solution, and stirs the mixture 2 hours.After reaction finishes, filter the gained potpourri, and remove the crystallization that is precipitated out in the course of reaction, thereby reclaim the thing that leaches that contains target product 2-amino-1-naphthalene sulfonic aicd methyl esters.Distill out the solvent in the solution that contains 2-amino-1-naphthalene sulfonic aicd methyl esters with evaporator, and reclaim crude product.

The crude product that obtains in this way with the silica gel column chromatography purifying, thus 2.45g 2-amino-1-naphthalene sulfonic aicd methyl esters obtained.

By ¹H-NMR (FT-NMR:Bruker DPX 400; Resonant frequency: 400 MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature) resulting polymers is analyzed, with clear and definite its structure.According to ¹H-NMR result finds that the gained compound is 2-amino-1-naphthalene sulfonic aicd methyl esters.

Next, under blanket of nitrogen, 2-amino-1-naphthalene sulfonic aicd methyl esters that the polymkeric substance that obtains among the 1.50g reference example A and 695mg are obtained above is placed in the 100-mL three-neck flask, and the 56mL pyridine is joined in the flask.After stirring the mixture, the 1.5mL triphenyl phosphite is joined in the flask, and 100 ℃ of following heating blends 6 hours.Reaction precipitates with ethanol again, and reclaims this sediment after finishing.Resulting polymers is stirred 2 hours washing in pure water, and this polymkeric substance of filtered and recycled.Drying under reduced pressure is dissolved in desciccate among the 150ml THF after this leaches thing.Then, with potpourri and 150ml 1N mixed in hydrochloric acid and stirring.After 14 hours, distill out THF in the mixed solution, reclaim the polymkeric substance in the solution then with evaporator.

By ¹H-NMR (FT-NMR:Bruker DPX 400; Resonant frequency: 400MHz; Measure nucleic: ¹H; Solvent for use: deuterate DMSO; Measure temperature: room temperature) and Fourier transform-infrared absorption (FT-IR) compose (Nicolet AVATAR 360 FT-IR) resulting polymers analyzed, with clear and definite its structure.

The IR measurement result shows, belongs to the peak 1 for carboxylic acid, 693cm ^-1Reduce, and ownership occurred and be the new peak 1 of amide group, 670cm ^-1

According to ¹H-NMR result is the pha copolymer that contains the PHA of the unit that chemical formula (8A) represents and contain 6mol% 2-amino-1-naphthalene sulfonic aicd methyl esters group because ownership, is therefore judged gained PHA for moving at the peak of naphthyl.

Use gel permeation chromatography (GPC device; Tosoh HLC-8020, post; Polymkeric substance laboratory PLgel 5 μ MIXED-C, solvent; DMF/LiBr 0.1% (w/v) is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 33,000, and weight-average molecular weight (Mw) is 43,000.

Reference example B

Prepare 20 and shake bottle (capacity 500mL), poly-peptone (Wako PureChemical Industries with 0.5wt%, Ltd.), the 5-phenoxy group valeric acid of 6mmol/L and the 10-undecenoic acid of 3.75mmol/L be dissolved in the above-mentioned M9 nutrient culture media of 200mL, then potpourri is placed on each 500-mL and shakes in the bottle.Shake bottle and in autoclave, sterilize, and be cooled to room temperature.(2mL) joins in the gained nutrient culture media with nutrient solution, and in this nutrient solution, and Pseudomonas cichorii strain YN2 is shaken cultivation 8 hours in advance in the M9 nutrient culture media that contains 0.5% poly-peptone, adds the back and cultivates 64 hours down at 30 ℃.After cultivate finishing, with each culture solution centrifugal collecting cell of putting together.With methanol wash cell and dry.After measuring the weight of dried cellular, to wherein adding chloroform.Then, under 35 ℃, stirred the mixture 72 hours, in order to the extraction polymkeric substance.Use membrane filter (0.45 μ m) to filter out the chloroform that has extracted polymkeric substance, use the evaporator concentrating filtrate then, in cold methanol, precipitate again afterwards, to reclaim this polymkeric substance.This polymkeric substance of drying under reduced pressure is to obtain subject polymer then.

Measure the weight of the weight (dry cell weight) of freeze drying cell as resulting polymers.In this embodiment, obtain 1,528mg PHA (dry weight).

Use gel permeation chromatography (GPC; Tosoh HLC-8220, post; TosohTSK-GEL Super HM-H, solvent; Chloroform is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 104,000, and weight-average molecular weight (Mw) is 231,000.

In addition, for the structure of clear and definite gained PHA, under following condition, carried out the NMR analysis.

＜measurement mechanism 〉

FT-NMR：Bruker?DPX400

Resonant frequency: ¹H=400MHz

＜measuring condition 〉

Measure nucleic: ¹H

Solvent for use: TMS/CDCl ₃

Measure temperature: room temperature

According to the result, find that gained PHA is a kind of pha copolymer, its 3-hydroxyl-5-phenoxy group valeric acid (A unit), 3-hydroxyl-10-undecenoic acid (B unit), 3-hydroxyl-8-nonenoic acid (C unit) and 3-hydroxyl-6-heptenoic acid (D unit) that contains following chemical formula (37) representative is as monomeric unit.

In addition, by ¹The H-NMR spectrum is determined the number percent of each unit.According to this result, find that hydroxyl-5-phenoxy group valeric acid (A unit) is 69mol% to 3-, the total amount (B+C+D) of 3-hydroxyl-10-undecenoic acid, 3-hydroxyl-8-nonenoic acid and 3-hydroxyl-6-heptenoic acid Unit three is 23mol%, and other compound (the straight chain 3-hydroxyl alkane acid and the 3-hydroxyl chain-5-olefin(e) acid that contains 10 or 12 carbon atoms that contain 4-12 carbon atom) is 8mol%.

According to this result, find that this PHA contains the 3-hydroxyl-ω-chain acid ester unit of chemical formula (24) representative.

The polyhydroxyalkanoatefrom of gained is used in the following reaction among this embodiment.

303mgPHA is joined in the 200-mL eggplant type flask, add the 20mL methylene chloride then with dissolving PHA.This flask is placed in the ice bath, is preced with-6 ethers to wherein adding 3mL acetate and 300mg 18-, and stirs the gained potpourri.Subsequently, 241mg potassium permanganate is slowly joined in the flask in the ice bath, and at room temperature stirred the mixture 20 hours.Reaction adds to 50mL water and sodium bisulfite in this flask after finishing.Then, use 1.0mol/L (1.0N) hydrochloric acid with potpourri pH regulator to 1.Distill out methylene chloride in the mixed solution with evaporator, reclaim the polymkeric substance in the solution afterwards.With 100mL methanol wash polymkeric substance, further wash three times with the 100mL pure water again, reclaim polymkeric substance afterwards.This polymkeric substance of drying under reduced pressure, thus 247mg target P HA obtained.

