CN100370365C - Novel polyhydroxyalkanoate having amide, sulfonic acid or sulfonate ester group, charge control agent and toner - Google Patents
Novel polyhydroxyalkanoate having amide, sulfonic acid or sulfonate ester group, charge control agent and toner Download PDFInfo
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- CN100370365C CN100370365C CNB2003801075715A CN200380107571A CN100370365C CN 100370365 C CN100370365 C CN 100370365C CN B2003801075715 A CNB2003801075715 A CN B2003801075715A CN 200380107571 A CN200380107571 A CN 200380107571A CN 100370365 C CN100370365 C CN 100370365C
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Abstract
The invention provides a novel polyester adapted for use in a charge control agent for a toner for an electrophotographic process, having a charge stability, a high charge amount, an improved dispersibility and a biodegradability, and a producing method and an application technology therefor. According to the invention, there is provided polyhydroxyalkanoate comprising at least one unit represented by the following chemical formula in a molecule: -(O-CH(-(CH2)m-CH2-p-C6H4-CONH-A1SO2R1)CH2CO)-(wherein R1 represents OH, a halogen atom, ONa, OK or OR1a; A1 and R1a each represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic cyclic structure or a substituted or unsubstituted heterocyclic structure; m represents an integer selected from a range of 0 to 7; and R1, A1, R1a and m have the aforementioned meanings independently for each unit when plural units are present), a charge control agent containing such polyhydroxyalkanoate, a toner utilizing such charge control agent, and an image forming method and an image forming apparatus utilizing such toner.
Description
Technical field
The present invention relates to a kind of novel polyhydroxyalkanoatehaving (below be abbreviated as PHA) and preparation method thereof.Have as the sulfonic group of hydrophilic group or polar group or polyhydroxy-alkanoates of its deriveding group and preparation method thereof in particular to a kind of.
The invention still further relates to a kind of charge control agent and a kind of electrostatic image-developing toner, be used to adopt the recording method of electrophotography, electrostatic recording or magnetic recording; Also relate to image forming method that adopts this toner and the image processing system that adopts this toner.
Background technology
The background technology of resin
(about the problem of the used resin of tradition)
Plastics such as poly terephthalic acid diethylester (PET) resin, vibrin, vestolit or polyolefin resin before were extensive use of as mechanograph, for example, and the container such as food containers, beverage bottle, cosmetics containers or flowerpot.
After using, most of these plastic products all are dropped.Plastic refuse before all had been to handle through burning or landfill.Yet, because incineration of waste generates a large amount of burning capacitys, they all have the problem such as the caused air pollution of generation that relates to incinerator permanance, the processing charges of high temperature resistant incinerator, poisonous burning gas such as carbon monoxide, sulphur compound, chlorine or dioxin that combustion temperatures causes.In addition, when plastic refuse during by landfill, they are not decomposed and temporary transient the preservation, and assemble in treatment plant as refuse, cause the social concern that is called the refuse problem thus.And because plastic refuse is present in the ground, they cause and relate to the instable problem of soil in the landfill point, and refuse can influence the physical environment and all kinds of biosome of the interior or neighboring area of landfill point, and this also is a danger.
Therefore, for addressing these problems, in these years biodegradable resin becomes the focus of concern.Use term " biodegradable resin " to represent a kind of resin herein, it has the plastics physical property much at one with common purposes during being used as starting material, but use the back in physical environment, to be decomposed by microorganism rapidly, for example on the ground, in, in the compost, in the active slurry and in the water.Resin is broken down into fine-powdered, and the biodegradable resin of some types finally can be converted into carbon dioxide and water.
Except specific polyester biodegradable resin, also known traditionally blending resin combination satisfies above-mentioned needs, and the example of this class blending resin combination comprises starch-ethylene-vinyl alcohol copoly type resin, ethylene-vinyl alcohol copoly type resin-aliphatic polyester resin and aliphatic polyester resin-polyolefin resin.Use these resins or resin combination with the various process equipments that are fit for various uses in the practice.Yet, a kind of resin combination is not proposed yet, it has the required working ability of excellent production run, required various physical propertys and abandons the required biodegradability in back.
(about polyhydroxy-alkanoates (PHA))
In recent years, as the problem of environmental pollution that solves about causing, the biodegradable resin that microorganism is synthetic has been proposed by way of parenthesis as the moulded parts starting material by discarded object such as moulded goods.The example of the known biodegradable resin that is derived from microorganism comprises polyhydroxy-alkanoates (below be sometimes referred to as PHA), for example the multipolymer (hereinafter referred to as PHB/V) of poly--3-hydroxyl n-butyric acie (below be sometimes referred to as PHB) or 3-hydroxyl n-butyric acie (below be sometimes referred to as 3HB) and the positive valeric acid of 3-hydroxyl (below be sometimes referred to as 3HV); Polysaccharide, for example bacteria cellulose or amylopectin; And poly-propylhomoserin, for example poly-gamma-glutamic acid or polylysin.Particularly, make PHA after the experience melt process, be used from various products with conventional plastics one.In addition, because PHA biodegradability excellence, therefore can expect this compound is applied on the soft component and be used for pharmaceutical applications etc.
Report multiple micro-organisms PHA and assembled this class product within it.The known kind of producing the microorganism of adopting, the composition and the condition of culture of nutrient culture media of depending on, this class PHA presents various compositions or structure; And be mainly the improvement physical property, also carried out controlling the research of this class The Nomenclature Composition and Structure of Complexes.Particularly, by making the simple relatively monomeric unit polymerization of structure, studied the biosynthesizing of PHA, this monomeric unit comprises 3HB, 3HV, 3-hydroxy-n-caproic acid (below be abbreviated as 3HHx) and 4-hydroxyl n-butyric acie (below be abbreviated as 4HB); And the manufacturing that report adopts multiple microorganism to carry out.Yet because fusing point and heat decomposition temperature are approaching mutually, the PHA that is made of the long 3-hydroxyl alkane acid of this short chain unit (the following scl-PHA of being abbreviated as) tends to pyrolysis, thereby causes extrusion molding performance deficiency.Because PHB has high crystal type, also tend to make the limited and mechanical property deterioration of elongation.
Recently, research work is active on the polyhydroxy-alkanoates (being abbreviated as mcl-PHA below this class PHA) that is made of the middle chain length 3-hydroxyl alkane acid unit with about 4～12 carbon atoms, and prepares mcl-PHA with acyclic aliphatic hydrocarbon, sad, caproic acid, gluconic acid sodium salt etc. as carbon source and be proved.Yet this class mcl-PHA fusing point is low, may cause viscosity or softening more than 50 ℃.
Above-mentioned all PHAs are the PHA that is made of such monomeric unit: this monomeric unit is by the beta oxidation of hydrocarbon or analog or is synthesized and only have at side chain the monomeric unit (following it can be abbreviated as usual-PHA) of alkyl by microorganism from sugared synthetic fatty acid; Or similar monomeric unit (for example, having the alkenyl that contains the two keys of nonterminal on the side chain).These materials are widely used on the physical property still not enough as plastic material.
For using PHA more in a wide range, importantly carry out broad research to improving its physical property, for this purpose, need exploitation and research to comprise the PHA of the monomeric unit of more diversified structure.On the other hand, based on the substituent character of introducing, by the substituting group of selecting according to desired character to introduce, expecting has substituent PHA on the side chain, i.e. " unusual-PHA " " functional polymer " for having extremely favourable sense and feature.Thereby the excellent PHA that R and D can obtain this class functionality and biodegradability simultaneously remains an important target.Substituent example comprises unsaturated alkyl (for example alkenyl or alkadienyl, particularly allyl), cyano group, halo alkyl and the epoxy radicals that contains aromatic ring group (for example phenyl or phenoxy group), ester group, has whole terminal double bond.For the PHA that contains phenyl or its part substituted radical, to have reported from the 5-phenylpentanoic acid and prepared PHA as substrate, it comprises 3-hydroxyl-5-phenylpentanoic acid as the unit; Prepare PHA from 5-(4 '-tolyl) valeric acid as substrate, it comprises 3-hydroxyl-5-(4 '-tolyl) valeric acid as the unit; And 5-(2 ', 4 '-dinitrophenyl) valeric acid is from preparing PHA as substrate, and it comprises 3-hydroxyl-5-(2 ', 4 '-dinitrophenyl) valeric acid and 3-hydroxyl-5-(4 '-nitrobenzophenone) valeric acid as the unit.For the PHA that contains phenoxy group or its part substituted radical, to have reported from 11-phenoxy group capric acid and prepared pha copolymer as substrate, it comprises 3-hydroxyl-5-phenoxy group valeric acid and 3-hydroxyl-9-phenoxy group n-nonanoic acid as the unit; Prepare PHA from 6-phenoxy group caproic acid, it comprises 3-hydroxyl-4-phenoxybutyhc unit and 3-hydroxyl-6-phenoxy group caproic acid unit; From the sad preparation of 8-phenoxy group PHA, it is sad that it comprises 3-hydroxyl-4-phenoxybutyhc, 3-hydroxyl-6-phenoxy group caproic acid unit and 3-hydroxyl-8-phenoxy group; And preparing PHA from 11-phenoxy group undecanoic acid, it comprises 3-hydroxyl-5-valeric acid unit and 3-hydroxyl-7-phenoxy group enanthic acid unit.Also reported the PHA homopolymer that constitutes by 3-hydroxyl-5-(single fluorophenoxy) pentanoate (3H5 (MFP) P) unit or 3-hydroxyl-5-(two fluorophenoxies) pentanoate (3H5 (DEP) P) unit, and the pha copolymer that comprises 3H5 (MEP) P unit at least or 3H5 (DFP) P unit, provide dystectic advantage that thereby stereoregularity and hydrophobicity are provided, keep gratifying operating characteristic simultaneously.Except the compound that fluorine replaces, studied the compound that cyano group and nitro replace equally.For example, reported from sad and cyano-benzene oxygen caproic acid and p-nitrophenyl oxygen base caproic acid prepared PHA as substrate, its comprise the 3-hydroxyl to cyano-benzene oxygen caproic acid or 3-hydroxyl p-nitrophenyl oxygen base caproic acid as monomeric unit.Being different from side chain is the common PHA of alkyl, on the PHA side chain in these reports aromatic ring is arranged, and helps to obtain to have the polymkeric substance of the physical property of being brought by this class aromatic ring.And, as the example of the special-PHA with cyclohexyl, reported from cyclohexyl butyric acid or cyclohexyl valeric acid and prepared this type of PHA.
As the new kind that is not limited to the physical property change, equally also studied the preparation of the PHA that has suitable functional group on the side chain, thereby made up new function with this substituting group.
Polymer, 41, report has had been found that the variation of solubleness in solvent among the 1703-1709 (2000), thereby make the 3-hydroxyl alkane acid at polar solvent such as methyl alcohol, acetone-water mixture (80/20, and soluble in non-polar solvent such as chloroform, tetrahydrofuran and acetone v/v) and solvable in the dimethyl sulfoxide; Described 3-hydroxyl alkane acid have on the side chain terminal glycol, through adopting potassium permanganate after PHA preparation oxidation reaction and synthesize, this PHA contains 3-hydroxyl alkane acid that the side chain terminal has unsaturated link as monomeric unit, usefulness 10-undecanoic acid is as substrate.Macromolecular Chemistry, 4, report has had been found that the improvement to the decomposition rate of PHA among the 289-293 (2001), this PHA comprises 3-hydroxyl-10-carboxyl n-nonanoic acid and reacts as monomeric unit, oxidation cleavage through adopting potassium permanganate after (preceding) PHA preparation and synthesize, should contain 3-hydroxyl-10-undecanoic acid as monomeric unit by (preceding) PHA, and use the 10-undecanoic acid as substrate.
The toner background technology
Known up to now multiple electrophotography.Usually, by adopting photoconductive material and the whole bag of tricks carrying upward formation electrostatic latent image of figure element (light activated element), make image development form visual image (toner image) with toner subsequently, when situation needs toner image is transferred on the offset medium, by heating or pressurization toner image is fixed on the offset medium then, obtains duplicating image.For the method that electrostatic latent image is formed visual image, cascade development, magnetic brush development, pressure develoment etc. are well known in the art.Another kind method also is known, and the rotation of wherein adopting magnetic color tuner and core to be furnished with magnetic pole is developed and overlapped roller, makes magnetic color tuner fly to light activated element by electric field from the cover roller that develops.
Used developing method during for latent electrostatic image developing, available have a bi-component development method, utilizes the two-component-type developer solution of being made up of toner and carrier; The single component development method is utilized the single component development liquid that does not adopt carrier and only be made of toner.The colored particulate that is commonly referred to toner is by constituting as the adhesive resin of solvent and colorant and nonessential magnetic material, charge control agent etc.
(charge control agent)
For making toner charged, can utilize the charged characteristic of adhesive resin self and do not adopt charge control agent, but, can not obtain gratifying image quality owing to lack the timely stability and the water proofing property of electric charge.Therefore, in order to keep and to control electric charge, usually charge control agent is added in the toner.The charge control agent that is used for the negative friction electricity known to the present technique field comprises for example metal complex, the metal complex of aromatic dicarboxylic acid and the metal complex of salicyclic acid derivatives of azo dyes at present.For positive charge control agent, known aniline black byestuffs, triphenyl methane pigment, various quaternary ammonium salt and for example organo-tin compound of tributyl tin oxide.Yet, depend on its composition, to the desired qualitative characteristics of toner such as chargeable property or timely stability, containing also may be not exclusively satisfactory as the toner of this type of material of charge control agent.
For example, the toner that contains the azo dyes metal complex is known to negative charge controlling agent, although it shows the quantity of electric charge to a certain extent, but because the azo dyes metal complex is low-molecular-weight crystalline solid, depend on the resinous type for the treatment of combination, it also may cause relatively poor dispersibility.In this case, charge control agent is not to be evenly distributed in the adhesive resin, and the toner that obtains thus shows extremely unsharp charge amount distribution, and image forms scarce capacity, and low grade image is provided.And because its special color, azo dyes is used for the toner of black or limited color; When being used for color toner, hamper the critical defect of the accurate color of toner with it, this accurate color be obtain to satisfy to the image of the strict demand of color needed.
And for almost colourless negative charge controlling agent, the aromatic dicarboxylic acid metal complex is known, but it still is not colourless fully, owing to be low-molecular-weight crystalline solid, also may show not satisfied dispersibility.
And known aniline black byestuffs and triphenyl methane pigment as positive charge control agent owing to have special color, are used for the toner of black or limited color, may be also not enough on the timely stability of toner in the continuous compound rate operation.The tradition quaternary ammonium salt also may cause relatively poor timely stability, and gratifying image can not be provided in repeated use in the water proofing property deficiency in the toner that forms.
From the position of environmental protection, discarded object and environmental contaminants are all expected further to reduce in the whole world at present.The electrophotography field has this requirement equally.In fact, the amount of abandoning of used toner after printer paper, the usefulness and copy paper increases with extensively popularizing of imaging device every year; From the position of protecting the global environment, the security of this class discarded object also is an important issue.Consider these arguments, carry out research based on the charge control agent of polymkeric substance.The example of this compounds comprises United States Patent (USP) 4,480, those that disclose in 021,4,442,189 and 4,925,765.Usually, the polymer charge controlling agent that provides negative electricity characteristic to toner is usually formed by styrene and/or α-Jia Jibenyixi and with the multipolymer of sulfonic (methyl) alkyl acrylate or (methyl) acrylic acid alkyl acid amides.Because colourless, this material is favourable, but the quantity of electric charge of expecting for acquisition must add in a large number.
As previously mentioned, as charge control agent, these compounds do not have enough performances, and lack the quantity of electric charge, charged initial characteristics, timely stability and environmental stability.In addition, not only consider functionality, also consider influence to human body and environment, strongly need a kind of charge control agent itself, reach a kind of charge control agent, its can realize waiting to be used in the synthetic method of synthetic-a kind of safer milder-in compound and the use of organic solvent and the minimizing of organic solvent amount.This charge control agent and and synthetic method still unknown, the space that still promising functionality and Environmental security are contributed.
(other prior art document)
Among the present invention, can adopt United States Patent (USP) 6,521,429 and 6,586, the microorganism described in 562.Can also adopt J.Biol.Chem., 218, the nutrient culture media described in the 97-106 (1956).Technology related to the present invention comprises that the two key oxidation cleavages under the oxygenant effect of carbon=carbon obtain technology (J.Chem.Soc., Perkin.Trans.1,806 (1973) of carboxylic acid, Org.Synth., 4,698 (1963), J.Org.Chem., 46,19 (1981) and J.Am Chem.Soc., 81,4273 (1959)), and the method for synthetic 5-(4-tolyl) valeric acid (Macromolecules, 29,1762-1766 (1996)).
Summary of the invention
The polyester of side chain band aromatic ring has dystectic characteristics usually and has wide range of application.Yet, having the polyhydroxy-alkanoates type polyester that contains the aromatic ring unit and be limited to previous example, described aromatic ring is replaced by the substituting group that can be used for various uses, therefore expects that still polyhydroxy-alkanoates type polyester further improves functionality or has new function.
The present invention will solve foregoing problems and novel polyhydroxyalkanoatehaving is provided, and the sulfonic group of wherein introducing formation hydrophilic group or polar group or its deriveding group are to improve various functionality; And provide its preparation method.
The present invention also provide a kind of comprise this polyhydroxy-alkanoates can electronegative charge control agent, also improved functionality, the for example higher Environmental security effect and higher performance (the higher quantity of electric charge, more charging quickly, more excellent timely stability and higher environmental stability), and show improved dispersibility; A kind of toner that is used to make developing electrostatic charge image; A kind of image forming method and a kind of image processing system that adopts this developing electrostatic charge image toner.
Result as to the thoroughgoing and painstaking research of the exploitation of novel polyhydroxyalkanoatehaving has introduced in this polyhydroxy-alkanoates and has thought that the inventor obtains the present invention of following elaboration to improving favourable hydrophilic radical of multiple function or polar group.
The inventor finds that also aforesaid PHA has extremely excellent characteristic as charge control agent, and to human body and environment high safety; Also find to comprise this type of charge control agent and this type of toner that is used for developing electrostatic lotus picture is used under the situation of the image processing system of being furnished with specific toning system, can obtain significant effect at the toner that is used for developing electrostatic lotus picture.
In this instructions, term " halogen " is meant halogen atom in substituent definition.