Use gel permeation chromatography (GPC; Tosoh HLC-8220, post; TosohTSK-GEL Super HM-H, solvent; Chloroform is with polystyrene equivalent) mean molecular weight of assessment gained PHA.As a result, number-average molecular weight (Mn) is 29,400, and weight-average molecular weight (Mw) is 102,800.

For the structure of clear and definite gained PHA, carry out NMR under these conditions and analyze.

According to this result, find that this PHA is a kind of pha copolymer, its 3-hydroxyl-5-carboxyl valeric acid that contains the 3-hydroxyl-7-carboxyl enanthic acid of 3-hydroxyl-9-carboxyl n-nonanoic acid, chemical formula (35) representative of 3-hydroxyl-5-phenoxy group valeric acid, chemical formula (34) representative of following chemical formula (38) representative and chemical formula (36) representative is as monomeric unit.

And, with the trimethyl silyl diazomethane carboxyl of PHA side chain terminal is carried out the esterification effect, to determine the number percent of each unit among the gained PHA.

50mg target P HA is added in the 100-mL eggplant type flask, add the 3.5mL chloroform afterwards and 0.7mL methyl alcohol dissolves this PHA.Then, (0.63mol/L, Tokyo Kasei Kogyo Co. Ltd.) adds in this flask, and at room temperature stirs the mixture 30 minutes with 2mL trimethyl silyl diazomethane-hexane solution.Reaction is used the evaporator distilling off solvent after finishing, and reclaims polymkeric substance then.With 50mL methanol wash resulting polymers, reclaim polymkeric substance afterwards.This polymkeric substance of drying under reduced pressure is to obtain 49mg PHA.

Carry out NMR according to the mode that is similar to said method and analyze, to determine the number percent of each unit.According to this result, find that hydroxyl-5-phenoxy group valeric acid is 83mol% to 3-, the total amount of 3-hydroxyl-9-carboxyl n-nonanoic acid, 3-hydroxyl-7-carboxyl enanthic acid and 3-hydroxyl-5-carboxyl valeric acid Unit three is 8mol%, and other compound (the straight chain 3-hydroxyl alkane acid and the 3-hydroxyl chain-5-olefin(e) acid that contains 10 or 12 carbon atoms that contain 4-12 carbon atom) is 9mol%.

Embodiment B-1

28.0mg para-totuidine-2-sulfonic acid and 16ml methylene chloride are joined in the 50-ml flask, and under ice-cooled, stirred the mixture 1 hour.Subsequently, the dichloromethane solution that adds 18.2mg I-hydroxybenzotriazole (HOBt), 9ml 150mg polymkeric substance successively, wherein this polymkeric substance contains the dichloromethane solution of the 3-hydroxyl-ω-carboxyl alkanoate unit that obtains among the 8mol% reference example B and 9ml 27.8mg two ring carbodiimides (DCC).Then, under 0 ℃, stirred the mixture 1 hour, and at room temperature stirred 24 hours.Reaction is removed insoluble product after finishing, and the solvent of reaction mixture is removed in distillation.Once more resulting polymers is dissolved in the methylene chloride, in ethanol, precipitates again afterwards.Then, wash, to reclaim polymkeric substance with the second alcohol and water.Down dry this polymkeric substance of decompression, thus 99mg PHA obtained.

Since new discovery the ownership for amide group 1,657cm ^-1With 1,631cm ^-1Peak, so this FT-IR demonstration formation amido link.Fig. 9 has shown the FT-IR spectrum of resulting polymers.

According to analyzing the PHA of gained with the similar mode of embodiment A-1.For mean molecular weight, the number-average molecular weight of PHA (Mn) is 33,300.And, according to the measurement result of sulfur content, find that gained PHA is the pha copolymer that contains 3.8mol% para-totuidine-2-sulfonic acid group.

Adopt the large-scale producing method of resulting polymers to obtain the 50g pha copolymer, and with this compound as example compound B-1, carry out the preparation and the assessment thereof of toner.

Embodiment B-2

Repeat the step of Embodiment B-1,, thereby obtain the 74mg polymkeric substance just with the 22.9mg para-totuidine-2-sulfonic acid that uses in the 21.3mg 2-amino phenyl sulfonyl acid substitution Embodiment B-1.

As shown in Figure 9,, be the new peak of amide group and ownership occurred owing to the peak of ownership for carboxylic acid reduces, so FT-IR demonstration formation amido link.Confirm that gained PHA contains the unit of chemical formula (7A) representative.

Analyze gained PHA according to the mode that is similar to embodiment A-1.For mean molecular weight, the number-average molecular weight of PHA (Mn) is 34,600.And, according to the measurement result of sulfur content, find that gained PHA is the pha copolymer that contains 3.6mol% 2-amino phenyl sulfonyl acid groups.

Adopt the large-scale producing method of resulting polymers to obtain the 50g pha copolymer, and with this compound as example compound B-2, carry out the preparation and the assessment thereof of toner.

Reference example C

The incubation step of repeated reference embodiment A and extraction step, just with the 6mmol/L 5-phenylpentanoic acid and the 2mmol/L 10-undecenoic acid that use among 4.8mmol/L5-(phenyl sulfenyl (sulfanyl)) valeric acid and the 2mmol/L 10-undecylene acid substitution reference example A, thereby obtain 1,934mg PHA (dry weight).Assess the mean molecular weight of gained PHA according to the mode that is similar to embodiment A.Number of results average molecular weight (Mn) is 430,000, and weight-average molecular weight (Mw) is 1,500,000.In addition, for the structure of clear and definite gained PHA, under the condition identical, carry out NMR and analyze with embodiment A.

According to the result, find that gained PHA is a kind of pha copolymer, it contains 3-hydroxyl-5 (phenyl sulfenyl (sulfanyl)) valeric acid (A of following chemical formula (39) representative ₁The unit), 3-hydroxyl-10-undecenoic acid (B ₁The unit), 3-hydroxyl-8-nonenoic acid (C ₁The unit) and 3-hydroxyl-6-heptenoic acid (D ₁The unit) as monomeric unit.

In addition, use ¹The H-NMR spectrum is confirmed the number percent of each unit.According to the result, find A ₁The unit is 78mol%, the total amount (B of Unit three ₁Unit+C ₁Unit+D ₁The unit) be 19mol%, and other compound (the straight chain 3-hydroxyl alkane acid and the 3-hydroxyl chain-5-olefin(e) acid that contains 10 or 12 carbon atoms that contain 4-12 carbon atom) is 3mol%.

302mg gained polyhydroxyalkanoatefrom is joined in the 200-mL eggplant type flask, add the 20mL methylene chloride with dissolving PHA.This potpourri is placed ice bath, and to wherein adding 3mL acetate and 1,154mg 18-is preced with-6 ethers, and stirs the gained potpourri.Subsequently, 917mg potassium permanganate is slowly joined in the flask in the ice bath, and at room temperature stirred the mixture 19 hours.After reaction finished, with 50mL water and 3, the 010mg sodium bisulfite added in this flask.Then, use 1.0N hydrochloric acid with potpourri pH regulator to 1.Distill out methylene chloride in the mixture solution with evaporator, reclaim the polymkeric substance in the solution afterwards.With this polymkeric substance of 100mL methanol wash, further wash three times with the 100mL pure water again, reclaim polymkeric substance afterwards.The drying under reduced pressure resulting polymers, thus 311mg target P HA obtained.

According to assessing the mean molecular weight of gained PHA with mode like the reference example category-A.As a result, number-average molecular weight (Mn) is 62,000, and weight-average molecular weight (Mw) is 260,000.

For the structure of clear and definite gained PHA, with reference example A in carry out NMR under the identical condition and analyze.

According to the result; find that this PHA is a kind of polyhydroxy alkanoate copolymer, its 3-hydroxyl-5-(phenyl sulfonyl) valeric acid, 3-hydroxyl-9-carboxyl n-nonanoic acid, 3-hydroxyl-7-carboxyl enanthic acid and 3-hydroxyl-5-carboxyl valeric acid that contains following chemical formula (40) representative is as monomeric unit.

And, with the trimethyl silyl diazomethane carboxyl of PHA side chain terminal is carried out the esterification effect, to calculate the number percent of each unit among the gained PHA.30mg target P HA is added in the 100-mL eggplant type flask, add the 2.1mL chloroform afterwards and 0.7mL methyl alcohol dissolves this PHA.Then, (2.0mol/L, Aldrich Co. Ltd.) add in this flask, and at room temperature stir the mixture 30 minutes with 0.5mL trimethyl silyl diazomethane-hexane solution.Reaction is used the evaporator distilling off solvent after finishing, and reclaims polymkeric substance then.With 50mL methanol wash resulting polymers, reclaim polymkeric substance afterwards.This polymkeric substance of drying under reduced pressure is to obtain 31mg PHA.

Carry out NMR according to the mode that is similar to said method and analyze, to measure the number percent of each unit.According to ¹The result of H-NMR spectrum; find that 3-hydroxyl-5-(phenyl sulfonyl) valeric acid is 89mol%; the total amount of 3-hydroxyl-9-carboxyl n-nonanoic acid, 3-hydroxyl-7-enanthic acid and 3-hydroxyl-5-valeric acid Unit three is 8mol%, and the total amount of other compound (the straight chain 3-hydroxyl alkane acid and the 3-hydroxyl chain-5-olefin(e) acid that contains 10 or 12 carbon atoms that contain 4-12 carbon atom) is 3mol%.

Embodiment C-1

Repeat the step of Embodiment C-1; just with the PHA among the reference example A used in the replacement of the PHA among the reference example C embodiment A-1; replace 22.9mg para-totuidine-2-sulfonic acid with 15.3mg 2-tarine (taurine), thereby obtain the 80mg polymkeric substance.

As shown in Figure 8,, be the new peak of amide group and ownership occurred owing to the peak of ownership for carboxylic acid reduces, so FT-IR demonstration formation amido link.Find that gained PHA contains the unit of chemical formula (2) representative.

Analyze gained PHA according to the mode that is similar to embodiment A-1.For mean molecular weight, the number-average molecular weight of PHA (Mn) is 27,800.

Next, use the compound for preparing by a kind of method that is selected from the inventive method, prepare multiple toner, and assess as charge adjusting agent.

(embodiment 1)

At first, in the 2 liter of four neck flask that has high-speed stirring apparatus T.K.Homo stirrer, add Na ₃PO ₃Aqueous solution, and be heated to 60 ℃, simultaneously agitator speed is adjusted to 10,000rpm.With CaCl ₂Aqueous solution joins in the above-mentioned solution gradually, contains small Ca with preparation ₃(PO ₄) ₂The aqueous dispersion medium of water-insoluble spreading agent.

On the other hand, use bowl mill that following component was disperseed 3 hours, add 10 mass parts releasing agents (ester type waxes) and 10 mass parts 2 afterwards, 2 '-azo two (2, the 4-methyl pentane nitrile) prepares polymerizable monomer composition as polymerization initiator.

Styrene 82 mass parts

Acrylic acid ethylhexyl 18 mass parts

Divinylbenzene 0.1 mass parts

Bluish-green colorant (C.I. pigment blue 15) 6 mass parts

Peo resin (Mw=3200, acid number=8) 5 mass parts

Example compound (A-1) 2 mass parts

Next, the monomer composition that obtains is in this way joined in the previously prepared water dispersion medium.With 10,000rpm stirs the gained potpourri, with the granulation monomer composition.Afterwards, 80 ℃ of following polymerizations 6 hours, use oar formula paddle wheel to stir this particle simultaneously through reaction under 65 ℃ after 3 hours.After polyreaction finished, the cooling reaction product added acid dissolving water-insoluble dispersing agent C a ₃(PO ₄) ₂, filter, wash with water and dry, thereby make blue polymer particle (1).Use Coulter Counter Multisizer (available from Beckman Coulter K.K.) to measure the granularity of gained blue polymer particle (1), the result shows that the average particle size of particle is 7.2 μ m.And this result shows that also it has the fine powder amount of 4.9% quantity (3.17 μ m or littler proportion of particles in the distributed number).

Hydrophobic silica fine powder (BET=270m with 1.3 mass parts through the hexamethyldisilazane processing ²/ g) join in the blue polymer particle (1) that 100 mass parts make in this way, as flow improving agent, mix with dry pigmentation with the Henschel mixer afterwards, obtain the blue toner (1) of embodiment 1.In addition, the gained blue toner (1) and 93 mass parts of 7 mass parts have been applied the magnetic ferrites carrier (particle mean size: 45 μ m) mix, be used for the blue developer (1) of two components of magnetic brush development with preparation of resin.

Embodiment 2-4

Repeat the step of embodiment 1, just replace example compound A-1, thereby obtain blue toner (2)-(4) of embodiment 2-4 with example compound A-4, A-8 and B-1.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use these toners, obtain blue developer (2)-(4) of two components of embodiment 2-4 according to the mode identical with embodiment 1.

(comparative example 1)

Repeat the step of embodiment 1, usage example compound not just, thus obtain the blue toner (5) of comparative example 1.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use this toner, obtain the blue developer (5) of two components of comparative example 1 according to the mode identical with embodiment 1.

＜estimate

For blue developer (1)-(4) of two components that obtain among the embodiment 1, with the blue developer (5) of two components that obtain in the comparative example 1, after the stirring of 10-second and 300-second, according to above-mentioned charge quantity measuring method, at normal temperature and (25 ℃ of normal ambient humidities, 60%RH) and high temperature and high ambient humidity (30 ℃, 80% RH) measure the toner charge amount down.The measured value of the two components discharging quantity of electric charge is rounded up to first decimal place, and based on following standard evaluation charging property.Table 1 has totally shown the gained result.