According to an aspect of the present invention, provide polyhydroxy-alkanoates, comprise the unit of a kind of chemical formula (1) representative in its molecule at least:
R wherein
1Represent OH, halogen atom, ONa, OK or OR
1aA
1And OR
1aEach representative replaces or unsubstituted aliphatic hydrocarbon structure, replacement or unsubstituted aromatic ring structure or replacement or unsubstituted heterocycle structure; The m representative is selected from 0～7 integer; And when having multiple unit, to every kind of unit R
1, A
1, R
1aHas aforementioned implication independently with m.
According to a further aspect in the invention, provide a kind of method for preparing polyhydroxy-alkanoates, comprising:
Preparation comprises polyhydroxy-alkanoates, and the step of the amines of at least a chemical formula (25) representative of the unit of chemical formula (24) representative; With
Make this polyhydroxy-alkanoates and amines carry out the step of condensation reaction, thereby obtain comprising the polyhydroxy-alkanoates of the unit of chemical formula (1) representative:
Wherein the p representative is selected from 0～7 integer; R
24Represent H, Na or K; When having multiple unit, to every kind of unit p and R
24Has aforementioned implication independently.
H
2N-A
1-SO
2R
1 (25)
R wherein
1Represent OH, halogen atom, ONa, OK or OR
1aA
1And OR
1aEach representative replaces or unsubstituted aliphatic hydrocarbon structure, replacement or unsubstituted aromatic ring structure or replacement or unsubstituted heterocycle structure.
According to a further aspect of the invention, provide a kind of method for preparing polyhydroxy-alkanoates, comprising:
The step for preparing the polyhydroxy-alkanoates of the unit that comprises chemical formula (26) representative;
R wherein
26Represent OH, halogen atom, ONa or OK; A
26Representative replaces or unsubstituted aliphatic hydrocarbon structure, replacement or unsubstituted aromatic ring structure or replacement or unsubstituted heterocycle structure; The m representative is selected from 0～7 integer; And when having multiple unit, R
26, A
26With m every kind of unit had aforementioned implication independently;
Make the step of this polyhydroxy-alkanoates and trimethyl silyl bisdiazo methane reaction, thereby obtain comprising the polyhydroxy-alkanoates of the unit of chemical formula (27) representative:
A wherein
27Representative replaces or unsubstituted aliphatic hydrocarbon structure, replacement or unsubstituted aromatic ring structure or replacement or unsubstituted heterocycle structure; The m representative is selected from 0～7 integer; And when having multiple unit, A
27With m every kind of unit had aforementioned implication independently.
In accordance with a further aspect of the present invention, provide a kind of improved charge control agent, in order to the state of charge of control dusty material, wherein this improvement comprises:
Comprise at least a unit in the unit of chemical formula (1) representative.
According to a further aspect in the invention, provide a kind of developing electrostatic charge image toner, it comprises at least a adhesive resin, a kind of colorant and above charge control agent.
According to a further aspect in the invention, provide a kind of image forming method, comprising: give the step of charge member impressed voltage, give the charging of electrostatic latent image load-carrying unit thus; On the electrostatic latent image load-carrying unit that has charged, form the step of electrostatic charge image; Development step makes developing electrostatic charge image with the developing electrostatic charge image toner, forms toner image thus on the electrostatic latent image load bearing unit; Transfer step is transferred to the toner image on the electrostatic latent image load bearing unit on the recording materials; And fixing step, the toner image heating is fixed on the recording materials; This method comprises uses above-mentioned developing electrostatic charge image toner.
According to a further aspect in the invention, provide a kind of image processing system, thereby comprise the device that impressed voltage is given the charging of electrostatic latent image load-carrying unit to the charge member; On the electrostatic latent image load-carrying unit that has charged, form the device of electrostatic charge image; Make developing electrostatic charge image on the electrostatic latent image load bearing unit, form the developing device of toner image thus with the developing electrostatic charge image toner; Toner image on the electrostatic latent image load bearing unit is transferred to transfer printing device on the recording materials; And toner image heating is fixed to immobilising device on the recording materials; This device comprises the developing electrostatic charge image toner that use is above-mentioned.
2-naphthylamine-1-the methylmesylate of chemical formula (67) representative is provided according to another aspect of the invention,
According to the present invention, a kind of novel polyhydroxyalkanoatehaving and preparation method thereof is provided, wherein sulfonic group or its deriveding group constitute hydrophilic group or polar group, and can be used for various application.This novel polyhydroxyalkanoatehaving is excellent for the performance of melt-processed for example, and and living tissue between show gratifying coupling, therefore can expect to be applied as the flexible material of pharmaceutical use.
In addition, polyhydroxy-alkanoates by comprising at least a chemical formula (1) representative in the developing electrostatic charge image toner is as charge control agent, a kind of developing electrostatic charge image toner is provided, its this compounds with excellent charge characteristic and improvement in toner resin dispersibility and used character; And it avoids the image knot mist on the image processing system output image, and the transfer printing excellence is fit to electrophotography very much.And colourless or very weak color is only arranged as charge control agent of the present invention, can select any colorant according to the tone of color toner, the initial tone of dyestuff or pigment is not hindered.In addition, developing electrostatic charge image toner of the present invention need not to use heavy metal and is biodegradable, thereby need not burn processing, provides important industrial advantage in Environmental security in air pollution or the global warming as preventing thus.
The accompanying drawing summary
Fig. 1 is the synoptic diagram of the image processing system that adopted in embodiment 25～30 and the Comparative Examples 7～12;
Fig. 2 is the partial cross section figure of the bi-component developing liquid developing device of employing in embodiment 25～30 and the Comparative Examples 7～12;
Fig. 3 is the synoptic diagram that the band toner of employing in embodiment 31～34 and the Comparative Examples 13～15 utilizes the image processing system of mechanical hook-up again;
Fig. 4 is the partial cross section figure of the single component development liquid developing apparatus of employing in embodiment 31～34 and the Comparative Examples 13～15;
Fig. 5 is the part decomposition diagram of the stationary installation that adopts in the embodiment of the invention;
Fig. 6 is the sectional view that amplifies, and the nothing that expression is in the stationary installation that adopts in the embodiment of the invention is driven the membrane stage in the state;
Fig. 7 is the synoptic diagram of emitting quantity of electric charge measurement mechanism that expression is used for measuring the toner quantity of electric charge;
Fig. 8 represents embodiment A-1 gained polyester
1The H-NMR spectrogram;
Fig. 9 represents embodiment A-2 gained polyester
1The H-NMR spectrogram;
Figure 10 represents embodiment A-3 gained polyester
1The H-NMR spectrogram;
Figure 11 represents Embodiment B-1 gained polyester
1The H-NMR spectrogram;
Figure 12 represents Embodiment B-3 gained polyester
1The H-NMR spectrogram;
Figure 13 represents Embodiment C-1 gained polyester
1The H-NMR spectrogram;
Figure 14 represents embodiment D-2 gained polyester
1The H-NMR spectrogram;
Figure 15 represents embodiment K-3 gained polyester
1The H-NMR spectrogram;
Figure 16 represents embodiment L-3 gained polyester
1The H-NMR spectrogram;
Figure 17 represents embodiment M-3 gained polyester
1The H-NMR spectrogram;
Implement best mode of the present invention
Below, will illustrate the present invention in more detail by its preferred implementation.As the result for realizing that aforementioned target is deeply and carefully studied, the inventor has been found that aforementioned polyhydroxy-alkanoates has extremely excellent characteristic as charge control agent, and to human body and environment high safety; Also find to comprise this type of charge control agent and this type of toner that is used for developing electrostatic lotus picture is used under the situation of the image processing system with specific toning system at the toner that is used for developing electrostatic lotus picture, can obtain significant effect, constitute the present invention thus.
Wait to adopt polyhydroxy-alkanoates in the present invention to have the basic boom identical, thereby, can be used for making various goods by melt-processed not only as being used for the conventional plastic goods with biodegradable resin; But also has the significant of the synthetic polymer that is different from petroleum derivation: by biodegradation and participate in natural material cycle.Therefore, it need not burn processing, can be used as the plastic material that can effectively prevent air pollution and global warming and make Environmental security and uses.
Below, will elaborate content of the present invention.
In polyhydroxy-alkanoates of the present invention, R
1aRepresentative has normal chain or branched alkyl or the replacement or the unsubstituted phenyl of 1～8 carbon atom.
In polyhydroxy-alkanoates of the present invention, A
1Can represent normal chain or branched alkylidene with 1～8 carbon atom, this alkylidene does not replace or by 1～16 SO
2R
3aReplace (R
3aRepresent OH, halogen atom, ONa, OK or OR
3b(R
3bRepresentative has normal chain or branched alkyl or the replacement or the unsubstituted phenyl of 1～8 carbon atom); And when having multiple unit, R
3aEvery kind of unit had aforementioned implication independently); And when having multiple unit, R
1aRepresentative has normal chain or branched alkyl or the replacement or the unsubstituted phenyl of 1～8 carbon atom.
In polyhydroxy-alkanoates of the present invention, substituting group-A
1SO
2R
1Can represent by following chemical formula (4 '):
R wherein
4a, R
4b, R
4c, R
4dAnd R
4eIn at least one represents SO
2R
4f(R wherein
4fBe OH, halogen atom, ONa, OK or OR
4hR
4hRepresentative has normal chain or branched alkylidene or the replacement or the unsubstituted phenyl of 1～8 carbon atom), and other each represent H, halogen atom, have the alkyl of 1～20 carbon atom, alkoxy, OH, NH with 1～20 carbon atom
2, NO
2, COOR
4g(R
4gRepresent H, Na or K), acetamido, OPh, NHPh, CF
3, C
2F
5Or C
3F
7And when having multiple unit, R
4a, R
4b, R
4c, R
4d, R
4e, R
4f, R
4gAnd R
4hEvery kind of unit had aforementioned implication independently.
In polyhydroxy-alkanoates of the present invention, substituting group-A
1SO
2R
1Expression is by the substituting group of following chemical formula (5a ') or (5b ') representative:
R wherein
5A, R
5B, R
5C, R
5D, R
5E, R
5FAnd R
5GIn at least one represents SO
2R
5O(R wherein
5OBe OH, halogen atom, ONa, OK or OR
5SR
5SRepresentative has normal chain or branched alkyl or the replacement or the unsubstituted phenyl of 1～8 carbon atom), and other each represent H, halogen atom, have the alkyl of 1～20 carbon atom, alkoxy, OH, NH with 1～20 carbon atom
2, NO
2, COOR
5P(R
5PRepresent H, Na or K), acetamido, OPh, NHPh, CF
3, C
2F
5Or C
3F
7And when having multiple unit, R
5A, R
5B, R
5C, R
5D, R
5E, R
5F, R
5G, R
5O, R
5PAnd R
5SEvery kind of unit had aforementioned implication independently.
R wherein
5H, R
5I, R
5J, R
5K, R
5L, R
5MAnd R
5NIn at least one represents SO
2R
5Q(R wherein
5QBe OH, halogen atom, ONa, OK or OR
5tR
5tRepresentative has normal chain or branched alkyl or the replacement or the unsubstituted phenyl of 1～8 carbon atom), and other each represent hydrogen atom, halogen atom, have the alkyl of 1～20 carbon atom, alkoxy, OH, NH with 1～20 carbon atom
2, NO
2, COOR
5R(R
5RRepresent H, Na or K), acetamido, OPh, NHPh, CF
3, C
2F
5Or C
3F
7The m representative is selected from 0～7 integer; And when having multiple unit, R
5H, R
5I, R
5J, R
5K, R
5L, R
5M, R
5N, R
5Q, R
5R, R
5tWith m every kind of unit had aforementioned implication independently.
In polyhydroxy-alkanoates of the present invention, substituting group-A
1SO
2R
1Can represent by following chemical formula (6 '):
R wherein
1Be OH, halogen atom, ONa, OK or OR
6b(R wherein
6bRepresentative has normal chain or branched alkyl or the replacement or the unsubstituted phenyl of 1～8 carbon atom); And when having multiple unit, R
6bEvery kind of unit had aforementioned implication independently.
In polyhydroxy-alkanoates of the present invention, A
1Can be to phenylene:
And R
1aBe normal chain or branched alkyl or replacement or unsubstituted phenyl with 1～8 carbon atom.
In polyhydroxy-alkanoates of the present invention, A
1Can be adjacent phenylene:
And R
1aBe normal chain or branched alkyl or replacement or unsubstituted phenyl with 1～8 carbon atom.
In polyhydroxy-alkanoates of the present invention, substituting group-A
1SO
2R
1Can be the group of chemical formula (9 ') representative:
R wherein
1aBe normal chain or branched alkyl or replacement or unsubstituted phenyl with 1～8 carbon atom.
In polyhydroxy-alkanoates of the present invention, substituting group-A
1SO
2R
1Can be the group of chemical formula (10 ') representative:
R wherein
1aBe normal chain or branched alkyl or replacement or unsubstituted phenyl with 1～8 carbon atom.
In polyhydroxy-alkanoates of the present invention, substituting group-A
1SO
2R
1Can be the group of chemical formula (52 ') representative:
R wherein
1aBe normal chain or branched alkyl or replacement or unsubstituted phenyl with 1～8 carbon atom.
In polyhydroxy-alkanoates of the present invention, A
1Can be 1, the 8-naphthylene:
And R
1aBe normal chain or branched alkyl or replacement or unsubstituted phenyl with 1～8 carbon atom.
Except the unit of chemical formula (1) representative, polyhydroxy-alkanoates of the present invention also can further comprise at least a in the following two class unit: the alkanoic acid unit of the 3-hydroxyl-ω-replacement of chemical formula (11) representative:
Wherein n is selected from 1～8 integer, R
11Represent a kind of residue, comprise the ring texture of phenyl structure or thienyl structure, and when having multiple unit, n and R
11Every kind of unit had aforementioned implication independently; With
3-hydroxyl-ω-hexamethylene alkanoic acid the unit of chemical formula (12) representative:
R wherein
12Expression H, CN, NO
2, halogen atom, CH
3, C
2H
5, C
3H
7, CF
3, C
2F
5Or C
3F
7K is selected from 0～8 integer; And when having multiple unit, R
12With k every kind of unit had aforementioned implication independently.
In polyhydroxy-alkanoates of the present invention, R
11Can represent any of chemical formula (13), (14), (15), (16), (17), (18), (19), (20), (21), (22) and (23), and when having multiple unit, this unit has aforementioned implication independently to every kind of cell cube:
R wherein
13Represent H, halogen atom, CN, NO
2, CH
3, C
2H
5, C
3H
7, CH=CH
2, COOR
13a(R
13aRepresent H, Na or K), CF
3, C
2F
5Or C
3F
7And when having multiple unit, this unit has aforementioned implication independently to every kind of cell cube;
R wherein
14Represent H, halogen atom, CN, NO
2, CH
3, C
2H
5, C
3H
7, SCH
3, CF
3, C
2F
5Or C
3F
7And when having multiple unit, this unit has aforementioned implication independently to every kind of unit;
R wherein
15Represent H, halogen atom, CN, NO
2, CH
3, C
2H
5, C
3H
7, CF
3, C
2F
5Or C
3F
7And when having multiple unit, this unit has aforementioned implication independently to every kind of unit;
R wherein
16Represent H, halogen atom, CN, NO
2, COOR
16a, SO
2R
16b(R
16aRepresent H, Na, K, CH
3Or C
2H
5R
16bRepresent OH, ONa, OK, halogen atom, OCH
3Or OC
2H
5), CH
3, C
2H
5, C
3H
7, (CH
3)
2CH or (CH
3)
3C; And when having multiple unit, this unit has aforementioned implication independently to every kind of unit;
R wherein
17Represent H, halogen atom, CN, NO
2, COOR
17a, SO
2R
17b(R
17aRepresent H, Na, K, CH
3Or C
2H
5R
17bRepresent OH, ONa, OK, halogen atom, OCH
3Or OC
2H
5), CH
3, C
2H
5, C
3H
7, (CH
3)
2CH or (CH
3)
3C; And when having multiple unit, this unit has aforementioned implication independently to every kind of unit;
R wherein
21Represent H, halogen atom, CN, NO
2, COOR
21a, SO
2R
21b(R
21aRepresent H, Na, K, CH
3Or C
2H
5R
21bRepresent OH, ONa, OK, halogen atom, OCH
3Or OC
2H
5), CH
3, C
2H
5, C
3H
7, (CH
3)
2CH or (CH
3)
3C; And when having multiple unit, this unit has aforementioned implication independently to every kind of unit;
R wherein
22Represent H, halogen atom, CN, NO
2, COOR
22a, SO
2R
22b(R
22aRepresent H, Na, K, CH
3Or C
2H
5R
22bRepresent OH, ONa, OK, halogen atom, OCH
3Or OC
2H
5), CH
3, C
2H
5, C
3H
7, (CH
3)
2CH or (CH
3)
3C; And when having multiple unit, this unit has aforementioned implication independently to every kind of unit;
In polyhydroxy-alkanoates of the present invention, number-average molecular weight can be in 1000～1000000 scopes.
In preparation method of the present invention, condensation reaction can be the reaction that forms amido link with condensation agent.Condensation agent can be that to be selected from phosphoric acid be that condensation agent, carbodiimide are that condensation agent and acid chloride are at least a in the condensation agent.
In preparation method of the present invention; condensation reaction can be such reaction: the carboxylic moiety of polyhydroxy-alkanoates that will comprise the unit of chemical formula (24) representative is converted into acid chloride, the compound with chemical formula (25) representative reacts then, forms amido link thus.It is that condensation agent is as condensation agent that condensation reaction can be adopted thionyl (two) chlorine.
In charge control agent of the present invention, dusty material can be the developing electrostatic charge image toner.
In image forming method of the present invention, transfer step can comprise: first transfer step is transferred to the toner image on the electrostatic latent image load-carrying unit on the intermediate transfer element; And second transfer step, the toner image on the intermediate transfer element is transferred on the recording materials.
In image processing system of the present invention, the transfer printing device can comprise: the first transfer printing device is transferred to the toner image on the electrostatic latent image load-carrying unit on the intermediate transfer element; And the second transfer printing device, the toner image on the intermediate transfer element is transferred on the recording materials.
Constitute theme of the present invention and by the polyhydroxy-alkanoates of chemical formula (1) expression by making polyhydroxy-alkanoates, it comprises 3-hydroxyl-ω-(4-carboxyl phenyl) alkanoic acid unit of chemical formula (24) representative, reacts with the compound of at least a chemical formula (25) representative and prepares.
(preparation comprises the method for polyhydroxy-alkanoates of the unit of chemical formula (24) representative)
The polyhydroxy-alkanoates that comprises 3-hydroxyl-ω-(4-carboxyl phenyl) alkanoic acid unit of chemical formula (24) representative prepares like this: by two keys oxidation cleavage partly of polyhydroxy-alkanoates, this polyhydroxy-alkanoates comprises 3-hydroxyl-ω-(4-ethenylphenyl) alkanoic acid unit of chemical formula (28) representative; Perhaps pass through the oxidation of the methyl moiety of polyhydroxy-alkanoates, this polyhydroxy-alkanoates comprises 3-hydroxyl-ω-(4-aminomethyl phenyl) alkanoic acid unit of chemical formula (54) representative.
(wherein 0～7 integer is selected in the s representative, exists under the situation of multiple unit, and s has aforementioned implication independently to every kind of unit),
(wherein 0～7 integer is selected in 1 representative, exists under the situation of multiple unit, and 1 pair of every kind of unit has aforementioned implication independently),
For by make two keys of carbon=carbon or methyl oxidation obtain carboxylic acid with oxygenant, known method (the J.Chem.Soc.Perkin.Trans.1 that for example adopts permanganate, 806 (1973)), adopt the method (Org.Synth. of dichromate, 4,698 (1963)), adopt the method (J.Org.Chem. of periodate, 46,19 (1981)), adopt the method (the open S59-190945 of Japanese Patent Laid) of nitric acid and the method (J.Am.Chem.Soc. that adopts ozone, 81,4279 (1959)); And, based on polyhydroxy-alkanoates, aforesaid MacromolecularChemistry, 4,289-293 (2001) reported a kind of with potassium permanganate as oxygenant and under acid condition, make the two key oxidations of carbon=carbon of polyhydroxy-alkanoates side chain terminal and obtain the method for carboxylic acid.Also can adopt similar method among the present invention.
The permanganate that will adopt as oxygenant is potassium permanganate normally.Because oxidation reaction is stoichiometric reaction, the unit of corresponding 1 mole of chemical formula (28) or (54) representative, the amount of permanganate is generally 1 molar equivalent or higher, preferred 2～10 molar equivalents.
In order under acid condition, to react, adopt mineral acid such as sulfuric acid, hydrochloric acid, acetate or nitric acid usually; Or organic acid.Yet use sulfuric acid, nitric acid or hydrochloric acid can cause that the ester group in the polyhydroxy-alkanoates main chain divides, thereby cause molecular weight to reduce.Therefore the preferred acetate that adopts.For the unit of per 1 mole of chemical formula (28) or (54) representative, the acid amount usually in 0.2～2000 molar equivalent scope, preferred 0.4～1000 molar equivalent.The amount that is less than 0.2 molar equivalent will cause low-yield, and decompose the generation accessory substance above the amount of 2000 molar equivalents through acid.Can also adopt crown ether that reaction is quickened.In this case, crown ether and permanganate form complex compound, and the effect that improves reactivity is provided thus.For crown ether, adopt dibenzo-19 crown ether-6, dibenzo (dicyclo)-18 crown ether-6 or 18 crown ethers-6 usually.For per 1 mole of permanganate, the amount of crown ether usually in 0.005～2.0 molar equivalent scope, preferred 0.01～1.5 molar equivalent.
For solvent used in the oxidation reaction of the present invention, can adopt any solvent of this reactionlessness and do not have particular restriction, for example water; Acetone; Ether, for example tetrahydrofuran or dioxane; Aromatic hydrocarbon, for example benzene, toluene or dimethylbenzene; Aliphatic hydrocarbon, for example hexane or heptane; Or halogenated hydrocarbons, for example chloromethanes, methylene chloride or chloroform.In these solvents, consider the dissolubility of polyhydroxy-alkanoates, preferably such as the halogenated hydrocarbons or the acetone of chloromethanes, methylene chloride or chloroform.
In aforesaid oxidation reaction of the present invention, the polyhydroxy-alkanoates, permanganate and the acid that comprise the unit of chemical formula (28) or (54) representative can be by just reacting with the common charging of solvent from beginning; Perhaps react by adding in the reaction system respectively continuously and off and on.This reaction also can be by at first only being dissolved or suspended in permanganate in the solvent, continuously or off and on polyhydroxy-alkanoates and acid added in this system then and carried out; Perhaps by at first only polyhydroxy-alkanoates being dissolved or suspended in the solvent, continuously or off and on permanganate and acid being added in this system then and carried out.This reaction can also be added to permanganate this system and carry out then continuously or off and on by polyhydroxy-alkanoates and the acid of packing into earlier; Perhaps, polyhydroxy-alkanoates is added to this system continuously or off and on then and carries out by permanganate and the acid of packing into earlier; By polyhydroxy-alkanoates and the permanganate of packing into earlier, acid is added to this system continuously or off and on then and carries out.
Temperature of reaction is chosen in-40～40 ℃ the scope usually, preferred-10～30 ℃.Reaction time is depended on chemical formula (28) or the unit of (54) representative and the stoichiometric proportion and the temperature of reaction of permanganate, but is selected from 2～48 hours scope usually.
In addition, except that 3-hydroxyl-ω-(4-aminomethyl phenyl) alkanoic acid unit that 3-hydroxyl-ω-(4-ethenylphenyl) the alkanoic acid unit and the chemical formula (54) of chemical formula (28) representative are represented, under the situation that also adopts following polyhydroxy-alkanoates: it comprises the 3-hydroxyl-ω-replacement alkanoic acid unit of chemical formula (11) representative or the 3-hydroxyl-ω-cyclohexyl alkanoic acid unit of chemical formula (12) representative, and reaction can be carried out under simulated condition.
(preparation comprises the method for polyhydroxy-alkanoates of the unit of chemical formula (28) or (54) representative)
The polyhydroxy-alkanoates of the stand-by unit that comprises chemical formula (28) or (54) representative in the present invention can prepare by the following method: adopt method that microorganism makes, through the method or the chemical polymerization method of genetic engineering cultivation system, although these class methods are not had particular restriction.Preparing by the method that comprises the microorganism manufacturing step under the situation of this compounds, above-mentioned polyhydroxy-alkanoates is the isotactic polymer that only is made of R unit, but this class isotactic multipolymer not necessarily, as long as the present invention can realize about the target of physical property and function, also can adopt atactic polymers.Aforementioned polyhydroxy-alkanoates also can obtain by the method that comprises the chemosynthesis step, and for example, this method adopts the ring-opening polymerization of lactone.
Below will elaborate a kind of microorganism and make, be used to prepare the polyhydroxy-alkanoates that comprises the unit of chemical formula (28) and (54) representative of the present invention.
Constituting raw-material polyhydroxy-alkanoates obtains by a kind of preparation method, this preparation method characteristic is in nutrient culture media to cultivate aforesaid microorganism, and this nutrient culture media comprises at least a in ω-(4-aminomethyl phenyl) alkanoic acid of ω-(4-ethenylphenyl) alkanoic acid of chemical formula (29) representative or chemical formula (55) representative.
(wherein t is selected from 0～7 integer).
(wherein q is selected from 0～7 integer).
Prepare the raw-material polyhydroxy-alkanoates that comprises the unit of chemical formula (28) or (54) representative by in nutrient culture media, cultivating as the present invention, the microorganism that is used in its preparation method can be the microorganism of any PHA of having manufacturing capacity, be any microorganism that can make PHA type polyester, this polyester comprises 3-hydroxyl-ω-(4-ethenylphenyl) the alkanoic acid unit of chemical formula (28) representative or 3-hydroxyl-ω-(4-aminomethyl phenyl) alkanoic acid unit of chemical formula (54) representative; Described nutrient culture media comprises ω-(4-ethenylphenyl) the alkanoic acid unit of chemical formula (29) representative or ω-(4-aminomethyl phenyl) alkanoic acid unit of chemical formula (55) representative.The preferred embodiment of the available microorganism with PHA manufacturing capacity comprises the microorganism that belongs to pseudomonas (Pseudomonas).Wherein, more preferred such bacterial strain, it has the PHA manufacturing capacity but do not show for example oxidation or epoxidised enzyme reaction on the vinyl that replaces on the phenolic group.
More particularly, in belonging to the microorganism of pseudomonad, can comprise Pseudomonas cichorii (Pseudomonas cichorii), pseudomonas putida (Pseudomonas putida), Pseudomonas fluorescens (Pseudomonas fluorecense), Pseudomonas oleovorans (Pseudomonas oleovolans), pseudomonas aeruginosa (Pseudomonasaeruginosa), Pseudomonas stutzeri (Pseudomonas stutzeri), Pseudomonas jessenii as the more preferably bacterial classification of the microorganism that is used for manufacture method of the present invention.
In addition, bacterial strain preferably comprises for example Pseudomonas cichorii strain YN2 (FERM BP-7375), Pseudomonas cichorii strain H45 (FERM BP-7374), jessenii pseudomonad strain P161 (FERMBP-7376) and pseudomonas putida strain P91 (FERM BP-7373).These four kinds of bacterial strains are preserved on November 20th, 2000 and are positioned at Japan, Ibaraki-Ken 305-8566, Tsukuba-shi, Higashi1-chome, 1-1, Tsukuba
The international patent organism preservation institute (IPOD) of the life engineering Industrial Technology Research Institute of Govement Industrial Research Inst., Ministry of Commerce (AIST) of Central6, and be described among open 2001-288256 of Japanese patent application and the open 2002-80751 of Japanese patent application.
In manufacture method of the present invention, the nutrient culture media that adopts in the microbe culture step can be the nitrogenous source of any inorganic salts medium and for example ammonium salt or nitrate, can also improve the throughput rate of PHA in the method for making PHA with microorganism by the concentration of adjusting nitrogenous source in the nutrient culture media.
In addition, the nutrients such as yeast extract, many peptones and meat extract can also be added in the nutrient culture media as matrix, to promote the breeding of microorganism.That is to say, can peptide be added as the energy and carbon source with nutraceutical form such as yeast extract, many peptones and meat extract.
Alternately, for nutrient culture media, carbohydrate and disaccharides can be used as the energy and carbon source, consume with the breeding of microorganism, carbohydrate for example: aldose, as glyceraldehyde, erythrose, arabinose, wood sugar, glucose, galactose, mannose and fructose; Alditol is as glycerine, antierythrite and xylitol; Glycuronic acid is as gluconic acid; Uronic acid is as glucuronic acid and galacturonic acid; Disaccharides is maltose, sucrose and lactose for example.
Substitute above-mentioned sugar, its organic acid or salt, can use organic acid that comprises in the TCA ring more specifically and organic acid or its water soluble salt of deriving from the biochemical reaction that lacks one or two step than the TCA circulation.For this organic acid or its salt, can use hydroxycarboxylic acid and oxo carboxylic acid, as pyruvic acid, butanone diacid, citric acid, isocitric acid, ketoglutaric acid, succinic acid, fumaric acid, malic acid and lactic acid, or its water soluble salt.Alternately, can use amino acid or its salt, for example, as amino acid or its salt of aspartic acid and glutamic acid.When adding organic acid or its salt, more preferably from pyruvic acid, butanone diacid, citric acid, isocitric acid, ketoglutaric acid, succinic acid, fumaric acid, malic acid, lactic acid and its salt, select one or more, and it is added to and is dissolved in the nutrient culture media.Alternately, when adding amino acid or its salt, more preferably from aspartic acid, glutamic acid and its salt, select one or more, and it is added to and is dissolved in the nutrient culture media.At this moment, as required, it is partly or entirely added with the form of water soluble salt, this salt does not influence uniform dissolution the pH value of nutrient culture media.
As the carbon source of growth of microorganism and the energy of manufacturing polyhydroxy-alkanoates, expectation is selected the concentration that is added to the above-mentioned coexistence matrix in the nutrient culture media, makes it usually at 0.05～5% (w/v), more preferably in the scope of every (volume) nutrient culture media of 0.2～2% (w/v).That is to say, for as peptide, yeast extract, organic acid or its salt, amino acid or its salt and the carbohydrate of above-mentioned coexistence matrix, can add wherein one or more; At this moment, the total concentration of these substrates of being added of expectation is in above-mentioned total concentration scope.
Be used to prepare the concentration of substrate of the polyhydroxy-alkanoates of expectation, be the concentration of ω-(4-ethenylphenyl) alkanoic acid or ω-(4-aminomethyl phenyl) alkanoic acid that chemical formula (55) is represented of chemical formula (29) representative, preferably from the scope of 0.01～1% (w/v), more preferably 0.02～0.2% (w/v).
In addition, except comprising the matrix of the polyhydroxy-alkanoates that is used to prepare expectation, be outside ω-(4-aminomethyl phenyl) alkanoic acid of ω-(4-ethenylphenyl) alkanoic acid of chemical formula (29) representative or chemical formula (55) representative, ω-cyclohexyl alkanoic acid that ω-replacements chain acid compound by comprising at least a chemical formula (30) representative or at least a chemical formula (31) are represented, make the such polyhydroxy-alkanoates of preparation possibility that become: it also comprises the 3-hydroxyl-ω-replacement alkanoic acid unit of chemical formula (11) representative or 3-hydroxyl-ω-cyclohexyl alkanoic acid unit that chemical formula (12) is represented except 3-hydroxyl-ω-(4-aminomethyl phenyl) alkanoic acid unit of 3-hydroxyl-ω-(4-ethenylphenyl) the alkanoic acid unit that comprises chemical formula (28) representative or chemical formula (55) representative.
(wherein u makes and is selected from 1～8 integer; R
30Comprise or the ring texture of phenyl structure or thiophene structure, and represent in aforementioned chemical formula (13), (14), (15), (16), (17), (18), (19), (20), (21), (22) and (23) any; And when having multiple unit, it has aforementioned implication independently to every kind of unit.)
(R wherein
31Represent the substituting group on the cyclohexyl; R
31Represent H, CN, NO
2, halogen atom, CH
3, C
2H
5, C
3H
7, CF
3, C
2F
5Or C
3F
7V is selected from 0～8 integer.)
Can its down any temperature that can suitably breed of microorganism used therefor bacterial strain be elected to be cultivation temperature, suitable temperature usually in about 15～37 ℃ of scopes, more preferably from about 20～30 ℃.
As long as can make microbial reproduction and make PHA, all can be used for cultivating such as any cultural method of Liquid Culture and solid culture.In addition, can adopt the cultural method of any kind of as batch culture, in batches feed cultivation, semicontinuous cultivation and Continuous Cultivation and so on.The method of supply oxygen and adopt the method for ventilating system that the stir when form of liquid batch culture is included in microorganism in the vibration vibration bottle to the fermentation tank supply oxygen.
Make and assemble the method for PHA for making microorganism, can adopt two-steps tissue culture method but not a step cultivation, microorganism was cultivated through two steps in the two-steps tissue culture method, microorganism is cultivated in minimal medium in the one step cultivation, and this nutrient culture media comprises phosphate, nitrogenous source such as ammonium salt or nitrate and adds wherein matrix with aforesaid predetermined concentration.In this two-steps tissue culture method, microorganism in minimal medium fully breeding once, this nutrient culture media comprises phosphate, nitrogenous source such as ammonium salt or nitrate and adds wherein matrix with aforesaid predetermined concentration, as primary culture; Then, after the content of contained nitrogenous source such as ammonium chloride, the former cell of supporting gained of being commissioned to train is relocated in the nutrient culture media in the restriction nutrient culture media, this nutrient culture media has with predetermined content adding matrix wherein, further cultivates, as secondary cultivation; Make microorganism make and gather PHA thus.Use this two-steps tissue culture method can improve the throughput rate of expectation PHA.
Usually, because the existence of hydrophobic atomic radical, the 4-aminomethyl phenyl group of the 4-ethenylphenyl group of 3-hydroxyl-ω-(4-ethenylphenyl) alkanoic acid unit or 3-hydroxyl-ω-(4-aminomethyl phenyl) alkanoic acid unit for example, the PHA type polyester that generates has the water dissolvable of reduction and accumulates in the cells of microorganisms that can make PHA, therefore can separate with nutrient culture media by collecting cell, this cell is by cultivating breeding and being involved in the manufacturing and gathering of expectation PHA type polyester.Behind washing and the dry cell of collecting, can collect the PHA type polyester of expectation.
In addition, polyhydroxy-alkanoates accumulates in this class usually and can make in the cells of microorganisms of PHA.Method for collecting the PHA of expectation from these microbial cells can adopt normally used method.For example, the most advantageously use organic solvent extraction (extraction), as chloroform, methylene chloride, acetone and ethyl acetate.Except that above-mentioned solvent, also can adopt two mouthfuls of oxanes, tetrahydrofuran and acetonitriles.In addition, in disadvantageous working environment with an organic solvent, can adopt such method: wherein be not to adopt solvent extraction, but make the fragmentation of microbial cell physics with any in the following processing, with surfactant such as SDS handle, chemical treatments with enzyme such as lysozyme processing, use-case such as hypochlorite, ammonium and EDTA, sonioation method, homogenizer method, crushing method, pearl towards method, polishing, immerse method and freeze-thaw method, remove cellular component subsequently rather than PHA collects PHA.
As the example that can be used on the minimal medium in the manufacture method of the present invention, below will show a kind of composition of inorganic salts M9 nutrient culture media, this nutrient culture media is used among the embodiment that will set forth in the back.
(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)
Be the throughput rate that obtains gratifying bacterial multiplication and improve gained PHA, must give the trace element of above-mentioned inorganic medium such as M9 culture media supplemented necessity, as minor metallic element, very effective with the following trace element solution of about 0.3% (w/v) adding.The adding of this class microcomponent solution is for being provided for minor metallic element in the bacterial multiplication etc.
[composition of microcomponent solution]
Nitrilotriacetic acid 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)。
(compound of chemical formula (25) representative)
By chemical formula (25) representative and employing compound in the present invention can more specifically be heterocycle structure compound, wherein A
25Representative has replacement or unsubstituted normal chain or branched alkylidene, replacement or unsubstituted phenyl, replacement or the unsubstituted naphthyl of 1～8 carbon atom or contains replacement at least a among N, S and the O or unsubstituted heterocycle structure.At A
25Has under the situation of ring texture further condensation of unsubstituted ring on it.