[charging property]

◎: very good (20 μ C/g or littler)

Zero: good (19.9--10.0 μ C/g)

△: feasible (9.9--5.0 μ C/g)

*: infeasible (4.9 μ C/g or bigger)

Embodiment 5-8

Repeat the step of embodiment 1, only be to use example compound A-1, A-4, A-8 and the B-1 of 2.0 mass parts, and use yellow colorants (hansa yellow G) to replace bluish-green colorant, thereby obtain Yellow toner (1)-(4) of embodiment 5-8.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use these toners, obtain two component yellow developer (1)-(4) according to the mode identical with embodiment 1.

Comparative example 2

Repeat the step of embodiment 1, usage example compound not just, and use yellow colorants (hansa yellow G) to replace bluish-green colorant, thus obtain the Yellow toner (5) of comparative example 2.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use this toner, obtain two component yellow developer (5) of comparative example 2 according to the mode identical with embodiment 1.

＜estimate

For two component yellow developer (1)-(4) that obtain among the embodiment 5-8, with the two component yellow developer (5) that obtain in the comparative example 2, after the stirring of 10-second or 300-second, according to above-mentioned charge quantity measuring method, at normal temperature and (25 ℃ of normal ambient humidities, 60% RH) and high temperature and high ambient humidity (30 ℃, 80% RH) measure the toner charge amount down.The measured value of the two components discharging quantity of electric charge is rounded up to first decimal place, and based on the standard evaluation charging property identical with embodiment 1-4.Table 1 has totally shown its result.

Embodiment 9-12

Repeat the step of embodiment 1, only be to use example compound A-2, A-3, A-5 and the B-2 of 2.0 mass parts, and (DBP oil absorbs: 110ml/100g) replace bluish-green colorant, thereby obtain black toner (1)-(4) of embodiment 9-12 with carbon black.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use these toners, obtain two component black reagent (1)-(4) according to the mode identical with embodiment 1.

Comparative example 3

Repeat the step of embodiment 1, usage example compound not just, and (DBP oil absorbs: 110ml/100g) replace bluish-green colorant, thereby obtain the black toner (5) of comparative example 3 to use carbon black.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use this toner, obtain two component black reagents (5) of comparative example 3 according to the mode identical with embodiment 1.

＜estimate

For two component black reagent (1)-(4) that obtain among the embodiment 9-12, with the two component black reagents (5) that obtain in the comparative example 3, after the stirring of 10-second or 300-second, according to above-mentioned charge quantity measuring method, at normal temperature and (25 ℃ of normal ambient humidities, 60% RH) and high temperature and high ambient humidity (30 ℃, 80% RH) measure the toner charge amount down.The measured value of the two components discharging quantity of electric charge is rounded up to first decimal place, and based on the standard evaluation quantity of electric charge identical with embodiment 8-14.Table 1 has totally shown the gained result.

Embodiment 13

Styrene-propene butyl acrylate copolymer resin (glass transition temperature is 70 ℃) 100 mass parts

Magenta pigment (C.I. paratonere 114) 5 mass parts

Example compound A-2 2 mass parts

Mixing said ingredients melts and then with biaxial extruder (L/D=30) kneading.Cooling gained kneading product.Pulverize the kneading product roughly with hammer-mill then, carry out meticulous pulverizing with airslide disintegrating mill again, carry out sorting afterwards.Thereby obtained pinkish red colored particles (1) by pulverizing.The average particle size of finding pinkish red colored particles (1) is 7.6 μ m, and the quantity of fine granular is 5.2%.

Use the Henschel mixer by dry pigmentation, with the hydrophobic silica fine powder (BET=250m of 1.5 mass parts through the hexamethyldisilazane processing ²/ g) mix with the pinkish red colored particles of 100 mass parts (1) as flow improving agent, obtain magenta (redness) toner (1) of present embodiment.In addition, pinkish red toner of the gained of 7 mass parts (1) and 93 mass parts have been applied the magnetic ferrites carrier (particle mean size: 45 μ m) mix, be used for two component magenta (redness) developers (1) of magnetic brush development with preparation of resin.

Embodiment 14-16

Repeat the step of embodiment 13, just replace example compound A-2, thereby obtain magenta (redness) toner (2)-(4) of embodiment 14-16 with example compound A-3, A-5 and B-2.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use these toners, obtain two component magenta (redness) developer (2)-(4) of embodiment 14-16 according to the mode identical with embodiment 13.

(comparative example 4)

Repeat the step of embodiment 13, usage example compound not just, thus obtain magenta (redness) toner (5) of comparative example 4.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use this toner, obtain two component magenta (redness) developers (5) of comparative example 4 according to the mode identical with embodiment 13.

＜estimate

For two component magenta (redness) developer (1)-(4) that obtain among the embodiment 13-16, with two component magenta (redness) developers (5) that obtain in the comparative example 4, after the stirring of 10-second and 300-second, according to above-mentioned charge quantity measuring method, at normal temperature and (25 ℃ of normal ambient humidities, 60% RH) and high temperature and high ambient humidity (30 ℃, 80% RH) measure the toner charge amount down.The measured value of the two components discharging quantity of electric charge is rounded up to first decimal place, and based on following standard evaluation charging property.Table 1 has totally shown the gained result.

[charging property]

◎: very good (20 μ C/g or littler)

Zero: good (19.9--10.0 μ C/g)

△: feasible (9.9--5.0 μ C/g)

*: infeasible (4.9 μ C/g or bigger)

Embodiment 17-20

Repeat the step of embodiment 13, only be to use example compound A-1, A-4, A-8 and the B-1 of 2.0 mass parts, and (DBP oil absorbs: 110ml/100g) substitute red, thereby black toner (6)-(9) of acquisition embodiment 17-20 with carbon black.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use these toners, obtain two component black reagent (6)-(9) according to the mode identical with embodiment 13.

Comparative example 5

Repeat the step of embodiment 13, usage example compound not just, and use carbon black (DBP oil absorbs: 110ml/100g) substitute red, thereby obtain the black toner (10) of comparative example 5.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use this toner, obtain two component black reagents (10) of comparative example 5 according to the mode identical with embodiment 13.

＜estimate

For two component black reagent (6)-(9) that obtain among the embodiment 17-20, with the two component black reagents (10) that obtain in the comparative example 5, after the stirring of 10-second and 300-second, according to above-mentioned charge quantity measuring method, at normal temperature and (25 ℃ of normal ambient humidities, 60% RH) and high temperature and high ambient humidity (30 ℃, 80% RH) measure the toner charge amount down.The measured value of the two components discharging quantity of electric charge is rounded up to first decimal place, and based on the standard evaluation quantity of electric charge identical with embodiment 13-16.Table 1 has totally shown the gained result.

(embodiment 21)

Vibrin 100 mass parts

(DBP absorbs carbon black: 110ml/100g) 5 mass parts

Example compound (A-1) 2 mass parts

Vibrin is synthetic by following mode.Use 2 parts of Dibutyltin oxides as catalyzer, 751 parts of bisphenol-A epoxy propane 2mol adducts, 104 parts of terephthalic acid (TPA)s and 167 parts of trimellitic anhydrides are carried out polycondensation reaction, obtain softening point and be 125 ℃ vibrin.