A
25For the example of the compound of the replacement that has 1～8 carbon atom or unsubstituted normal chain or branched alkylidene comprises 2-aminoethane sulfonic acid (taurine), 3-aminopropyl sulfonic acid, 4-ammonia butyl sulfonic acid, 2-amino-2-methyl propane sulfonic acid and alkali metal salt thereof.
A25 is replace or the situation of unsubstituted phenyl under, it is by chemical formula (32 representative):
(R wherein
32a, R
32b, R
32c, R
32dAnd R
32eIn at least one represents SO
2R
32f(R wherein
32fBe OH, halogen atom, ONa, OK, OR
32hAnd R
32hRepresentative replaces or unsubstituted aliphatic hydrocarbon structure, replacement or unsubstituted aromatic ring structure or replacement or unsubstituted heterocycle structure), and other representative hydrogen atom, halogen atom, the alkyl with 1～20 carbon atom, the alkoxy with 1～20 carbon atom, OH, NH
2, NO
2, COOR
32g(R
32gRepresent H, Na or K), acetamido, OPh, NHPh, CF
3, C
2F
5Or C
3F
7).
The example of the compound of chemical formula (32) representative comprises the derivant of aminophenyl sulfonic acid or its salt, sulfanilic acid for example, metanilic acid, orthanilic acid, meta-aminotoluene-4-sulfonic acid, ortho-aminotoluene-4-sulfonate sodium, para-totuidine-2-sulfonic acid, 4-aminoanisole-2-sulfonic acid, adjacent anicidine-5-sulfonic acid, to anicidine-5-sulfonic acid, 3-nitroaniline-4-sulfonic acid, 2-nitroaniline-4-sulfonate sodium, 4-nitroaniline-2-sulfonate, 1,5-dinitroaniline-4-sulfonic acid, 2-amino-phenol-4-hydroxyl-5-nitrobenzene-sulfonic acid, 2,4-xylidin-5-sulfonate sodium, 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-oxybenzene amine-5-sulfonic acid, or 4-carboxyl aniline-6-sulfonic acid; Ester, for example methyl esters of aminobenzenesulfonic acid or its salt or phenyl ester, for example 2-aminobenzenesulfonic acid methyl esters, 4-aminobenzenesulfonic acid methyl esters, 2-amino phenyl sulfonyl acid phenenyl ester or 4-amino phenyl sulfonyl acid phenenyl ester-
At A
25Be under the situation of replacement or unsubstituted naphthyl, it is represented by chemical formula (32a) with (32b):
(R wherein
33A, R
33B, R
33C, R
33D, R
33E, R
33FAnd R
33GIn at least one represents SO
2R
33O(R wherein
330Be OH, halogen atom, ONa, OK, OR
33OAnd R
33ORepresentative replaces or unsubstituted aliphatic hydrocarbon structure, replacement or unsubstituted aromatic ring structure or replacement or unsubstituted heterocycle structure), and other representative hydrogen atom, halogen atom, the alkyl with 1～20 carbon atom, the alkoxy with 1～20 carbon atom, OH, NH
2, NO
2, COOR
33P(R
33PRepresent H, Na or K), acetamido, OPh, NHPh, CF
3, C
2F
5Or C
3F
7); And
(R wherein
33H, R
33I, R
33J, R
33K, R
33L, R
33MAnd R
33NIn at least one represents SO
2R
33Q(R wherein
33QBe OH, halogen atom, ONa, OK, OR
33tAnd R
33tRepresentative replaces or unsubstituted aliphatic hydrocarbon structure, replacement or unsubstituted aromatic ring structure or replacement or unsubstituted heterocycle structure), and other representative hydrogen atom, halogen atom, the alkyl with 1～20 carbon atom, the alkoxy with 1～20 carbon atom, OH, NH
2, NO
2, COOR
33R(R
33RRepresent H, Na or K), acetamido, OPh, NHPh, CF
3, C
2F
5Or C
3F
7).
Chemical formula (33a) and the examples for compounds of (33b) representing comprise naphthylamine sulfonic acid derivant and salt thereof, for example naphthalidine-4-sulfonic acid, 1-naphthylamine-5-sulfonic acid, naphthalidine-6-sulfonic acid, naphthalidine-7-sulfonic acid, naphthalidine-8-sulfonic acid, 2-naphthylamines-1-sulfonic acid, 2-naphthylamines-5-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-sulfonate sodium or 1-amino-8-naphthol-3, the 6-sulfonate sodium; Ester, for example methyl esters of naphthylamine sulfonic acid derivant and salt thereof or phenyl ester are as naphthalidine-8-methylmesylate, 2-naphthylamines-1-methylmesylate, naphthalidine-8-phenyl sulfonate or 2-naphthylamines-1-phenyl sulfonate.
Contain N in A25 representative, S or O one of at least heteroatomic replacement or during unsubstituted heterocycle structure, it can be, for example, pyridine ring, piperidine ring, furan nucleus or mercaptan ring.
(manufacture method of the polyhydroxy-alkanoates of chemical formula (1) representative)
Below will describe the condensation reaction of the sulfamic acid compound that polyhydroxy-alkanoates and chemical formula (25) that the present invention comprises the unit of chemical formula (24) representative represent in detail.Carry out method that carboxyl and amino condensation reaction can be by using condensation agent, through dehydration form salt and carry out condensation method, use dewatering agent method or with carboxyl be converted into acid chloride and with the method for amino reaction.
For the manufacture method among the present invention, below will elaborate the method for using condensation agent.
For condensation agent, can use phosphoric acid is that condensation agent, carbodiimide are that condensation agent or acid chloride are condensation agent; For example, be condensation agent for phosphoric acid, can adopt the phosphite ester condensation agent.Chloro phosphoric acid condensation agent, phosphoric anhydride condensation agent, phosphate condensation agent, phosphoamide condensation agent or thiophene chlorine condensation agent.
In reaction of the present invention, the preferred condensation agent that adopts based on phosphite ester.The example of phosphite ester to be adopted comprises that triphenyl phosphite, Trimethyl phosphite, triethyl phosphite, phosphorous acid diphenyl ester, tricresyl phosphite o-toluene ester, phosphorous acid two o-toluene esters, tricresyl phosphite m-tolyl ester, phosphorous acid two m-tolyl esters, tri-p-cresyl phosphite, two pairs of toluene esters of phosphorous acid, phosphorous acid two adjacent chlorobenzene esters, tricresyl phosphite are to chlorobenzene ester and two pairs of chlorobenzene esters of phosphorous acid.Wherein, preferably adopt triphenyl phosphite.The example of carbodiimide condensation agent can comprise dicyclohexylcarbodiimide (DCC), DIC (DIPC), N-ethyl-N '-3-dimethyl aminopropyl carbodiimide (EDC=WSCI) and hydrochloride (WSCIHCl) thereof.DCC or WSCI can with N-hydroxy-succinamide (HONSu), I-hydroxybenzotriazole (HOBt) or 3-hydroxyl-4-oxa--3,4-dihydro-1,2,3-benzotriazole (HOObt) etc. is used in combination.The amount of condensation agent is 0.1 times of compound of chemical formula (25) representative or bigger in mole, preferred equimolar amounts or bigger.Condensation agent itself can also be used as solvent.
The compound of chemical formula (25) representative be used for amount of the present invention in mole be chemical formula (24) representative as 0.1～50.0 times of the unit of raw material, preferably in 1.0～20.0 times of moles.
In reaction of the present invention, can adopt solvent as required.The example of solvent for use comprises hydrocarbon, for example hexane, cyclohexane or heptane; Ketone, for example acetone or MEK; Ether, for example dimethyl ether, diethyl ether or tetrahydrofuran; Chlorohydrocarbon, for example methylene chloride, chloroform, phenixin, ethylene dichloride or trichloroethanes; Aromatic hydrocarbon, for example benzene or toluene; Aprotic polar solvent, N for example, dinethylformamide or dimethyl sulfoxide (DMSO); And pyridine derivate.Especially preferably adopt pyridine.According to the kind and the reaction conditions of raw material and basic thing, can determine the The suitable solvent amount.
In the method for the invention, temperature of reaction is not particularly limited, but usually in 0 ℃～solvent boiling point scope.React yet be desirably under the optimum temperature of mating with used condensation agent.
In the method for the invention, usually can't the defined reaction time, but substantially in 1～48 hour scope.
Among the present invention, available conventional method is removed reaction liquid through distillation, and this reaction liquid comprises the polyhydroxy-alkanoates of chemical formula (1) representative of generation.In addition, can be by the solvent of reaction liquid with the polyhydroxy-alkanoates that does not dissolve chemical formula (1) representative be evenly mixed, through the polyhydroxy-alkanoates that the chemical formula (1) of precipitation recovery expectation is again represented, described solvent for example is a water; Alcohol, for example methyl alcohol or ethanol; Ether, for example dimethyl ether, diethyl ether or tetrahydrofuran.If desired, polyhydroxy-alkanoates segregation or the purifying that the chemical formula (1) that so obtains can be represented.This class segregation or purification process are not subjected to particular determination, for example can adopt with the reppd method of solvent of the polyhydroxy-alkanoates that do not dissolve chemical formula (1) representative or based on the method for column chromatography.
(manufacture method of the polyhydroxy-alkanoates of chemical formula (27) representative)
R in chemical formula (1)
1When being depicted as OH, halogen atom, ONa or OK, adopt trimethyl silyl bisdiazo methane can synthesize R to be shown in the chemical formula (27)-A for the esterification agent as chemical formula (26)
39-SO
3CH
3Polyhydroxy-alkanoates.Below will elaborate this class reaction.
In reaction of the present invention, can adopt solvent as required.The example of solvent for use comprises hydrocarbon, for example hexane, cyclohexane or heptane; Alcohol, for example methyl alcohol or ethanol; Ether, for example dimethyl ether, diethyl ether or tetrahydrofuran; Chlorohydrocarbon, for example methylene chloride, chloroform, phenixin, ethylene dichloride or trichloroethanes; Aromatic hydrocarbon, for example benzene or toluene; Aprotic polar solvent, N for example, dinethylformamide or dimethyl sulfoxide (DMSO); And pyridine derivate.Especially preferably adopt chloroform or methyl alcohol.According to raw material type and reaction conditions, can determine the The suitable solvent amount.
The amount of trimethyl silyl bisdiazo methane is 0.1～50 times of compound of chemical formula (26) representative in mole.
In the method for the invention, temperature of reaction is not particularly limited, but usually in-20～30 ℃ of scopes.In the method for the invention, usually can't the defined reaction time, but substantially in 1～48 hour scope.
Among the present invention, available conventional method is removed reaction liquid through distillation, and this reaction liquid comprises the polyhydroxy-alkanoates of chemical formula (27) representative of generation.In addition, can be by the solvent of reaction liquid with the polyhydroxy-alkanoates that does not dissolve chemical formula (27) representative be evenly mixed, through the polyhydroxy-alkanoates that the chemical formula (27) of precipitation recovery expectation is again represented, described solvent for example is a water; Alcohol, for example methyl alcohol or ethanol; Ether, for example dimethyl ether, diethyl ether or tetrahydrofuran.If desired, polyhydroxy-alkanoates segregation or the purifying that the chemical formula (27) that so obtains can be represented.This class segregation or purification process are not subjected to particular determination, for example can adopt with the reppd method of solvent of the polyhydroxy-alkanoates that do not dissolve chemical formula (27) representative or based on the method for column chromatography.
The application of toner
Be applied to electrostatic latent image developing toner and use in the image forming method of this toner through polyhydroxy-alkanoates of the present invention.Particularly, polyhydroxy-alkanoates of the present invention can be as the inner or outside charge control agent that adds.
Even also say, the present invention relates to a kind of charge control agent that comprises above polyhydroxy-alkanoates, and relate to a kind of electrostatic latent image developing toner that comprises this charge control agent.In addition, the present invention relates to a kind of image forming method, comprise: give the charge step of charge member impressed voltage, make the electrostatic latent image carrier uniform charged; Development step forms toner image on the electrostatic latent image carrier that charges; Transfer step is used or without the intermediate transfer element toner image on the electrostatic latent image carrier is transferred on the target record material; And the heating fixing step, the toner image heating is fixed on this material.In addition, the invention still further relates to a kind of image processing system, comprise the device of above each step of corresponding above method, be i.e. charging device, developing device, transfer printing device and heating immobilising device.
(as the use of charge control agent)
In the structure of used polyhydroxy-alkanoates, for the monomeric unit of chemical formula (1) representative, importantly side chain has the structure that comprises the sulfonic group or derivatives thereof among the present invention.It is preferred that charging property can be born for further raising in the unit that has this class electronegativity or an electron withdraw group, and charge control agent of the present invention has the excellent charging born property really.
Polyhydroxy-alkanoates and adhesive resin used among the present invention have gratifying mutual solubility, particularly with the polyester binder resin.The toner that contain polyhydroxy-alkanoates of the present invention, has high certain amount of charge and gratifying timely stability can stably provide picture rich in detail during electrostatic image forms, though prolong preserve after; It is colourless or utmost point weak color is only arranged and can bear charging satisfactorily, can constitute black or the color toner that can bear charging.
And, constitute the type/composition of the monomeric unit of polyhydroxy-alkanoates of the present invention by suitable selection, can in wide region, adjust this mutual solubility.
By adopting the composition of selecting resin in such a way, make charge control agent in toner binder, present the micron-scale phase separation structure, owing to do not form electric continuity in the toner, toner can stably be held electric charge.And polyhydroxy-alkanoates of the present invention do not contain heavy metal, do not have the heavy metal inhibition that the containing metal charge control agent is faced, and can stably produce toner by suspension polymerization or emulsion polymerization in the toner preparation.
(interpolation of PHA in the toner)
Among the present invention, can aforesaid compound be added in the toner by inside interpolation or outside the interpolation.Under the situation of adding in inside, in the mass ratio of charge control agent to toner binder, addition usually in 0.1～50 quality % scope, preferred 0.2～20 quality %.Owing to be not enough to improve the charging ability of toner, do not expect to be lower than the amount of 0.1 quality %.Equally, owing to consideration, do not expect to surpass the amount of 50 quality % to economy yet.In addition, externally under the situation of Tian Jiaing, charge control agent preferably in the scope of 0.01～5 quality %, and preferably is fixed to toner surface with charge control agent in the mechanochemistry mode to the mass ratio of toner binder.In addition, polyhydroxy-alkanoates of the present invention can be used in combination with known charge control agent.
As under the situation of charge control agent, polyhydroxy-alkanoates of the present invention has 1 usually, 000-1, and 000,000 number-average molecular weight, preferred 1,000-300,000.Molecular weight is lower than at 1,000 o'clock, and it is dissolved in the toner binder fully, is not easy to form discontinuous territory, thereby causes the quantity of electric charge to lack and influence unfriendly the flowable of toner.And molecular weight surpasses at 1,000,000 o'clock, and it is difficult that its dispersion in toner becomes.
The molecular weight of polyhydroxy-alkanoates of the present invention is measured by GPC (gel permeation chromatography).Particularly, elder generation is dissolved in dimethyl formamide (DMF) with polyhydroxy-alkanoates of the present invention or contains in the chloroform of 0.1 quality %LiBr, and measure a plurality of samples with similar mobile phase, determine molecular weight distribution from the reticle of polystyrene standard resin then.
In the present invention, as under the situation of charge control agent, preferably adopt such polyhydroxy-alkanoates: the ratio (Mw/Mn) of its weight-average molecular weight Mw and number-average molecular weight Mn is in 1～10 scope.
In the present invention, the polyhydroxy-alkanoates that is preferably used as charge control agent has the fusing point in 20～150 ℃ of scopes, particularly 40～150 ℃; Perhaps do not have fusing point and have glass transition temperature in 10～150 ℃ of scopes, particularly 20～150 ℃.Be lower than 20 ℃ or do not have fusing point and glass transition temperature is lower than under 20 ℃ the situation at fusing point, the flowable of toner and storage stability are tended to be influenced unfriendly.And be higher than 150 ℃ or do not have fusing point and glass transition temperature is higher than under 150 ℃ the situation at fusing point, this charge control agent potpourri go into to become in toner difficulty and charge amount distribution tended to broaden.
Can measure fusing point Tm and glass transition temperature Tg, for example by interior defeated component type high precision scanning differential thermal analysis instrument, as Perkin Elmer DSC-7.
In developing electrostatic charge image toner of the present invention, charge control agent to the weight ratio of toner binder usually in 0.1～50 quality % scope, preferred 0.2～20 quality %, more preferably 0.5～20 quality %.Developing electrostatic charge image toner of the present invention has such composition: based on toner qualities, comprise the aforementioned charge control agent of 0.1～50 quality %, 20～95 quality % toner binders and 0～15 quality % colorant, and if desired, can also comprise with the amount that is no more than 60 quality % the magnetic that also serves as colorant (the feeromagnetic metal powder, for example iron, cobalt, nickel or as the compound of magnetic iron ore, haematite or limonite and so on).Can also comprise various adjuvants (lubricant (as teflon, low-molecular-weight polyolefin, fatty acid or its slaine or its acid amides)) and another kind of charge control agent (for example metallized azo dye or salicylic acid metal salt).Can also improve the flowable of toner with hydrophobic silicon rubber powder or analog.Based on the quality of toner, the amount of these adjuvants is no more than 10 quality % usually.
In toner of the present invention, preferably to small part toner binder formation external phase, and the Partial charge controlling agent constitutes discontinuous territory at least.The situation that is dissolved in fully in the toner binder with charge control agent and does not form discontinuous territory is compared, and the charge control agent of adding tends to be exposed to more the surface of toner, thereby shows the effect of less addition.The dispersion particle diameter in this territory preferably in 0.01～4 mu m range, more preferably 0.05～2 μ m.Particle diameter surpasses 4 μ m and causes the charge amount distribution of dispersibility deficiency and broad, thereby makes the transparency deteriorates of toner.On the other hand, particle diameter is similar to such situation less than the situation of 0.01 μ m: charge control agent does not form discontinuous territory but is dissolved in the toner binder fully, thereby needs to add a large amount of charge control agents.By observe the toner section with transmission electron microscope(TEM) or its analog, can confirm that Partial charge controlling agent at least forms the state and the size distribution thereof in discontinuous territory.For the clear view inside surface, it is more effective to carry out electron microscope observation after with the toner section statining with ruthenium tetroxide or osmium tetroxide.
In order to reduce the particle diameter in the discontinuous territory that polyhydroxy-alkanoates of the present invention constitutes, can add polymkeric substance as mutual solvent, this polymkeric substance and polyhydroxy-alkanoates of the present invention have mutual solubility, and also have mutual solubility with toner binder.The example comprises polymkeric substance, and its polymeric chain comprises 50mol% structure monomer at least, and this structure monomer is basic identical with the monomer that constitutes polyhydroxy-alkanoates of the present invention; The monomer whose chain comprises 50mol% structure monomer at least with grafting or block form, and this structure monomer is basic identical with the monomer that constitutes toner binder.With respect to polyhydroxy-alkanoates of the present invention, the amount of mutual solvent is no more than its 30 quality % usually, preferably in 1～10 quality % scope.
(other composition material)
Below will describe other composition material that constitutes electrostatic latent image developing toner of the present invention in detail.Electrostatic latent image developing toner of the present invention comprises adhesive resin, colorant and other adjuvant that adds as required, and above-mentioned charge control agent.
(adhesive resin)
Preferably adhesive resin of the present invention is used as adhesive resin.Yet common thermoplastic resin also can be used as adhesive resin.For example can use following resin: polystyrene, polyacrylate, copolymer in cinnamic acrylic ester, polyvinyl chloride, polyvinyl acetate (PVA), poly-inclined to one side vinylidene chloride, phenol resin, epoxy resin or vibrin.This analog thermoplastic resin is not subjected to particular restriction, can use any thermoplastic resin, as long as it is usually used in the production of toner.
Can before forming toner, earlier charge control agent of the present invention be mixed with adhesive resin,, have the electric charge control ability as toner binder composition of the present invention.The example of this class adhesive resin comprises styrene polymer, polyester polymers, epoxy polymer, polyolefin polymer and polyether polyols with reduced unsaturation, and they can use separately or with potpourri.
(other biodegradable plastic)
(object lesson of other resin)
The example of styrene-based polymer comprises: the multipolymer of styrene and (methyl) acrylate, these monomers and other can with the multipolymer of the monomer of its copolymerization, the multipolymer of styrene and dialkylene monomer (butadiene, isoprene etc.), these monomers and other can with the multipolymer of the monomer of its copolymerization, and analog.Polyester based polymer comprises polycondensation product or the analog between the alkylene oxide addition product of aromatic dicarboxilic acid and aromatic diol.The epoxy-based polymerization thing comprises reaction product, its modified product and the analog between aromatic diol and the chloropropylene oxide.Polyolefin based polymer comprise tygon, polypropylene, these monomers and other can with the copolymer chain of the monomer of its copolymerization, and analog.The polyurethane-base polymkeric substance comprises polyaddition products and the analog between the alkylene oxide addition product of aromatic diisocyanate and aromatic diol.
The object lesson of the adhesive resin that is used in combination with charged particles controlling agent of the present invention comprises and followingly gathers polymer of monomers, these mixture of polymers or followingly gather the copolymerization product that monomer obtains with two or more.Particularly, this base polymer comprises for example styrene-based polymer, as styrene/acrylic acid co-polymer or styrene/methacrylic acid base co-polymer; Polyester based polymer; The epoxy-based polymerization thing; Polyolefin based polymer; Polyurethane-base polymkeric substance and suitable analog.
The object lesson that can gather monomer comprises styrene and styrene derivative, for example: styrene; Styrene derivative, as o-methyl styrene, a 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 is as ethene, propylene, butylene and isobutylene; Unsaturated polyene is as butadiene; Halogen ethene is as vinyl chloride, vinylidene chloride, bromine ethene and fluorothene; Vinyl esters is as vinyl acetate, propionate and vinyl benzoate; Alpha-methylene aliphatic monocarboxylic acid ester is as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, methacrylate, n-BMA, isobutyl methacrylate, n octyl methacrylate, metering system dodecyl gallate, methacrylic acid 2-Octyl Nitrite, octadecyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; Acrylate is as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic acid n-octyl, dodecyl acrylate, 2-EHA, octadecyl acrylate, acrylic acid 2-chloroethene ester and phenyl acrylate; Vinyl ether, as vinyl methyl ether, EVE and vinyl isobutyl ether; Vinyl ketone is as ethenyl methyl ketone, vinyl hexyl ketone and methyl isopropyl Ketone; The N-vinyl compound is as N-vinyl pyrrole, N-vinylcarbazole, N-vinyl indoles and N-vinyl pyrrolidone; Vinyl naphthalene; The acrylic or methacrylic acid derivative is as vinyl cyanide, methacrylonitrile and acrylamide; Dicarboxylic acid is as maleic acid, phthalic acid, succinic acid, terephthalic acid (TPA); The ester of above-mentioned alpha, beta-unsaturated esters and the diester of dibasic acid are as maleic acid methyl esters, maleic acid butyl ester and dimethyl maleate; Polyol is as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butylene glycol, 1, the bisphenol-A of 6-hexanediol, bisphenol-A, hydrogenated bisphenol A and polyoxyethyleneization; Isocyanates is as PPDI, P-xylene diisocyanate and 1,4-tetramethylene diisocyanate; Amine is as ethamine, butylamine, ethylenediamine, 1,4-diaminobenzene, 1,4-diaminobutane and monoethanolamine; Epoxy compound is as two glycerin ethers, ethylene glycol bisthioglycolate glycerin ether, bisphenol-A glycidol ether and p-dihydroxy-benzene diglycidyl ether; Or the like.
(crosslinking chemical)
During forming adhesive resin, can use following crosslinking chemical if desired, it is used in combination with charged particles controlling agent of the present invention.The example of bi-functional cross-linking agent comprises divinylbenzene, two (4-propenyl oxidation polyethoxy phenyl) propane, ethylene glycol diacrylate, 1, the 3-butanediol diacrylate, 1, the 4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1, the 6-hexanediyl ester, diacrylate nonanediol ester, the diacrylate binaryglycol ester, the diacrylate triglycol ester, diacrylate TEG ester, polyglycol #200 diacrylate, polyglycol #400 diacrylate, polyglycol #600 diacrylate, dipropylene glycol diacrylate, polypropyleneglycol diacrylate, polyester-type diacrylate (trade mark MANDA, can be from Nippon Kayaku Co., Ltd obtains) with and the above-mentioned diacrylate that replaced by dimethacrylate of acrylate moiety.
More than bifunctional, be that polyfunctional crosslinking agent can comprise the above-claimed cpd and 2 that pentaerythritol triacrylate, trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, acrylate oligomer, its acrylate moiety are replaced by methacrylic acid, 2-two (4-methylpropenyl oxidation polyethoxy phenyl) propane, diallyl phthalate, triallyl isocyanate, triallyl azo isocyanates, triallyl isocyanate and diaryl chlorendic acid ester.
(polymerization initiator)
During forming adhesive resin, can use following polymerization initiator if desired, it is used in combination with charged particles controlling agent of the present invention.Polymerization initiator comprises for example peroxide-2-ethyl hexanoic acid tert-butyl, peroxidating neopentanoic acid isopropyl benzene ester, the peroxidating 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), 2,2 '-azo two (4-methoxyl-2, the 4-methyl pentane nitrile), 1,1-two (t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane, 1,1-two (t-butylperoxy) cyclohexane, 1,4-two (tert-butyl hydroperoxide carbonyl) cyclohexane, 2,2-two (t-butylperoxy) octane, normal-butyl-4,4-two (t-butylperoxy) valerate, 2,2-two (t-butylperoxy) butane, 1,3-two (t-butyl peroxy isopropyl) benzene, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, 2,5-dimethyl-2,5-two (benzyl peroxy) hexane, diperoxy base m-phthalic acid di tert butyl carbonate, 2,2-two (4,4-di-t-butyl peroxide cyclohexyl) propane, peroxidating-Alpha-Methyl succinic acid di tert butyl carbonate, peroxidating dimethylated pentanedioic acid di-t-butyl ester, peroxidating six hydrogen terephthalic acid (TPA) di tert butyl carbonates, peroxidating azelaic acid di tert butyl carbonate, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, diethylene glycol two (t-butylperoxy carbonic ester), peroxy trimethyladipic acid di tert butyl carbonate, three (t-butylperoxy) triazine, vinyl three (t-butylperoxy) silane and analog.These materials can separately or be used in combination.As for its consumption, can use preferred 0.1～15 mass parts with per 100 mass parts monomers, 0.05 mass parts or more content.
(other biodegradable plastic)
In addition, the preferred biodegradable plastic of using among the present invention.The example of biodegradable plastic is " Ecostar ", " Ecostar plus " (Hagiwara Industries, Inc. make), " Biopole " (Monsanto Company manufacturing), " Ajicoat " (Ajinomoto Co., Ltd makes), " Cell Grain " (Daicel Chem., Ind., Ltd. make), " Bionolle " (Showa Highpolymer K.K. manufacturing), " Eco-plastic " (Toyota MotorCorporation manufacturing), " Lacea " (Mitsui Chemicals, Inc. makes), " Biogreen " (Mitsubishi Gas Chemical Company Inc. manufacturing), " Natureworks " (Cargilldow manufacturing), " Biomax " (Dupont) and analog.
Wherein, preferred especially polycaprolactone (being the multipolymer of 6-caprolactone) or PLA, because these compounds are easily also fully by decomposition such as lipase, esterases, also because they are easy to be easy to change by copolymerization or similar procedure with other mixed with resin and its physical property.
In a kind of combination of this class adhesive resin and charge control agent of the present invention, the paradigmatic structure of preferred adhesive resin is similar to the paradigmatic structure of charge control agent polymeric chain as much as possible.Significant difference in the paradigmatic structure of the paradigmatic structure of adhesive resin and charge control agent polymeric chain tends to cause the dispersion deficiency of charge control agent in adhesive resin.
The mass ratio that inside is added the charge control agent of the present invention in the adhesive resin to is generally 0.1～50 quality %, preferred 0.2～20 quality %.The mass ratio of the charge control agent that add this inside is less than 0.1 quality % and causes the low quantity of electric charge, and surpasses the charge stability deterioration that 50 quality % will make toner.
The charged particles controlling agent of＜non-PHA 〉
Charged particles controlling agent commonly used can use with charge control agent of the present invention.The object lesson of this class charged particles controlling agent can comprise aniline black byestuffs, quaternary ammonium salt and Monoazo metal complex salt dyestuff.Consider the charge characteristic of the charge characteristic of various conditions such as adhesive resin, the manufacture method that relates to the colorant addition, process for dispersing and other adjuvant, can determine the addition of charged particles controlling agent.For 100 mass parts adhesive resins, usually the ratio with 0.1～20 mass parts adds the charged particles controlling agent, preferably with the ratio of 0.5～10 mass parts.Except that above-mentioned substance, the inorganics that also can use inorganic, metal oxide particle or its surface to handle with above organism.These charged particles controlling agents can be mixed into adhesive resin, perhaps can be attached to the surface of toner-particle.
(colorant)
For the colorant that constitutes developing electrostatic charge image toner of the present invention, can use anyly to be generally used for making the colorant of toner and not have particular restriction.For example can use carbon black, titanium white, monoazo red, disazo yellow pigment, quinacridone magenta pigment, anthraquinone pigment, any other pigment and/or dyestuff.
More specifically, when with developing electrostatic charge image toner of the present invention when the magnetic color toner, operable colorant for example 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 rouge 30, C.I. are 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, C.I. Viride Nitens 6 etc.
As pigment, can use chrome yellow, cadmium yellow, the mineral fast yellow, the navel Huang, the yellow S of phenol, hansa yellow G, permanent yellow NCG, tartrazine lake, chrome orange, molybdate orange, solid forever orange GTR, the pyrrolinone orange, Benzidine orange G, cadmium red, permanent bordeaux 4R, look red calcium salt, eosine lake, bright fuchsin 3B, manganese violet, Fast violet B, the methyl violet color lake, Prussian blue (barba hispanica), cobalt blue, alkali blue lake, the Victoria blue color lake, phthalocyanine blue, fast sky blue, indanthrene blue BC, chrome green, chrome green, pigment green B, the peacock green color lake, ultimate yellowish green G and analog.
In addition, when developing electrostatic charge image toner of the present invention was used for the bi-component full-color toner as toner, available following material was as colorant.The example that is used for the colorant of pinkish red color 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, C.I. pigment violet 19, C.I. urn red 1,2,10,13,15,23,29 and 35 etc.
Among the present invention, aforementioned pigment can use separately.But consider the image quality of full-colour image, more preferably be used in combination dyestuff and pigment to improve the acutance of pigment.In this case, the example that is used for pinkish red dyestuff comprises oily soluble dye, as 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, C.I. disperse violet 1 etc.; Basic-dyeable fibre, as 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, C.I. alkaline purple 1,3,7,10,14,15,21,25,26,27 and 28 etc.
Other pigment comprises cyano group pigment, as C.I. alizarol saphirol 2,3,15,16 and 17, and C.I. vat blue 6, the copper phthalocyanine that C.I. acid blue 45 and phthalocyanine frame are replaced by 1～5 phthalimidomethyl.
For yellow, the example of 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, C.I. vat yellow 1,3 and 20 etc.
Above-mentioned dyestuff and pigment can use separately, perhaps use for the toner tone that obtains expectation mixes arbitrarily.Consider environmental protection or human body safety, can suitably adopt edible pigment such as edible color lake.The example of this based food pigment can comprise Food Red 40 aluminium color lakes, Food Red 2 aluminium color lakes, Food Red 3 aluminium color lakes, azogeramine 6 aluminium color lakes, the yellow 5 aluminium color lakes of food, the yellow 4 aluminium color lakes of food, the blue 1 aluminium color lake of food and the blue 2 aluminium color lakes of food.
The insoluble food pigment of above-mentioned water can be used as the charged particles controlling agent.In this case, for negative charge, preferred above-mentioned aluminium color lake.Thereby, when the insoluble food pigment of water has function as the charged particles controlling agent, can not only improve toner to environmentAL safety, also help and reduce the toner cost.
Depend on desired color effect or other factors, above-mentioned colorant content in toner can broadly change.Usually, for obtaining best toner characteristic, promptly consider the dispersing etc. of shape stability, toner of colouring power, the toner of printing, colorant uses with the ratio of per 100 mass parts adhesive resins, 0.1～60 mass parts usually, preferred 0.5～20 mass parts.
(other components of toner)
Except that containing above-mentioned adhesive resin and colorant set branch, developing electrostatic charge image toner of the present invention can also comprise following compound in the scope that they do not have a negative impact to effect of the present invention.The example of this compounds comprises aliphatics or alicyclic hydrocarbon resin and aromatic petroleum resin, for example organic siliconresin, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, low molecular weight polyethylene, low-molecular-weight polypropylene, chloroalkane hydrocarbon, paraffin wax etc.The wherein preferred especially wax that uses comprises low-molecular-weight ethylenic and accessory substance, low molecular weight polyester and ester group wax thereof and its aliphatic derivatives.And, preferably will be used for the present invention by the prepared wax of these waxes of the whole bag of tricks rectifying according to molecular weight.In addition, after the rectifying, can implement oxidation, block copolymerization and graft modification.
Especially, show that in the observation of the laminagraphy that carries out with transmission electron microscope (TEM) the wax component is dispersed in the form on sphere and/or spindle island basically under the situation in the adhesive resin, developing electrostatic charge image toner of the present invention shows splendid characteristic.
(method for preparing toner)
For making the concrete grammar with developing electrostatic charge image toner of above-mentioned composition of the present invention, can adopt in the known method method any.Developing electrostatic charge image toner of the present invention can wherein for example obtain toner by following process by so-called comminuting method manufacturing.
Promptly, particularly, the following acquisition of developing electrostatic charge image toner of the present invention: the wax of resin such as adhesive resin, charged particles controlling agent and interpolation is as required fully mixed in mixer, and mixer instance is as being Henschel mixer, bowl mill or analog; With molten the pinching of heat kneading machine resin is held each other mutually then, heat kneading machine for example is hot-rolling, kneader or extruder.Then, adjuvant such as metallic compound as pigment, dyestuff or the magnetic material of colorant and interpolation as required are dispersed or dissolved in the resin that kneaded, cooling is also solidified.With comminutor such as jet mill or bowl mill this solid is pulverized and gradation, had the developing electrostatic charge image toner of the present invention of expectation particle diameter with manufacturing.In the gradation step, preferably adopt multistage sizer to enhance productivity.
Developing electrostatic charge image toner of the present invention also can obtain by the following method.That is, (aromatic hydrocarbons is as toluene and dimethylbenzene with a kind of solvent or solvent mixture; Halogenide is as chloroform and dichloroethylene; Ketone is as acetone and MEK; Acid amides is as dimethyl formamide; And analog) adhesive resin is mixed with the solution form with the charged particles controlling agent and stirs.Afterwards, this mixed solution poured into make it in the water to precipitate again, with solid filtering, dry and with comminutor as jet mill or bowl mill pulverize, gradation obtains having the developing electrostatic charge image toner of the present invention of expecting particle diameter subsequently.In the gradation step, preferably adopt multistage sizer to enhance productivity.
In addition, developing electrostatic charge image toner of the present invention also can obtain by so-called polymerization as described below.In this case, with the polymerisable monomer of adhesive resin, charged particles controlling agent, as the material such as pigment, dyestuff and magnetic material of colorant, and non-essential crosslinking chemical, polymerization initiator, wax, other resin binder and other adjuvant mix, disperse and make it to carry out suspension polymerization in liquid dispersion medium in the presence of surfactant or analog, synthesizes polymerizable color resin particle.Then, make the separation of gained particle experience solid-liquid, the dry gradation that carries out as required that reaches, obtain developing electrostatic charge image toner of the present invention.
In addition, can not contain the colored particulate of charge control agent, then, can pass through mechanochemistry method or similar approach, polyhydroxy-alkanoates is added and is fixed to particle surface separately or with external additive such as silica gel by method for preparing.