Mixing said ingredients melts and then with biaxial extruder (L/D=30) kneading.Cooling gained kneading product.Pulverize the kneading product roughly with hammer-mill then, carry out meticulous pulverizing with airslide disintegrating mill again, carry out sorting afterwards.Thereby obtained black colorant particle (11) by pulverizing.The average particle size of finding black colorant particle (11) is 7.4 μ m, and the quantity of fine particle is 5.0%.

Use the Henschel mixer by dry pigmentation, with the hydrophobic silica fine powder (BET=250m of 1.5 mass parts through the hexamethyldisilazane processing ²/ g) mix with the black colorant particle (11) of 100 mass parts as flow improving agent, obtain the black toner (17) of present embodiment.In addition, the gained black toner (17) and 93 mass parts of 7 mass parts have been applied the magnetic ferrites carrier (particle mean size: 44 μ m) mix, be used for two component black reagents (11) of magnetic brush development with preparation of resin.

Embodiment 22-24

Repeat the step of embodiment 21, just replace example compound A-1, thereby obtain black toner (11)-(14) of embodiment 22-24 with example compound A-4, A-8 and B-1.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use these toners, obtain two component black reagent (11)-(14) of embodiment 22-24 according to the mode identical with embodiment 21.

Comparative example 6

Repeat the step of embodiment 21, usage example compound not just, thus obtain the black toner (15) of comparative example 6.Measure the characteristic of toner according to the mode identical with embodiment 1, the gained result is as shown in table 1.Use this toner, obtain two component black reagents (15) of comparative example 6 according to the mode identical with embodiment 21.

＜estimate

For two component black reagent (11)-(14) that obtain among the embodiment 21-24, with the two component black reagents (15) that obtain in the comparative example 6, after the stirring of 10-second or 300-second, according to above-mentioned charge quantity measuring method, at normal temperature and (25 ℃ of normal ambient humidities, 60% RH) and high temperature and high ambient humidity (30 ℃, 80% RH) measure the toner charge amount down.The measured value of the two components discharging quantity of electric charge is rounded up to first decimal place, and based on following standard evaluation charging property.Table 1 has totally shown the gained result.

[charging property]

◎: very good (20 μ C/g or littler)

Zero: good (19.9--10.0 μ C/g)

△: feasible (9.9--5.0 μ C/g)

*: infeasible (4.9 μ C/g or bigger)

(embodiment 25-30 and comparative example 7-12)

In each embodiment of embodiment 25-30 and comparative example 7-12, use respectively by embodiment 1,5,9,13,17 and 21 and two component developers that make of one of the toner of comparative example 1-6.At first, the imaging device that uses in the formation method to embodiment 25-30 and comparative example 7-12 is described.Fig. 1 is a synoptic diagram, shows the xsect of the imaging device of the formation method be used to implement the embodiment of the invention and comparative example.The photosensitive drums 1 that shows among Fig. 1 comprises photographic layer 1a, and this photographic layer 1a has organic photosemiconductor on substrate 1b, and photosensitive drums 1 is configured to and can rotates in the direction of arrows.In addition, use charging roller 2, make the surface charging of photosensitive drums 1, this charging roller regard to photosensitive drums 1 and rotate with the surface potential of pact-600V to contact with photosensitive drums 1 as charge member.As shown in Figure 1, charging roller 2 is constructed, conductive elastic layer 2a is applied on the core metal 2b.

Next, on the photosensitive drums 1 of surface charging, light 3 is exposed.At this moment,, utilizing polygon mirror to open or close exposure on the photo-sensitive cell, can form the exposure current potential and be-100V according to digital image information, dark potential is-electrostatic image of 600V.Subsequently, use a plurality of developing devices 4 (4-1,4-2,4-3 and 4-4), on photosensitive drums 1, produce electrostatic image by discharged-area development, and on photosensitive drums 1, form toner image.At this moment, use two component developers that obtain among embodiment 4-21 and the comparative example 1-6, utilize Yellow toner, magenta toner, bluish-green toner or black toner to form toner image as developer.Fig. 2 is the amplification view of the critical piece of each developing device 4, and this developing device uses two component developers at this moment.

Next, the toner image with photosensitive drums 1 is transferred on the intermediate transfer element 5.Photosensitive drums 1 and the 5 common rotations of intermediate transfer element by contacting with each other.As a result, form the coloured image that develops on intermediate transfer element 5, this image forms by overlapping four kinds of colors.The transfer printing remaining toner that is not transferred on the photosensitive drums 1 can be recovered in the remaining toner container 9 by cleaning element 8.

As shown in Figure 1, to construct intermediate transfer element 5 as the core metal 5b of supporting element and the elastic layer 5a that is laminated on the core metal 5b.What use in this embodiment is the intermediate transfer element 5 that obtains with elastic layer 5a covering tube core metal 5b, uses the carbon black conduct to give the material of electric conductivity in this elastic layer, and it is well dispersed in nitrile-butadiene rubber (NBR).The hardness of the elastic layer 5a that records based on " JIS K-6301 " is 30 degree, and specific insulation is 10 ⁹Ω cm.Image is transferred to intermediate transfer element 5 required transfer printing electric currents by photosensitive drums 1 is about 5 μ A, this electric current can by power supply to core metal 5b apply+voltage of 500V obtains.

By transfer roll 7, will be on intermediate transfer element 5 overlapping four kinds of colors and the developed color image that forms is transferred to recording medium, for example on the paper, afterwards by fuser spare H photographic fixing on recording medium.Transfer roll 7 is configured to, and elastic layer 7a is formed on the core metal 7b that external diameter is 10mm.Applied material containing carbon on the elastic layer 7a, the material of electric conductivity is given in wherein contained carbon conduct, and is well dispersed in the foam of being made by ethylene-propylene-diene terpolymer (EPDM).The specific insulation that records used elastic layer 7a based on " JIS K-6301 " is 10 ⁶Ω cm, hardness is 35 degree.In addition, on transfer roll 7, apply voltage, so that the transfer printing electric current of 15 μ A flows through.

In device shown in Figure 1, used fuser spare H is the hot-rolling type photographic fixing device shown in Fig. 5 and 6, does not have refuel mechanism.In this case, for top roller and bottom roller, used photographic fixing device has the superficial layer of being made by fluororesin.In addition, the diameter of this roller is 60mm.Fixing temperature during photographic fixing is set at 160 ℃, and nip width is set at 7mm.In addition, utilize again by utilizing the machine-processed transfer printing remaining toner that will clean on the photosensitive drums 1 that reclaims to be transferred on the developing machine again.

＜estimate

Under these conditions, under normal temperature and home humidity (25 ℃, 60% RH) and high temperature and high ambient humidity (30 ℃, 80% RH), print-output test, printing-output speed be 8 (A-4 sizes)/minute.Two component developers that use is made by each toners of embodiment 1,5,9,13,17 and 21, two component developers that make with each toner by comparative example 1-6, at monochromatic intermittent mode (promptly, as long as one of machine printout, then developing machine stops 10 seconds, when restarting, impel the pattern of toner degraded during this time by pre-operation) under print-output test, developer is provided simultaneously successively.Gained printing-output image is carried out the evaluation of following items.Evaluation result is summarised in the table 2.

[evaluation of printing-output image]

1. image density

Used in copy machines plain weave paper (75g/m commonly used at predetermined number ²) on print off image.Image is estimated image density with respect to the maintenance degree of the density of original image when finishing according to printing.Use Macbeth reflection-densitometer (being made by Macbeth Co.), measure image density according to following standard, this image density is to be the image that prints off of 0.00 white background part with respect to original density:

◎: excellent (image density of printing when finishing is 1.40 or bigger)

Zero: good (image density is 1.35 or bigger when printing end, and less than 1.40)

△: still can (print image density is 1.00 or bigger when finishing, and less than 1.35)

*: defective (image density is less than 1.00 when printing end)

2. image fog

Used in copy machines plain weave paper (75g/m commonly used at predetermined number ²) on print off certain image, and when printing off-test, estimate and print off image with respect to the whole white image.Specifically, estimate by following mode.Use reflection-densitometer (REFLECTOMETER ODELTC-6DS, by Tokyo Denshoku Co., Ltd. makes) is measured reflection density worst-case value Ds that prints off the image white background parts and the reflection density mean value Dr that prints preceding paper.Obtain (Ds-Dr) value according to these values, it is defined as the fog amount, and according to following standard evaluation.

◎: very good (the fog amount is 0% or bigger, and less than 1.5%)

Zero: good (the fog amount is 1.5% or bigger, and less than 3.0%)

△: feasible (the fog amount is 3.0% or bigger, and less than 5.0%)

*: infeasible (the fog amount is 5.0% or bigger)

3. transfer printing ability

Used in copy machines plain weave paper (75g/m commonly used at predetermined number ²) on print off all black image, the amount of coming off by the ocular estimate detected image when print finishing, and estimate according to following standard.

◎: very good (almost not coming off)

Zero: good (slightly coming off)

△: feasible

*: infeasible

In addition, in embodiment 25-30 and comparative example 7-12, on 5,000 paper, carry out image output.Estimate adhering to of the damage that occurs on photosensitive drums, the intermediate transfer element surface, remaining toner respectively and to the influence of printing off image the coupling of imaging device (that is, with) by ocular estimate.As a result, in the system of two component developers that adopt embodiment 25-30, do not have scratch fully on photosensitive drums and the intermediate transfer element surface, not confirming has adhering to of remaining toner, and has extraordinary matching with imaging device.On the other hand, in the system of two component developers that adopt comparative example 7-12, confirm all under all situations that toner is attached on the photosensitive drum surface.In addition, in the system of two component developers that adopt comparative example 7-12, be attached on the intermediate transfer element surface and surface distress takes place owing to confirm toner, and on image, formed image deflects, vertical stripes for example, therefore the coupling with imaging device has produced problem.

Embodiment 31-33 and comparative example 13-15

When carrying out each formation method of embodiment 31-33 and comparative example 13-15, use embodiment 1,5 and 9 and comparative example 1-3 in each toner of obtaining as developer.As imaging tool, as shown in Figure 3, use to change commercially available laser beam printer (Inc makes for LBP-EX, Canon) and the imaging device that obtains, promptly this imaging device will utilize mechanism to be connected on the printer again and reset and obtain.That is to say, imaging device shown in Figure 3 has a system, in this system, elastic blade 22 on the clearer 21 contacts with photosensitive drums 20 and scrapes off the toner that is retained in the not transfer printing on the photosensitive drums 20 after the transfer printing, with clearer the toner that scrapes off is delivered in the clearer 21 then, and further carries by clearer re-use device 23.Subsequently, use the feed pipe 24 that has feeding spiro rod toner to be turned back in the developing apparatus 26, use the toner that reclaims afterwards by loading hopper 25.

In imaging device shown in Figure 3, make the surface charging of photosensitive drums 20 with main charging roller 27.The rubber rollers (diameter be 12mm, contact press be 50gf/cm) of main charging roller 27 for being coated with nylon resin wherein is dispersed with electrically conductive graphite.By laser explosure (600dpi, not shown), go up the formation electrostatic latent image at electrostatic latent image load-carrying unit (photosensitive drums 20), the dark potential VD of this electrostatic latent image is-700V that bright current potential VL is-200V.Use development sleeve 28 as the toner load-carrying unit, its surface roughness Ra is 1.1, and its surface-coated is dispersed with the resin of carbon black.Element as restriction toner film thickness uses chemglaze scraper 29, and its surface with development sleeve 28 is contacted.

Fig. 4 has shown for the monocomponent toner that uses among embodiment 31-33 and the comparative example 13-15, the amplification view of used developing apparatus critical piece.As the condition of developing electrostatic latent image, the speed setting of development sleeve 28 is 1.1 times of photosensitive drums 20 surperficial velocities of rotation, and wherein this photosensitive drums 20 regards to development sleeve 28.In addition, the distance alpha between photosensitive drums 20 and the development sleeve 28 (between S and the D) is defined as 270 μ m.Element as restriction toner film thickness uses chemglaze scraper 29, and its surface with development sleeve 28 is contacted.In addition, the predetermined temperature that will be used for the fuser spare of fusing toner image is set at 160 ℃.And the photographic fixing device shown in using among Fig. 5 and 6 separately is as the photographic fixing device.

[transformation of image density in the operating process]

Used in copy machines plain weave paper (75g/m commonly used at predetermined number ²) on print off image.Image is estimated image density with respect to the maintenance degree of the image density of original image when finishing according to printing.Use Macbeth reflection-densitometer (being made by Macbeth Co.), measure image density according to following standard, this image density is to be the image that prints off of 0.00 white background part with respect to original density:

◎: excellent (image density of printing when finishing is 1.40 or bigger)

Zero: good (image density is 1.35 or bigger when printing end, and less than 1.40)

△: still can (print image density is 1.00 or bigger when finishing, and less than 1.35)

*: defective (image density is less than 1.00 when printing end)

[image fog]

Used in copy machines plain weave paper (75g/m commonly used at predetermined number ²) on print off certain image, and when print finishing, estimate and print off image with respect to white background zone (or whole white image).Specifically, estimate with following method.Use reflection-densitometer (REFLECTOMETER ODEL TC-6DS, by Tokyo Denshoku Co., Ltd. makes) to measure the reflection density in the white background zone of printing off image, its worst-case value is called " Ds ".The mean value of copier paper reflection density is called " Dr " before printing.Obtain (Ds-Dr) value according to these values, it is defined as the fog amount, and according to following standard evaluation.