(silicon dioxide external additive)
Among the present invention, preferably with fine silica from the outside is added toner by method for preparing to, to improve charge stability, development property, flowable and permanance.To this situation, use to have 20m
2/ g or higher (in the scope), particularly 30～400m
2The fine silica of/g specific surface area can obtain excellent results, and the nitrogen adsorption method of this specific surface area such as foundation BET method is surveyed.In this case, preferably use fine silica, preferred about 0.1～about 5 mass parts with the amount of about 0.01～about 8 mass parts of per 100 mass parts toner-particles.For used fine silica, preferred those silicon dioxide of handling with treating agent in order to make toner have the chargeable property of hydrophobicity or control toner that adopts, described treating agent for example is silicone varnish, various modified organic silicon varnish, silicone oil, various modified silicon oil, silane coupling agent, the silane coupling agent with functional group and other organo-silicon compound as required.These treating agents can use by potpourri.
(inorganic powder)
For improving the development property and the permanance of toner, preferably add inorganic powder, for example: metal oxide powder, metal for example are magnesium, zinc, aluminium, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin and antimony; Composite metal oxide is as calcium titanate, magnesium titanate and strontium titanates; Slaine is as lime carbonate, magnesium carbonate and aluminium carbonate, clay mineral, as porcelain earth; Phosphate cpd is as apatite; Silicon compound is as silit and silicon nitride; And carbon dust, as carbon black and graphite.Wherein, preferably adopt zinc paste, aluminium oxide, cobalt oxide, manganese dioxide, strontium titanates and magnesium titanate.
(lubricant)
In addition, following lubricant powder can be added in the toner.The example of lubricant powder comprises fluororesin, as special teflon, poly-inclined to one side vinylidene fluoride; Fluorine compounds are as fluorocarbons; Fatty acid metal salts is as zinc stearate; Fatty acid; Derivative of fatty acid is as stearate; Molybdenum sulfide and analog.
(carrier)
Developing electrostatic charge image toner of the present invention with said structure and character can be used for various known toners; For example, can be used as nonmagnetic toner, it is used alone as the non-magnetic mono-component developer solution, perhaps with the magnetic carrier carrier as magnetic bi-component developer solution; Perhaps be used alone as the magnetic color tuner of magnetic single component development liquid.Any conventionally known carrier can be as the carrier in the bi-component development method.Particularly, constitute by metal such as iron, nickel, cobalt, manganese, chromium and rare earth element, its alloy or oxide, mean grain size is that 20～300 μ m, surface oxidation or unoxidized particle can be used as carrier granular.Preferred carrier used in this invention comprises above-mentioned carrier granular, scribbles on its surface such as phenethyl resin, acrylic based resin, organic siliconresin, fluoro resin, vibrin or analog; Perhaps be attached with this class material on the surface.
(magnetic color tuner)
Developing electrostatic charge image toner of the present invention can comprise magnetic material to constitute magnetic color tuner in toner-particle.In this case, magnetic material also can be used as colorant.The magnetic material that can be used for this situation comprises ferriferous oxide, as magnetic iron ore, haematite and limonite; And metal, as iron, cobalt and nickel, or the alloy of these metals and other metal and oxide, other metal for example is aluminium, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium.The magnetic material that can be used as among the present invention preferably has 2 μ m or littler mean grain size, more preferably from about 0.1～about 0.5 μ m.Preferably they are included in the toner with the amount of per 100 mass parts adhesive resins, 20～200 mass parts, preferred especially per 100 mass parts adhesive resins, 40～150 mass parts.
In addition, for obtaining high image quality, the finer latent image dots of must accurately developing.For this purpose, for example preferably control developing electrostatic charge image toner of the present invention particle so that its weight average particle diameter in 4～9 mu m ranges.That is, the weight average particle diameter of not expecting toner-particle is less than 4 μ m, because, with this toner, the image transfer efficiency tends to reduce, after the transfer printing, the toner of many not transfer printings is easy to stay on the light activated element, and owing to haze/the transfer printing failure, this tends to cause image inhomogeneous.If the weight average particle diameter of toner-particle surpasses 9 μ m, then tend to occurrence characteristics scattering and line image.
Among the present invention, by adopting and interface (Nikkaki Bios Co., Ltd.) connection is measured the particle diameter and the size distribution of toner with Coulter Counter TA-II or the Coulter Multisizer (can obtain from Beckman Coulter Electronics Inc.) and the personal computer PC 9801 of output numeric distribution and volume distributed median.Used electrolytic solution is the 1%NaCl aqueous solution with grade sodium chloride preparation in the mensuration.This 1%NaCl aqueous solution also can be buied, for example ISOTONR-II (Coulter Scientific Japan Co. manufacturing).Particularly, for measuring, 0.1～5mL is added to the sample to be formed for measuring in 100～150mL electrolytic solution as the surfactant (preferred alkyl benzene sulfonate) of spreading agent and other 2～20mg measurement sample.In the measurement, make gained measure the suspending liquid of sample in electrolytic solution and experience about 1～3 minute dispersion treatment of ultrasonic dispersion, experience is measured as the size distribution that grating carries out with the above-mentioned CoulterCounter TA-II that is furnished with 100 μ m apertures then, to obtain to be equal to and greater than the volume and the quantity of 2 μ m toner-particles.From these volume calculated basal granules directly distribute and the numerical value basal granule directly distribute.Then, derive equal particle of volume basic weight (D4) related to the present invention and the long equal particle diameter (D1) of quantity base respectively from volume base and the distribution of quantity base.
(quantity of electric charge)
The every element quality of preferred developing electrostatic charge image toner of the present invention has the electric weight (bi-component method) of-10～-80 μ C/g, and more preferably-15～-70 μ C/g is to improve transfer efficiency in the printing transferring method that uses the negative pressure transferring member.
With as described below in order to the method for measuring the quantity of electric charge by the bi-component method in the present invention.For measuring, adopt electrical quantity measurement arrangement as shown in Figure 7.At first, under certain environment, with the EFV 200/300 (trade mark of 9.5g as carrier, Powdertech Co., Ltd. manufacturing) potpourri with 0.5g toner to be measured adds in the polyethylene bottle of volume a 50～100mL, puts it to then in the vibrating device, and vibration condition is fixed amplitude 100mm, vibration velocity 100 arteries and veins per minutes, the vibration preset time.The potpourri that 1.0～1.2g was shaken is packed into and is covered in the measuring vessel 42 (metallic) and with crown cap 44 then, and this measuring vessel is positioned at the bottom of electrical quantity measurement arrangement shown in Figure 7 and has 500 mesh sieves 43.The gross mass of weighing measuring vessel 42 also is labeled as W1 (g).Then, operation aspirator (not shown) is found time through bleeding point 47, and the part that contacts with measuring vessel 42 at least in this aspirator is made of insulator, adjusts pressure by adjusting control damper 46 simultaneously, and making the vacuum meter reading is 2450Pa (250mmAg).At this state, keep finding time 1 minute to remove toner.Voltmeter 49 reading at this moment is labeled as V (volt).Here, 48 expression electric capacitys are the capacitor of C (μ F).Weighing find time the back measurement mechanism gross mass and be labeled as W2 (g).Then, calculate the friction electric weight (μ C/g) of toner with following equation:
Friction electric weight (μ C/g)=C * V/ (W1-W2).
The molecular weight distribution of＜adhesive resin 〉
Preferably the adhesive resin as developing electrostatic charge image toner composition material of the present invention shows peak, low-molecular-weight zone in 3,000～15,000 range of molecular weight distributions of colloidal sol permeation chromatography (GPC), particularly when it is prepared by comminuting method.That is,, become not enough under some situation of the raising of transfer efficiency if the GPC peak in the harmonic component zone surpasses 15,000.On the other hand, do not wish to use the GPC peak at the adhesive resin that is lower than in 3, the 000 low-molecular-weight scopes, because when surface treatment, tend to take place fusion.
Among the present invention, measure the molecular weight of adhesive resin with gel permeation chromatography (GPC).Be used for to comprise following method: be solvent extraction 20 hour with the Soxhlet extractor with THF (tetrahydrofuran) with toner in advance with the concrete grammar of gpc measurement, and the Shodex A-801,802,803,804,805, the 806 and 807 (trade (brand) names that are connected in series by employing, Showa Denko.K.K. makes) and the calibration curve that adopts the polystyrene standard resin, the sample that so obtains is used for molecular weight measurement.Among the present invention, preferred use (Mw/Mn) in 2～10 scopes adhesive resin, this ratio is the weight-average molecular weight (Mw) measured thus and the ratio of number-average molecular weight (Mn).
＜glass transition temperature 〉
Consider fixedly character and storage life, preferably by using so preparation toner of the present invention of suitable material, so that its glass transition temperature Tg is 40～75 ℃, more preferably 52～70 ℃.In this case, according to ASTM D3418-82, the imported high precision differential scanning calorimeter of hot component in adopting, as Perkin Elmer Co., the DSC-7 of manufacturing, the glass transition temperature Tg of measurement toner.Among the present invention, when measuring glass transition temperature Tg, the temperature of the sample to be measured that raises is earlier cooled off then fast to write down all thermo-lags.With in 0～200 ℃ scope, raise the once more temperature of sample of 10 ℃/minute programming rates.DSC curve based on the measurement result gained under these conditions can be used aptly.
＜image forming method 〉
Especially preferably the developing electrostatic charge image toner with the invention described above is used for such image forming method: it comprises the step to the charge member impressed voltage, gives the charging of electrostatic latent image load-carrying unit thus; On the electrostatic latent image load-carrying unit that has charged, form the step of electrostatic charge image; Development step makes developing electrostatic charge image with toner, forms toner image thus on the electrostatic latent image load bearing unit; Transfer step is transferred to the toner image on the electrostatic latent image load bearing unit on the recording medium; And the heat fixation step, with the toner image heat fixation to recording medium.Selectively, toner of the present invention can be used for said method especially aptly, the transfer step in this method comprises first transfer step, and the toner image on the electrostatic latent image load-carrying unit is transferred on the intermediate transfer element; And second transfer step, the toner image on the intermediate transfer element is transferred on the recording medium.
Among the present invention, the cultivation of microorganism, PHA from the recovery of bacterial cell and the reaction dissolvent the chemical reaction, temperature of reaction, reaction time and purification process and charge control agent all be not limited to aforesaid those.
(embodiment)
Below, will describe the present invention in more detail by embodiment, but the present invention never is limited to these embodiment.
Embodiment A-1
Peptone more than 0.5% (Wako Pure Chemical Co. provides), 6mmol/L5-phenylpentanoic acid and 1.5mmol/L are dissolved into 1 as 5-(4-ethenylphenyl) valeric acid of ω-(4-ethenylphenyl) alkanoic acid, in the aforementioned M9 nutrient culture media of 000mL, pack 2 then into, in the shaking flask of 000mL, sterilization and be cooled to room temperature in autoclave sterilizer.Then with 2mL in advance in containing the M9 nutrient culture media of peptone more than 0.5% in 30 ℃ of shaken cultivation 8 hours Pseudomonascichorii YN2 strain cultured solution be added in the nutrient culture media of being prepared, cultivated 64 hours in 30 ℃.After the cultivation, reclaim bacterial cell, with washed with methanol and dry through centrifugal filtration.The bacterial cell of the drying of weighing adds chloroform wherein then, stirs 88 hours with extracting polymer at 35 ℃ subsequently.Chloroform extract is filtered and in evaporator, concentrate.The gained solid sediment reclaims and drying under reduced pressure with cold methanol, obtains the polymkeric substance of expectation.
The structure determination of resulting polymers is used
1H-NMR carries out (FT-NMR:BrukerDPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent C DCl
3Measure temperature: room temperature).
Fig. 8 represents resulting polymers
1The H-NMR spectrogram.As a result of, confirmed to comprise the polyhydroxy-alkanoates multipolymer of the unit of following chemical formula (34) representative, content is than (mol%) A: B=80: 20.
The mean molecular weight of resulting polymers is measured (GPC) (TosoHLC-8220 GPC, post: Toso TSK-GEL Super HM-H, solvent: chloroform, molecular weight are converted to polystyrene) with the colloidal sol permeation chromatography.Resulting polymers weight (PDW) is 0.44g/L, and number-average molecular weight Mn is 86,000, and weight-average molecular weight Mw is 242,000.
Embodiment A-2
Pack in the flask of 200mL the polyester that contains 20mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid monomer of gained in the 1.0017g embodiment A-1,0.817 gram 18-hat-6-ether, 60.0mL methylene chloride and 10mL acetate and stirring.Flask is immersed in the ice bath reaction system is cooled to 0 ℃.After 45 minutes, adding 0.6932g potassium permanganate also stirred 15 hours.After the reaction, add 5% aqueous solution of sodium bisulfite and stirring, make the pH=1 of liquid with the hydrochloric acid of 1.0N.After in evaporator, the methylene chloride in the liquid mixture being steamed, reclaim the polymkeric substance in the solution.Also use the 100ml methanol wash by the washed twice of purifying waste water with 100ml, reclaim polymkeric substance.Drying under reduced pressure obtains the PHA of 0.8053g expectation.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent C DCl
3Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (Nicolet AVATAR360FT-IR) mensuration.Measure based on IR, by the carboxylic acid that reduces 1,693cm
-1The new absorption peak that causes determines that gained PHA contains 3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit.
In addition, can adopt trimethyl silyl bisdiazo methane,, calculate the unit ratio of gained PHA by esterification to PHA side chain terminal carboxyl.
18.7mL target P HA packed into make it dissolving in the 100ml flask and by adding 1.4ml chloroform and 0.35mL methyl alcohol.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane of 0.4ml 2.0mol/L, and at room temperature stirred 30 minutes.After the reaction, in evaporator, solvent is steamed to reclaim polymkeric substance.By using 50ml methanol wash pinching compound back and forth.Drying under reduced pressure obtains 8.9mgPHA.
Analyze to carry out NMR with identical before mode.Resulting polymers
1The H-NMR spectrogram is shown among Fig. 9.As a result of, confirmed to comprise the polyhydroxy-alkanoates multipolymer of the unit of following chemical formula (3 5) representative, content is than (mol%) A: B=83: 17.
In addition, with gel permeation chromatography (GPC:Toso, post: Polymer LaboratoriesPLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v), be converted to polystyrene) mean molecular weight of estimation PHA, this PHA is for making the carboxyl ester gained of aforementioned PHA side chain terminal with trimethyl silyl bisdiazo methane.As a result of, gained number-average molecular weight Mn is 61,000, and weight-average molecular weight Mw is 82,000.
Embodiment A-3
In the blanket of nitrogen, with gained in the 0.2007g embodiment A-2 and comprise the polymkeric substance of 17mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 54.7mg para-totuidine-2-sulfonic acid is packed in the 50ml double-neck flask, stir with the adding of 10ml pyridine then, add the 0.08ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, reaction product is precipitated in 250ml ethanol again, and reclaim through centrifugal filtration.Resulting polymers agitator treating 3 days in water is used 1N salt acid elution 1 day, drying under reduced pressure 1 day again.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.Measure based on IR, carboxylic acid is at 1,693 cm
-1The peak that causes weakens, and observes by amide group 1 669cm
-1The new peak that causes.
Resulting polymers
1The H-NMR spectrogram is shown among Figure 10.
1The result of H-NMR shows that peak transfer that the methyl by para-totuidine-2-carboxylic acid causes is from peak that the methyl of para-totuidine-2-carboxylic acid causes, based on this result, confirm that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 13mol% (36) representative.
Also use the mean molecular weight of gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 18,000, and weight-average molecular weight Mw is 38,000.Obtain this compound of 50g by the scale that enlarges preparation process, be used for toner manufacturing and evaluation used as embodiment compd A-1.
Embodiment A-4
0.1005g embodiment A-3 gained and the polymkeric substance that comprises the unit of 13mol% chemical formula (37) representative are packed in the 50ml eggplant type flask, add 7ml chloroform and 1.8ml methyl alcohol and make it dissolving, be cooled to 0 ℃.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane (Aldrich Inc. manufacturing) of 2.7ml 2.0mol/L, and stirred 4 hours.After the reaction, in evaporator, solvent is steamed to reclaim polymkeric substance.Add 7ml chloroform and 1.8ml methyl alcohol polymkeric substance is dissolved again, steam solvent with evaporator.Repeat this operation three times, drying under reduced pressure obtains 0.0845 gPHA subsequently.
The structure of resulting polymers 1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) measure.
1The result of H-NMR shows the peak of 3～4ppm that methylmesylate causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 11mol% (37) representative.
Adopt the acid number titration of potentiometric titrimeter AT510 (Kyoto Denshi Co. manufacturing) also not show the peak that sulfonic acid causes, this shows that sulfonic acid has changed into methylmesylate.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 17,000, and weight-average molecular weight Mw is 36,000.Obtain this compound of 50g by the scale that enlarges preparation process, be used for toner manufacturing and evaluation used as embodiment compd A-2.
Embodiment B-1
Peptone more than 0.5% (Wako Pure Chemical Co.), 6mmol/L5-phenylpentanoic acid and 3.0mmol/L are dissolved into 1 as 5-(4-ethenylphenyl) valeric acid of ω-(4-ethenylphenyl) alkanoic acid, in the aforementioned M9 nutrient culture media of 000mL, pack 2 then into, in the shaking flask of 000mL, sterilization and be cooled to room temperature in autoclave sterilizer.Then with 2mL in advance in containing the M9 nutrient culture media of peptone more than 0.5% in 30 ℃ of shaken cultivation 8 hours Pseudomonas cichoriiYN2 strain cultured solution be added in the nutrient culture media of being prepared, cultivated 63 hours in 30 ℃.After the cultivation, reclaim bacterial cell, with washed with methanol and dry through centrifugal filtration.The bacterial cell of the drying of weighing adds chloroform wherein then, stirs 72 hours with extracting polymer at 35 ℃ subsequently.Chloroform extract is filtered and in evaporator, concentrate.The gained solid sediment reclaims and drying under reduced pressure with cold methanol, obtains the polymkeric substance of expectation.
The structure determination of resulting polymers is used
1H-NMR carries out (FT-NMR:BrukerDPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent C DCl
3Measure temperature: room temperature).
Figure 11 represents resulting polymers
1The H-NMR spectrogram.As a result of, confirmed to comprise the polyhydroxy-alkanoates multipolymer of the unit of following chemical formula (3 8) representative, content is than (mol%) A: B=60: 40.
The molecular weight of resulting polymers colloidal sol permeation chromatography mensuration (GPC) (TosoHLC-8220 GPC, post: Toso TSK-GEL Super HM-H, solvent: chloroform is converted to polystyrene).Resulting polymers weight (PDW) is 0.33g/L, and number-average molecular weight Mn is 82,000, and weight-average molecular weight Mw is 262,000.