◎: very good (the fog amount is 0% or bigger, and less than 1.5%)

Zero: good (the fog amount is 1.5% or bigger, and less than 3.0%)

△: feasible (the fog amount is 3.0% or bigger, and less than 5.0%)

*: infeasible (the fog amount is 5.0% or bigger)

To with the evaluation of the matching of development sleeve

After printing off off-test, by the ocular estimate evaluation attached to the outward appearance of the lip-deep remaining toner of development sleeve with to printing off the influence of image.

◎: very good (not occurring)

Zero: good (a small amount of appearance)

△: feasible (some attachment portions are arranged, but very little to the image influence)

*: infeasible (many attachment portions are arranged, and image is inhomogeneous)

To with the evaluation of the matching of photosensitive drums

Estimate the destruction that remaining toner takes place in its surface or adhere to by ocular estimate, and to printing off the influence of image.

◎: very good (not occurring)

Zero: good (a small amount of destruction, very little) to the image influence

△: feasible (some attachment portions and destruction are arranged, but very little to the image influence)

*: infeasible (many attachment portions are arranged, and image deflects are arranged, for example vertical stripes)

To with the evaluation of the matching of photographic fixing device

Observe the appearance of photographic fixing film, and the result of comprehensive average surface quality and the adhesion condition of remaining toner, in order to estimate permanance.

(1) surface quality

After printing off off-test, range estimation lip-deep destruction of photographic fixing film and the outward appearance of splitting, and estimate.

◎: very good (not occurring)

Zero: good (a small amount of appearance)

△: feasible

*: infeasible

(2) adhesion condition of remaining toner

After printing off off-test, estimate remaining toner at the lip-deep adhesion condition of photographic fixing film, and estimate.

◎: very good (not occurring)

Zero: good (a small amount of appearance)

△: feasible

*: infeasible

(embodiment 34)

Utilize mechanism to remove again toner from the imaging device of Fig. 3.Then, adopt the mode identical to print off test with embodiment 31-33, just print-out rate is set at 16 (A4 sizes)/minute.Test with continuous mode (that is, not stopping the consumption that developing device promotes toner), simultaneously the blue toner (1) of embodiment 8 without interruption.At with embodiment 31-33 and comparative example 13-15 in identical project, to printing off image and estimating with the matching of used picture appraisal device.The result is fine for each project.

The size-grade distribution of toner and charging property in table 1 shades of colour

(for easy, Yellow toner is called Huang, and magenta toner is called red)

Claims (26)

1. a polyhydroxyalkanoatefrom is characterized in that, comprises the unit of at least one following chemical formula (1) representative in its molecule,

R represents-A ₁(SO ₂R ₁) _xR ₁Be selected from OH, ONa, OK and OR _1a, R _1aBe methyl or phenyl, A ₁Be selected from the phenyl of isopropyl, phenyl, naphthyl, methyl or methoxy replacement, x is 1; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit, R ₁, R _1a, A ₁, m and x independently of one another as above-mentioned definition.

2. according to the polyhydroxyalkanoatefrom of claim 1, it is characterized in that the unit of chemical formula (1) representative is the unit of following chemical formula (2) representative,

R ₂Be selected from OH, ONa, OK and OR _2aR _2aBe methyl or phenyl; A ₂Be selected from the phenyl of isopropyl, phenyl, naphthyl, methyl or methoxy replacement; In addition, x is 1, and m is the integer that is selected from 1-8, and when having two or more unit, the A of each unit ₂, R ₂, R _2a, m and x independently of one another as above-mentioned definition.

3. according to the polyhydroxyalkanoatefrom of claim 1, it is characterized in that the unit of chemical formula (1) representative is the unit of following chemical formula (3) representative,

R _3a, R _3b, R _3c, R _3dAnd R _3eOne of be selected from SO ₂R _3f, R _3fBe selected from OH, ONa, OK and OR _3f1, R _3f1Be methyl or phenyl, in addition, all the other R _3a, R _3b, R _3c, R _3dAnd R _3eBe selected from hydrogen atom, methyl and methoxyl; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit _3a, R _3b, R _3c, R _3d, R _3e, R _3f, R _3f1With m independently of one another as above-mentioned definition.

4. according to the polyhydroxyalkanoatefrom of claim 1, it is characterized in that the unit of chemical formula (1) representative is the following chemical formula (4A) or (4B) unit of representative,

R _4a, R _4b, R _4c, R _4d, R _4e, R _4fAnd R _4gOne of be selected from SO ₂R _4o, R _4oBe selected from OH, ONa, OK and OR _4o1R _4o1Be methyl; In addition, all the other R _4a, R _4b, R _4c, R _4d, R _4e, R _4fAnd R _4gBe selected from hydrogen atom; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit _4a, R _4b, R _4c, R _4d, R _4e, R _4f, R _4g, R _4o, R _4o1With m independently of one another as above-mentioned definition;

R _4h, R _4i, R _4j, R _4k, R _4l, R _4mAnd R _4nOne of be selected from SO ₂R _4o, R _4oBe selected from OH, ONa, OK and OR _4o1R _4o1Be methyl; In addition, all the other R _4h, R _4i, R _4j, R _4k, R _4l, R _4mAnd R _4nBe selected from hydrogen atom; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit _4h, R _4i, R _4j, R _4k, R _4l, R _4m, R _4n, R _4o, R _4o1With m independently of one another as above-mentioned definition.

5. according to the polyhydroxyalkanoatefrom of claim 1, it is characterized in that the unit of chemical formula (1) representative is the unit of following chemical formula (5) representative,

R ₅Be selected from OH, ONa, OK and OR _5aR _5aBe methyl; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit ₅, R _5aWith m independently of one another as above-mentioned definition.

6. according to the polyhydroxyalkanoatefrom of claim 1, the unit that it is characterized in that chemical formula (1) representative is the unit of following chemical formula (6) representative,

R _6a, R _6cAnd R _6eOne of be selected from SO ₂R _6f, R _6fBe selected from OH, ONa, OK; In addition, all the other R _6a, R _6b, R _6c, R _6dAnd R _6eBe selected from hydrogen atom; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit _6a, R _6b, R _6c, R _6d, R _6e, R _6fWith m independently of one another as above-mentioned definition.

7. according to the polyhydroxyalkanoatefrom of claim 1, it is characterized in that the unit of chemical formula (1) representative is the unit of following chemical formula (7B) representative,

R _7aBe selected from OH, ONa, OK and OR _7cR _7cBe methyl or phenyl; R _7bBe selected from hydrogen atom or methoxyl; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit _7a, R _7b, R _7cWith m independently of one another as above-mentioned definition.

8. according to the polyhydroxyalkanoatefrom of claim 1, the unit that it is characterized in that chemical formula (1) representative is the following chemical formula (8A) or (8B) unit of representative,

R ₈Be selected from OH, ONa, OK and OR _8aR _8aBe methyl; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit ₈, R _8aWith m independently of one another as above-mentioned definition;

R ₈Be selected from OH, ONa, OK and OR _8aR _8aBe methyl; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit ₈, R _8aWith m independently of one another as above-mentioned definition.