Embodiment B-2
Pack in the flask of 500mL the polyester that contains 40mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit of gained in the 1.6041g Embodiment B-1,2.7259 gram 18-hat-6-ethers, 96mL methylene chloride and 16mL acetate and stirring.Flask is immersed in the ice bath reaction system is cooled to 0 ℃.After 40 minutes, adding 2.1745g potassium permanganate also stirred 12 hours.After the reaction, add 5% aqueous solution of sodium bisulfite and stirring, make the pH=1 of liquid with the hydrochloric acid of 1.0N.After in evaporator, the methylene chloride in the liquid mixture being steamed, reclaim the polymkeric substance in the solution.Also with the polymkeric substance of 200ml methanol wash distilation steps gained, reclaim the PHA of expectation by the washed twice of purifying waste water with 200ml.Drying under reduced pressure obtains the PHA of 1.6043g expectation.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent C DCl
3Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (Nicolet AVATAR360FT-IR) mensuration.Measure based on IR, by carboxylic acid 1,693cm
-1The new absorption peak that causes determines that gained PHA contains 3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit.
In addition, with embodiment A-2 in identical mode, adopt trimethyl silyl bisdiazo methane, by esterification, calculate the unit ratio of gained PHA to PHA side chain terminal carboxyl.
As a result of, confirmed to comprise the polyhydroxy-alkanoates multipolymer of the unit of following chemical formula (39) representative, content is than (mol%) A: B=62: 38.
In addition, with gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v), be converted to polystyrene) mean molecular weight of estimation PHA, this PHA is for making the carboxyl ester gained of aforementioned PHA side chain terminal with trimethyl silyl bisdiazo methane.As a result of, gained number-average molecular weight Mn is 68,000, and weight-average molecular weight Mw is 89,000.
Embodiment B-3
In the blanket of nitrogen, with gained in the 0.2000g Embodiment B-2 and comprise the polymkeric substance of 38mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 112.0mg para-totuidine-2-sulfonic acid is packed in the 50ml double-neck flask, stir with the adding of 10ml pyridine then, add the 0.16ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, reaction product is precipitated in 200ml ethanol again, and reclaim through centrifugal filtration.Resulting polymers is with 1N salt acid elution 1 day, agitator treating 1 day in water again, drying under reduced pressure 1 day.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 668cm
-1The new peak that causes.
Resulting polymers
1The H-NMR spectrogram is shown among Figure 12.
1The result of H-NMR shows that peak transfer that the methyl by para-totuidine-2-carboxylic acid structure causes is from peak that the methyl of para-totuidine-2-carboxylic acid causes, based on this result, confirm that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 30mol% (40) representative:
Also use the mean molecular weight of gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 24,000, and weight-average molecular weight Mw is 40,000.
Embodiment C-1
In the blanket of nitrogen, with gained in the 0.2008g embodiment A-2 and comprise the polymkeric substance of 17mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 50.8mg 4-aminobenzenesulfonic acid is packed in the 50ml double-neck flask, stir with the adding of 10ml pyridine then, add the 0.08ml triphenyl phosphite and 100 ℃ of heating 4 hours.After the reaction, reaction product is precipitated in 200ml ethanol again, and reclaim through centrifugal filtration.Resulting polymers agitator treating 3 days in water is used 1N salt acid elution 1 day, drying under reduced pressure 1 day again.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
In IR measures, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 668cm
-1The new peak that causes.Resulting polymers
1The H-NMR spectrogram is shown among Fig. 13.
1The result of H-NMR shows 7.70 and 7.57 and observes the peak that aromatic ring causes, this aromatic ring is brought by introducing the 4-aminobenzenesulfonic acid, based on this result, confirms the polyhydroxy-alkanoates multipolymer of gained PHA for the unit that contains the following chemical formula of 11mol% (41) and represent:
Also use the mean molecular weight of gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 20,000, and weight-average molecular weight Mw is 39,000.Obtain this compound of 50g by the scale that enlarges preparation process, be used for toner manufacturing and evaluation used as embodiment Compound C-1.
Embodiment C-2
0.1010g Embodiment C-1 gained and the polymkeric substance that comprises the unit of 11mol% chemical formula (41) representative are packed in the 50ml eggplant type flask, add 7ml chloroform and 1.8ml methyl alcohol and make it dissolving, be cooled to 0 ℃.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane (Aldrich Inc. manufacturing) of 2.7ml 2.0mol/L, and stirred 4 hours.After the reaction, in evaporator, solvent is steamed to reclaim polymkeric substance.Add 7ml chloroform and 1.8ml methyl alcohol polymkeric substance is dissolved again, steam solvent with evaporator.Repeat this operation three times, drying under reduced pressure obtains 0.0855gPHA subsequently.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) measure.
1The result of H-NMR shows the peak of 3～4ppm that methylmesylate causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 10mol% (42) representative.
Adopt the acid number titration of potentiometric titrimeter AT510 (Kyoto Denshi Co. manufacturing) also not show the peak that sulfonic acid causes, this shows that sulfonic acid has changed into methylmesylate.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 18,000, and weight-average molecular weight Mw is 36,000.Obtain this compound of 50g by the scale that enlarges preparation process, be used for toner manufacturing and evaluation used as embodiment Compound C-2.
Embodiment D-1
Polyester, 1.8509g18-hat-6-ether, 180mL methylene chloride and the 30mL acetate that 3.01g is contained 14mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit is packed in the flask of 500mL and is stirred.Flask is immersed in the ice bath reaction system is cooled to 0 ℃.After 60 minutes, adding 1.4762g potassium permanganate also stirred 20 hours.After the reaction, add 5% aqueous solution of sodium bisulfite and stirring, make the pH=1 of liquid with the hydrochloric acid of 1.0N.After in evaporator, the methylene chloride in the liquid mixture being steamed, reclaim the polymkeric substance in the solution.Purify waste water and 200ml methanol wash resulting polymers with 200ml.With 100ml purify waste water and again with 100ml methyl alcohol further washing to reclaim polymkeric substance.Drying under reduced pressure obtains the PHA of 2.9601g expectation.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent C DCl
3Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (Nicolet AVATAR360FT-IR) mensuration.As a result, by carboxylic acid 1,693cm
-1The new absorption peak that causes determines that gained PHA contains 3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit.
In addition, with embodiment A-2 in identical mode, adopt trimethyl silyl bisdiazo methane, by esterification, calculate the unit ratio of gained PHA to PHA side chain terminal carboxyl.
As a result of, confirmed to comprise the polyhydroxy-alkanoates multipolymer of the unit of following chemical formula (43) representative, content is than (mol%) A: B=87: 13.
In addition, with gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v), be converted to polystyrene) mean molecular weight of estimation PHA, this PHA is for making the carboxyl ester gained of aforementioned PHA side chain terminal with trimethyl silyl bisdiazo methane.As a result of, gained number-average molecular weight Mn is 68,000, and weight-average molecular weight Mw is 89,000.
Embodiment D-2
In the blanket of nitrogen, with gained among the 1.4999g embodiment D-1 and comprise the polymkeric substance of 13mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 347.1mg 2-amino-1-naphthalene sulfonic aicd is packed in the 100ml three-neck flask, stir with the adding of 60ml pyridine then, add the 0.42ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, reaction product is precipitated in 800ml ethanol again, and reclaim through centrifugal filtration.Resulting polymers agitator treating 2 hours in 250ml purifies waste water reclaims, drying under reduced pressure then after filtration, is dissolved in then among the 150ml THF and with the adding of 150ml 1N hydrochloric acid and stirs.After 14 hours, steam THF in the liquid mixture, to reclaim the polymkeric substance in the solution with evaporator.With the 100ml washing three times of purifying waste water, drying under reduced pressure obtains the PHA of 1.0119g expectation with resulting polymers.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 669cm
-1The new peak that causes.
Resulting polymers
1The H-NMR spectrogram is shown among Fig. 14.Based on
1The result of H-NMR confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 10mol% (44) representative:
Also use the mean molecular weight of gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 25,000, and weight-average molecular weight Mw is 38,000.
Embodiment E-1
Peptone more than 0.5% (Wako Pure Chemical Co. provides), 6mmol/L5-phenylpentanoic acid and 0.5mmol/L are dissolved into 1 as 5-(4-ethenylphenyl) valeric acid of ω-(4-ethenylphenyl) alkanoic acid, in the aforementioned M9 nutrient culture media of 000mL, pack 2 then into, in the shaking flask of 000mL, sterilization and be cooled to room temperature in autoclave sterilizer.Then with 2mL in advance in containing the M9 nutrient culture media of peptone more than 0.5% in 30 ℃ of shaken cultivation 8 hours Pseudomonascichorii YN2 strain cultured solution be added in the nutrient culture media of being prepared, cultivated 40 hours in 30 ℃.After the cultivation, reclaim bacterial cell, with washed with methanol and dry through centrifugal filtration.The bacterial cell of the drying of weighing adds chloroform wherein then, stirs 15 hours with extracting polymer at 35 ℃ subsequently.Chloroform extract is filtered and in evaporator, concentrate.The gained solid sediment reclaims and drying under reduced pressure with cold methanol, obtains the polymkeric substance of expectation.
The structure determination of resulting polymers is used
1H-NMR carries out (FT-NMR:BrukerDPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent C DCl
3Measure temperature: room temperature).
As a result of, confirmed to comprise the polyhydroxy-alkanoates multipolymer of the unit of following chemical formula (45) representative, content is than (mol%) A: B=94: 6.
The molecular weight of resulting polymers is measured (GPC) (TosoHLC-8220 GPC, post: Toso TSK-GEL Super HM-H, solvent: chloroform is converted to polystyrene) with the colloidal sol permeation chromatography.Resulting polymers weight (PDW) is 0.56g/L, and number-average molecular weight Mn is 61,000, and weight-average molecular weight Mw is 197,000.
Embodiment E-2
Pack in the flask of 500mL the polyester that contains 6mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit of gained in the 3.3006g embodiment E-1,0.8824 gram 18-hat-6-ether, 200mL methylene chloride and 33mL acetate and stirring.Flask is immersed in the ice bath reaction system is cooled to 0 ℃.After 120 minutes, adding 0.7061g potassium permanganate also stirred 15 hours.After the reaction, add 4.044g sodium bisulfite and stirring, make the pH=1 of liquid with the hydrochloric acid of 1.0N.After in evaporator, the methylene chloride in the liquid mixture being steamed, reclaim the polymkeric substance in the solution.Purify waste water and 300ml methanol wash resulting polymers with 450ml.With purify waste water washed twice and use the 100ml methanol wash of 300ml, reclaim polymkeric substance again.Drying under reduced pressure obtains the PHA of 2.9168g expectation.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent C DCl
3Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (Nicolet AVATAR360FT-IR) mensuration.Measure based on IR, by carboxylic acid 1,693cm
-1The new absorption peak that causes determines that gained PHA contains 3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit.
In addition, with embodiment A-2 in identical mode, adopt trimethyl silyl bisdiazo methane, by esterification, calculate the unit ratio of gained PHA to PHA side chain terminal carboxyl.
As a result of, confirmed to comprise the polyhydroxy-alkanoates multipolymer of the unit of following chemical formula (46) representative, content is than (mol%) A: B=95: 5.
In addition, with gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v), be converted to polystyrene) mean molecular weight of estimation PHA, this PHA is for making the carboxyl ester gained of aforementioned PHA side chain terminal with trimethyl silyl bisdiazo methane.As a result of, gained number-average molecular weight Mn is 65,000, and weight-average molecular weight Mw is 88,000.
Embodiment E-3
In the blanket of nitrogen, with gained in the 1.3013g embodiment E-2 and comprise the polymkeric substance of 5mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 401.9mg 2-amino-1-naphthalene sulfonic aicd is packed in the 100ml three-neck flask, stir with the adding of 50ml pyridine then, add the 0.94ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, reaction product is precipitated in 500ml ethanol again, and reclaim through centrifugal filtration.Resulting polymers agitator treating 2 hours in 250ml purifies waste water reclaims, drying under reduced pressure then after filtration, is dissolved in then among the 130ml THF and with the adding of 130ml 1N hydrochloric acid and stirs.After 14 hours, steam THF in the liquid mixture, to reclaim the polymkeric substance in the solution with evaporator.With the 100ml washing three times of purifying waste water, drying under reduced pressure obtains the PHA of 1.0059g expectation with resulting polymers.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 669cm
-1The new peak that causes.Based on
1The result of H-NMR confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 4mol% (47) representative:
Also use the mean molecular weight of gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 22,000, and weight-average molecular weight Mw is 32,000.
Embodiment F-1
Adopt with embodiment E-1 similar methods and make the polyhydroxy-alkanoates that 132.20g comprises 6mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit and 94mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment F-2
With with embodiment E-2 in synthetic polyhydroxy-alkanoates among the similar methods Processing Example F-1, obtain the polyhydroxy-alkanoates that 120.6g comprises 5mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 95mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment F-3
In the blanket of nitrogen, with gained in the 0.4010g embodiment F-2 and comprise the polymkeric substance of 5mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 163.1mg 4-amino phenyl sulfonyl acid phenenyl ester is packed in the 50ml double-neck flask, stir with the adding of 15ml pyridine then, add the 0.34ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, reclaim reaction product by in 150ml ethanol, precipitating again.Resulting polymers agitator treating 2 hours in 250ml purifies waste water, then after filtration recovery, drying under reduced pressure, be dissolved among the 40ml THF and and stir with the adding of 40ml 1N hydrochloric acid.After 14 hours, steam THF in the liquid mixture, to reclaim the polymkeric substance in the solution with evaporator.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 669cm
-1The new peak that causes.Based on
1The result of H-NMR confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 4mol% (48) representative:
Also use the mean molecular weight of gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 22,000, and weight-average molecular weight Mw is 32,000.Obtain this compound of 50g by the scale that enlarges preparation process, be used for toner manufacturing and evaluation used as embodiment compound F 17-hydroxy-corticosterone-1.
Embodiment G-1
Similar methods in employing and the embodiment A-1, except replace 1.5mmol/L5-(4-ethenylphenyl) valeric acid with 0.75mmol/L, make 2,999mg comprises the polyhydroxy-alkanoates of 9mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit and 91mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment G-2
With with embodiment A-2 in synthetic polyhydroxy-alkanoates among the similar methods Processing Example G-1, obtain 2,998mg comprises the polyhydroxy-alkanoates of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 93mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment G-3
In the blanket of nitrogen, with gained among the 0.4025g embodiment G-2 and comprise the polymkeric substance of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 199.6mg 2-amino phenyl sulfonyl acid phenenyl ester is packed in the 50ml double-neck flask, stir with the adding of 15ml pyridine then, add the 0.42ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, reclaim reaction product by in 150ml ethanol, precipitating again.Resulting polymers agitator treating 2 hours in 250ml purifies waste water, then after filtration recovery, drying under reduced pressure, be dissolved among the 40ml THF and and stir with the adding of 40ml 1N hydrochloric acid.After 14 hours, steam THF in the liquid mixture, to reclaim the polymkeric substance in the solution with evaporator.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMS0; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 669cm
-1The new peak that causes.Based on
1The result of H-NMR confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 5mol% (49) representative:
Also use the mean molecular weight of gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 22,000, and weight-average molecular weight Mw is 32,000.Obtain this compound of 50g by the scale that enlarges preparation process, G-1 is used for toner manufacturing and evaluation used as the embodiment compound.
Embodiment H-1
Adopt with embodiment E-1 similar methods and make the polyhydroxy-alkanoates that comprises 6mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit and 94mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment H-2
Polyhydroxy-alkanoates synthetic among the 132.20g embodiment H-1 is put into the four neck flasks of 3L, add 1, the 586ml acetone solution.Solution is immersed in the ice bath, add 264ml acetate and 1.35g18-hat-6-ether and stirring.Slowly add 32.34g potassium permanganate then, this potpourri was stirred in ice bath 2 hours and at room temperature stirred 3 hours.Standing over night stirred this potpourri 3 hours again under the room temperature.After the reaction, add 3,996ml ethyl acetate, 1,983ml water and 73.40g sodium bisulfite.Make this liquid pH=1 with 1.0mol/L (1.0N) hydrochloric acid.This extract of distillation is to reclaim polymkeric substance in evaporator.By purify waste water with 8.4L, then with 8.4L methyl alcohol, purify waste water repeatedly time and use 8.4L methanol wash pinching compound back and forth at last with 8.4L.Resulting polymers is dissolved in the 986ml tetrahydrofuran, in the 50L stainless steel disc of 32L methyl alcohol is housed with one day one night of dialysis membrane (Spectrum Inc., make, Spectra/por standard regenerated cellulose dialysis membrane 3) dialysis.Reclaim the polymkeric substance in the dialysis membrane, and it be dissolved in the 986ml tetrahydrofuran once more, in the 50L stainless steel disc of 32L methyl alcohol is housed with one day one night of dialysis membrane (Spectrum Inc. makes Spectra/por standard regenerated cellulose dialysis membrane 3) dialysis.The polymkeric substance and the pressurization of reclaiming in the dialysis membrane are dry, obtain the PHA of 120.6g expectation.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent C DCl
3Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (Nicolet AVATAR360FT-IR) mensuration.As a result of, confirm that PHA comprises 3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 3-hydroxyl-5-phenylpentanoic acid unit as monomeric unit.
In addition, adopt trimethyl silyl bisdiazo methane,, calculate the unit ratio of gained PHA by esterification to PHA side chain terminal carboxyl.Pack into 61mL target P HA in the 100ml eggplant type flask and add the 4.2ml chloroform and 1.4mL methyl alcohol makes it dissolving.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane (Aldrich Inc. makes) of 0.5ml 2.0mol/L, and at room temperature stirred 30 minutes.After the reaction, in evaporator, distill to reclaim polymkeric substance.By using 50ml methanol wash pinching compound back and forth.Drying under reduced pressure obtains 60mgPHA.
The analysis showed that with NMR that identical before mode is implemented gained PHA comprises 5.7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit, 92-0mol%3-hydroxyl-5-phenylpentanoic acid unit and 2.3mol% other (with straight chain 3-hydroxyl alkane acid and 3-hydroxyl alkenoic acid of 4～12 carbon atoms).