9. according to each polyhydroxyalkanoatefrom among the claim 1-8, it is characterized in that, also comprise the unit of at least one m=2, m=4, m=6 or m=8 in the polyhydroxyalkanoatefrom molecule that chemical formula (1)-(8) are represented separately.

10. according to each polyhydroxyalkanoatefrom among the claim 1-8, it is characterized in that,, also comprise the unit of following chemical formula (9) representative at least except comprising the unit of chemical formula (1)-(8) representative,

N is the integer that is selected from 1-8, R ₉Expression phenyl, phenoxy group, phenyl sulfenyl or phenyl sulfonyl, and when having two or more unit, the n of each unit and R ₉Independently of one another as above-mentioned definition.

11. the polyhydroxyalkanoatefrom according to claim 10 is characterized in that, the R in the chemical formula (9) ₉The substituting group that contains residue with phenyl structure, it is the group of one of following chemical formula (11), (12), (14) and (20) representative, and when having two or more unit, for following each unit, R ₉Independently as above-mentioned definition:

By not replacing and group that substituted-phenyl is formed of following chemical formula (11) representative;

R _11aBe selected from the H atom, and when having two or more unit, the R of each unit ₁₁Independently as above-mentioned definition;

By not replacing and group that substituent phenoxy is formed of following chemical formula (12) representative;

R ₁₂Be selected from the H atom, and when having two or more unit, the R of each unit ₁₂Independently as above-mentioned definition;

The group of forming by the not replacement and the substituted-phenyl sulfenyl (sulfanyl) of following chemical formula (14) representative;

R _14aBe selected from the H atom, and when having two or more unit, the R of each unit _14aIndependently as above-mentioned definition;

By not replacing and group that the substituted phenyl sulfonyl base is formed of following chemical formula (20) representative; With

R _17aBe selected from the H atom, and when having two or more unit, the R of each unit _17aIndependently as above-mentioned definition.

12. the preparation method of a polyhydroxyalkanoatefrom is characterized in that comprising the following steps:

Preparation contains the unit polyhydroxyalkanoatefrom matrix of chemical formula (22) representative and the amines of at least a chemical formula (23) representative; With

Condensation reaction by polyhydroxyalkanoatefrom matrix and amines obtains containing the polyhydroxyalkanoatefrom of the unit of chemical formula (1) representative;

13. for being selected from the integer of 1-8, R ₁₈Be selected from H atom, Na atom and K atom, and when having two or more unit, 1 and R of each unit ₁₈Independently of one another as above-mentioned definition;

H ₂N-A ₃(-SO ₂R ₁₉) _y (23)

R ₁₉Be selected from OH, ONa, OK and OR _19a, R _19aBe methyl or phenyl, A ₃For the 2-methyl-propyl, to benzyl, 4-methoxyphenyl, phenyl or naphthyl; Y is the integer that is selected from 1-8, and when having two or more unit, the R of each unit ₁₉, R _19a, A ₃With y independently of one another as above-mentioned definition;

R represents-A ₁(SO ₂R ₁) _xR ₁Be selected from OH, ONa, OK and OR _1aR _1aBe methyl or phenyl, A ₁Be selected from the phenyl of isopropyl, phenyl, naphthyl, methyl or methoxy replacement, x is 1; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit, R ₁, R _1a, A ₁, m and x independently of one another as above-mentioned definition.

14. the preparation method according to claim 12 is characterized in that, described condensation reaction is to use condensation agent to form the reaction of amido link.

15. the preparation method according to claim 13 is characterized in that, uses at least a condensation agent that is selected from phosphate condensation agent, carbodiimide condensation agent and acid chloride condensation agent to implement this method.

16. preparation method according to claim 12; it is characterized in that; described condensation reaction is the reaction that forms amido link by following manner: the carboxylic moiety that will contain the polyhydroxyalkanoatefrom of unit shown in the chemical formula (22) is converted into acid chloride, the amines reaction that itself and chemical formula (23) are represented.

17. the preparation method according to claim 15 is characterized in that, uses thionyl chloride to form acid chloride.

18. the preparation method according to claim 12 is characterized in that, the R when chemical formula (1) ₁Part is when being one of OH, ONa and OK, and this method further is included in after the condensation reaction R part esterification formation-A with chemical formula (1) ₁-SO ₃CH ₃Step.

19. the preparation method according to claim 17 is characterized in that, uses the trimethyl silyl diazomethane to carry out described esterification step.

20. a charge adjusting agent that is used to control the electriferous state of powder is characterized in that, this charge adjusting agent is included in the polyhydroxyalkanoatefrom of the unit that contains at least one chemical formula (1) representative in the molecule,

R represents-A ₁(SO ₂R ₁) _xR ₁Be selected from OH, ONa, OK and OR _1aR _1aBe methyl or phenyl, A ₁Be selected from the phenyl of isopropyl, phenyl, naphthyl, methyl or methoxy replacement, x is 1; In addition, m is the integer that is selected from 1-8, and when having two or more unit, the R of each unit, R ₁, R _1a, A ₁, m and x independently of one another as above-mentioned definition.

21. according to the charge adjusting agent of claim 19, wherein this powder comprises static charge image developing toner.

22. a static charge image developing toner is characterized in that, comprises at least a adhesive resin, colorant and according to the charge adjusting agent of claim 19.

23. a formation method is characterized in that comprising the following steps: at least

Apply voltage from the outside to charge member, use so that give the electrostatic latent image load-carrying unit charged;

On charged electrostatic latent image load-carrying unit, form electrostatic image;

Make electrostatic image development with static charge image developing toner, thereby form toner image on the electrostatic latent image load-carrying unit, wherein this static charge image developing toner is the static charge image developing toner according to claim 21;

Toner image on the electrostatic latent image load-carrying unit is transferred on the recording medium; With

This toner image of hot photographic fixing on recording medium.

24. the formation method according to claim 22 is characterized in that:

Described transfer step comprises the toner image on the electrostatic latent image load-carrying unit is transferred to first transfer step of intermediate transfer element and the toner image on the intermediate transfer element is transferred to second transfer step on the recording medium.

25. an imaging device is characterized in that comprising at least:

Apply voltage from the outside to charge member, use so that the charged device of electrostatic latent image load-carrying unit;

On charged electrostatic latent image load-carrying unit, form the device of electrostatic image;

Make electrostatic image development with static charge image developing toner, thereby form the device of toner image on the electrostatic latent image load-carrying unit, wherein this static charge image developing toner is the static charge image developing toner according to claim 21;

Toner image on the electrostatic latent image load-carrying unit is transferred to device on the recording medium; With

The device of hot this toner image of photographic fixing on recording medium.

26. imaging device according to claim 24, it is characterized in that, described transfer device comprises the toner image on the electrostatic latent image load-carrying unit is transferred to first transfer device of intermediate transfer element and the toner image on the intermediate transfer element is transferred to second transfer device on the recording medium.

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