In addition, for the reaction product of resulting polymers and trimethyl silyl bisdiazo methane, (GPC:Toso, post: Toso TSK-GEL Super HM-H, solvent: chloroform is converted to polystyrene) estimates its mean molecular weight with gel permeation chromatography.As a result of, gained number-average molecular weight Mn is 30,000, and weight-average molecular weight Mw is 62,000.
Embodiment H-3
In the blanket of nitrogen, with gained among the 103.46g embodiment H-2 and comprise the polymkeric substance of 5.7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 36.19g 2-naphthylamine sulfonic acid is packed in the 10L four neck flasks, then with 5, the adding of 405ml pyridine is stirred, and adds the 100.6g triphenyl phosphite and 100 ℃ of heating 6 hours.
After the reaction, make reaction product precipitation and recovery more after filtration in 54L ethanol.Resulting polymers agitator treating 6 hours in the 54L ion exchange water.After decant is removed washing lotion, polymer dissolution is also stirred with 10.3L 1N mixed in hydrochloric acid in 10.3L THF again.Stir after 5.5 hours,, steam wherein THF with evaporator then the mixed solution standing over night.With 4L ion-exchange water washing resulting polymers three times, drying under reduced pressure obtains the PHA of 95g expectation.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 669cm
-1The new peak that causes.Based on resulting polymers
1The result of H-NMR confirms that it is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 4.6mol% (50) representative:
Also use the mean molecular weight of gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 22,000, and weight-average molecular weight Mw is 32,000.Obtain this compound of 50g by the scale that enlarges preparation process, be used for toner manufacturing and evaluation used as embodiment compound H-1.
Embodiment H-4
Gained PHA among the 30g embodiment H-3 is packed in the 2L eggplant type flask, add 2,100ml chloroform and 525ml methyl alcohol make it dissolving, are cooled to 0 ℃.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane (Aldrich Inc. manufacturing) of 51ml2.0mol/L, and stirred 4 hours.After the reaction, in evaporator, solvent is steamed to reclaim polymkeric substance.
Add 750ml chloroform and 200ml methyl alcohol polymkeric substance is dissolved again, in evaporator, steam solvent.Repeat this operation three times.
Under reduced pressure carry out drying, obtain 28gPHA.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) measure.
1The result of H-NMR shows the peak of 3～4ppm that methylmesylate causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 3.7mol% (51) representative.
Adopt the acid number titration of potentiometric titrimeter AT510 (Kyoto Denshi Co. manufacturing) also not show the peak that sulfonic acid causes, this shows that sulfonic acid has changed into methylmesylate.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 16,000, and weight-average molecular weight Mw is 35,000.Obtain this compound of 50g by the scale that enlarges preparation process, be used for toner manufacturing and evaluation used as embodiment compound H-2.
Example I-1
According to Macromolecules, 29, the method described in the 1762-1766 (1996), synthetic 5-(4-tolyl) valeric acid.
Peptone more than 0.5% (Wako Pure Chemical Co. provides), 1.0g 5-phenylpentanoic acid and 0.2g 5-(4-tolyl) valeric acid are added to 1, in the 000mLM9 nutrient culture media, pack 2 then into, in the shaking flask of 000mL, sterilization is with the preparation nutrient culture media in autoclave sterilizer.
To carry out shaken cultivation 8 hours with the preparation inoculum in the M9 nutrient culture media of peptone more than the Pseudomonas cichorii YN2 inoculation to 0.5% and in 30 ℃.This nutrient solution of 10ml is added in the aforementioned 0.9g of containing 5-phenylpentanoic acid and the nutrient culture media of 5-(4-tolyl) valeric acid as substrate, implements to cultivate 40 hours in 30 ℃.After the cultivation, reclaim bacterial cell through centrifugal filtration, with washed with methanol and drying under reduced pressure.
After weighing, the bacterial cell of drying and chloroform stirred at 25 ℃ accumulated in polymkeric substance in the bacterial cell with extraction in 72 hours.Chloroform extract is filtered, and filtrate is concentrated in evaporator, polymkeric substance is dissolved in the acetone and with insoluble part again removes by filter.Then filtrate is concentrated in evaporator, add cold methanol, collect solid sediment and drying under reduced pressure, obtain the polymkeric substance of expectation.Weighing is by the dry weight of the polymkeric substance of aforementioned recovery method recovery.
The structure determination of resulting polymers is used
1H-NMR carries out (FT-NMR:BrukerDPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent C DCl
3Measure temperature: room temperature).
As a result of, confirmed to comprise the polyhydroxy-alkanoates multipolymer of the unit of following chemical formula (56) representative, content is than (mol%) A: B=93: 7.
The molecular weight of resulting polymers is measured (GPC) (TosoHLC-8220 GPC, post: Toso TSK-GEL Super HM-H, solvent: chloroform, molecular weight are converted to polystyrene) with the colloidal sol permeation chromatography.
Resulting polymers weight (PDW) is 0.41g/L, and number-average molecular weight Mn is 69,000, and weight-average molecular weight Mw is 156,000.
Example I-2
With with embodiment E-2 similar methods Processing Example I-1 in synthetic polyhydroxy-alkanoates, obtain the polyhydroxy-alkanoates that 2.9537g contains 6mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 94.0mol%3-hydroxyl-5-phenylpentanoic acid unit.
Example I-3
With with embodiment E-3 similar methods Processing Example I-2 in synthetic polyhydroxy-alkanoates, the result has confirmed to contain the polyhydroxy-alkanoates multipolymer of the unit that the following chemical formula of 5mol% (57) represents:
Also use with embodiment E-3 in the mean molecular weight of identical method estimation gained PHA.As a result of, gained number-average molecular weight Mn is 19,000, and weight-average molecular weight Mw is 41,000.
Embodiment J-1
With making 3 with embodiment G-1 similar methods, 000mg contains the polyhydroxy-alkanoates of 9mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit and 91mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment J-2
With with embodiment A-2 similar methods Processing Example J-1 in synthetic polyhydroxy-alkanoates, obtain 2,990mg contains the polyhydroxy-alkanoates of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 93mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment J-3
In the blanket of nitrogen, with gained among the 1.5002g embodiment J-2 and comprise the polymkeric substance of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 448.6mg2-amino-2-methyl propane sulfonic acid is packed in the 100ml three-neck flask, stir with the adding of 56.5ml pyridine then, add the 1.53ml triphenyl phosphite and 100 ℃ of heating 6 hours.
After the reaction, by in 565ml ethanol, precipitating again and filtering and reclaim reaction product.Resulting polymers in 565ml purifies waste water agitator treating 5.5 hours, filtered and recycled, drying under reduced pressure, be dissolved among the 150mlTHF and stir with the adding of 150ml1N hydrochloric acid.After 14 hours, steam THF in the liquid mixture, reclaim the polymkeric substance in the solution with evaporator.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 669cm
-1The new peak that causes.
1The result of H-NMR shows by methyl and transferred by the introducing of 2-amino-2-methyl propane sulfonic acid at the peak that 1.446ppm causes, based on this result, confirmed to comprise the polyhydroxy-alkanoates multipolymer of the unit of the following chemical formula of 7mol% (58) representative.
Also use the mean molecular weight of gel permeation chromatography (GPC:Toso, post: Toso PLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 21,000, and weight-average molecular weight Mw is 33,000.
Embodiment J-4
The PHA of 1.0020g embodiment J-3 gained is packed in the 300ml eggplant type flask, add 70ml chloroform and 17.5ml methyl alcohol and make it dissolving, be cooled to 0 ℃.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane (Aldrich Inc. manufacturing) of 27.9ml 2.0mol/L, and stirred 4 hours.After the reaction, in evaporator, solvent is steamed to reclaim polymkeric substance.
Add 70ml chloroform and 17.5ml methyl alcohol polymkeric substance is dissolved again, steam solvent with evaporator.Repeat this operation three times.
The down dry polymkeric substance that is reclaimed of decompression obtains 0.9560gPHA.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) measure.
1The result of H-NMR shows the peak of 3～4ppm that methylmesylate causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 7mol% (59) representative.
Adopt the acid number titration of potentiometric titrimeter AT510 (Kyoto Denshi Co. manufacturing) also not show the peak that sulfonic acid causes, this shows that sulfonic acid has changed into methylmesylate.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 17,000, and weight-average molecular weight Mw is 32,000.
Embodiment K-1
Adopt with embodiment G-1 similar methods and make 2,990mg contains the polyhydroxy-alkanoates of 9mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit and 91mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment K-2
With with embodiment A-2 similar methods Processing Example K-1 in synthetic polyhydroxy-alkanoates, obtain 2,975mg contains the polyhydroxy-alkanoates of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 93mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment K-3
In the blanket of nitrogen, with gained among the 1.4996g embodiment K-2 and comprise the polymkeric substance of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 507.2 milligrams of 2-aminobenzenesulfonic acids are packed in the 100ml three-neck flask, stir with the adding of 56.5ml pyridine then, add the 1.53ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, by in 565ml ethanol, precipitating again and filtering and reclaim reaction product.Resulting polymers in 565ml purifies waste water agitator treating 5.5 hours, filtered and recycled, drying under reduced pressure, be dissolved among the 150mlTHF and stir with the adding of 150ml1N hydrochloric acid.After 14 hours, steam THF in the liquid mixture, reclaim the polymkeric substance in the solution with evaporator.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 671cm
-1The new peak that causes.
Figure 15 represents resulting polymers
1The H-NMR spectrogram.Can observe by introducing the peak that aromatic ring that the 2-aminobenzenesulfonic acid brought causes, based on this 7.71 and 8.50
1H-NMR result confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that comprises the unit of the following chemical formula of 7mol% (60) representative.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 25,000, and weight-average molecular weight Mw is 37,000.
Embodiment K-4
The PHA of 1.0010g embodiment K-3 gained is packed in the 300ml eggplant type flask, add 70ml chloroform and 17.5ml methyl alcohol and make it dissolving, be cooled to 0 ℃.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane (Aldrich Inc. manufacturing) of 27.9ml 2.0mol/L, and stirred 4 hours.After the reaction, in evaporator, solvent is steamed to reclaim polymkeric substance.
Add 70ml chloroform and 17.5ml methyl alcohol polymkeric substance is dissolved again, in evaporator, steam solvent.Repeat this operation three times.
The down dry polymkeric substance that is reclaimed of decompression obtains 0.9023 gram PHA.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) measure.
1The result of H-NMR shows the peak of 3～4ppm that methylmesylate causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 7mol% (61) representative.
Adopt the acid number titration of potentiometric titrimeter AT510 (Kyoto Denshi Co. manufacturing) also not show the peak that sulfonic acid causes, this shows that sulfonic acid has changed into methylmesylate.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 23,000, and weight-average molecular weight Mw is 34,000.
Embodiment L-1
With making 3 with embodiment G-1 similar methods, 120mg contains the polyhydroxy-alkanoates of 9mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit and 91mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment L-2
With with embodiment A-2 similar methods Processing Example L-1 in synthetic polyhydroxy-alkanoates, obtain 3,050mg contains the polyhydroxy-alkanoates of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 93mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment L-3
In the blanket of nitrogen, with gained among the 1.5020g embodiment L-2 and comprise the polymkeric substance of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 595.7 milligrams of 4-aminoanisole-2-sulfonic acid are packed in the 100ml three-neck flask, stir with the adding of 56.5ml pyridine then, add the 1.53ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, by in 565ml ethanol, precipitating again and filtering and reclaim reaction product.Resulting polymers in 565ml purifies waste water agitator treating 5.5 hours, filtered and recycled, drying under reduced pressure, be dissolved among the 150mlTHF and stir with the adding of 150ml 1N hydrochloric acid.After 13 hours, steam THF in the liquid mixture, reclaim the polymkeric substance in the solution with evaporator.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 670cm
-1The new peak that causes.
Fig. 16 expression resulting polymers
1The H-NMR spectrogram.Can observe by introducing the peak that the 4-aromatic ring that aminoanisole-2-sulfonic acid is brought causes, based on this 8.40
1H-NMR result confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that comprises the unit of the following chemical formula of 6mol% (62) representative.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 35,000, and weight-average molecular weight Mw is 48,000.
Embodiment L-4
The PHA of 0.9887g embodiment L-3 gained is packed in the 300ml eggplant type flask, add 70ml chloroform and 17.5ml methyl alcohol and make it dissolving, be cooled to 0 ℃.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane (Aldrich Inc. manufacturing) of 27.9ml 2.0mol/L, and stirred 4 hours.After the reaction, in evaporator, solvent is steamed to reclaim polymkeric substance.
Add 70ml chloroform and 17.5ml methyl alcohol polymkeric substance is dissolved again, in evaporator, steam solvent.Repeat this operation three times.
The down dry polymkeric substance that is reclaimed of decompression obtains 0.9331 gram PHA.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) measure.
1The result of H-NMR shows the peak of 3～4ppm that methylmesylate causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 6mol% (63) representative.
Adopt the acid number titration of potentiometric titrimeter AT510 (Kyoto Denshi Co. manufacturing) also not show the peak that sulfonic acid causes, this shows that sulfonic acid has changed into methylmesylate.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 32,000, and weight-average molecular weight Mw is 43,000.
Embodiment M-1
Adopt with embodiment G-1 similar methods and make 3,300mg contains the polyhydroxy-alkanoates of 9mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit and 91mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment M-2
With with embodiment A-2 similar methods Processing Example M-1 in synthetic polyhydroxy-alkanoates, obtain 3,230mg contains the polyhydroxy-alkanoates of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 93mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment M-3
In the blanket of nitrogen, with gained among the 1.5003g embodiment M-2 and comprise the polymkeric substance of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 653.2 milligrams of naphthalidine-8-sulfonic acid are packed in the 100ml three-neck flask, stir with the adding of 56.5ml pyridine then, add the 1.53ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, by in 565ml ethanol, precipitating again and filtering and reclaim reaction product.Resulting polymers in 565ml purifies waste water agitator treating 5.5 hours, filtered and recycled, drying under reduced pressure, be dissolved among the 150mlTHF and stir with the adding of 150ml 1N hydrochloric acid.After 14 hours, steam THF in the liquid mixture, reclaim the polymkeric substance in the solution with evaporator.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 669cm
-1The new peak that causes.
Figure 17 represents resulting polymers
1The H-NMR spectrogram.
1The peak transfer that naphthyl causes has been shown among the H-NMR,, has confirmed that gained PHA is the polyhydroxy-alkanoates multipolymer that comprises the unit of the following chemical formula of 7mol% (64) representative based on this result.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 30,000, and weight-average molecular weight Mw is 43,000.
Embodiment M-4
The PHA of 1.0030g embodiment M-3 gained is packed in the 300ml eggplant type flask, add 70ml chloroform and 17.5ml methyl alcohol and make it dissolving, be cooled to 0 ℃.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane (Aldrich Inc. manufacturing) of 27.9ml 2.0mol/L, and stirred 4 hours.After the reaction, in evaporator, solvent is steamed to reclaim polymkeric substance.
Add 70ml chloroform and 17.5ml methyl alcohol polymkeric substance is dissolved again, in evaporator, steam solvent.Repeat this operation three times.
The down dry polymkeric substance that is reclaimed of decompression obtains 0.9023gPHA.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) measure.
1The result of H-NMR shows the peak of 3～4ppm that methylmesylate causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 7mol% (65) representative.
Adopt the acid number titration of potentiometric titrimeter AT510 (Kyoto Denshi Co. manufacturing) also not show the peak that sulfonic acid causes, this shows that sulfonic acid has changed into methylmesylate.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 28,000, and weight-average molecular weight Mw is 42,000.
Embodiment N-1
Adopt with embodiment G-1 similar methods and make 3,085mg contains the polyhydroxy-alkanoates of 9mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit and 91mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment N-2
With with embodiment A-2 similar methods Processing Example N-1 in synthetic polyhydroxy-alkanoates, obtain 2,997mg contains the polyhydroxy-alkanoates of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 93mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment N-3
In the blanket of nitrogen, with gained among the 1.5023g embodiment N-2 and comprise the polymkeric substance of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 548.2 milligrams of 2-aminobenzenesulfonic acid methyl esters are packed in the 1 00ml three-neck flask, stir with the adding of 56.5ml pyridine then, add the 1.53ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, by in 565ml ethanol, precipitating again and filtering and reclaim reaction product.Resulting polymers in 565ml purifies waste water agitator treating 5.5 hours, filtered and recycled, drying under reduced pressure, be dissolved among the 150mlTHF and stir with the adding of 150ml 1N hydrochloric acid.After 14 hours, steam THF in the liquid mixture, reclaim the polymkeric substance in the solution with evaporator.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 670cm
-1The new peak that causes.
1H-NMR has shown the transfer at the peak that aromatic ring causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that comprises the unit of the following chemical formula of 7mol% (66) representative.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 30,000, and weight-average molecular weight Mw is 45,000.
Embodiment O
In 10.00 gram 2-amino-1-naphthalene sulfonic aicd (Tokyo Kasei Kasei Kogyo Co. manufacturing) 2L eggplant type flasks of packing into, add 1,400ml chloroform and 460ml methyl alcohol make it dissolving, are cooled to 0 ℃.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane (Aldrich Inc. manufacturing) of 113ml 2.0mol/L, and stirred 2 hours.After the reaction, remove by filter the crystal that deposits in the reaction, reclaim the filtrate of the 2-amino-1-naphthalene sulfonic aicd methyl esters that contains expectation.In evaporator, handle this solution that contains 2-amino-1-naphthalene sulfonic aicd methyl esters to steam solvent, reclaim crude product thus.
With the crude product of silica gel column chromatography purifying gained, obtain 2.45 gram 2-amino-1-naphthalene sulfonic aicd methyl esters.
The structure of gained compound is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) measure.
1The result of H-NMR shows the peak of 3～4ppm that methylmesylate causes, based on this result, confirms the 2-amino-1-naphthalene sulfonic aicd methyl esters of following chemical formula (67) representative.
Embodiment P-1
Adopt with embodiment G-1 similar methods and make 3,150mg contains the polyhydroxy-alkanoates of 9mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit and 91mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment P-2
With with embodiment A-2 similar methods Processing Example P-1 in synthetic polyhydroxy-alkanoates, obtain 3,018mg contains the polyhydroxy-alkanoates of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 93mol%3-hydroxyl-5-phenylpentanoic acid unit.
Embodiment P-3
In the blanket of nitrogen, with gained among the 1.5005g embodiment P-2 and comprise the polymkeric substance of 7mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit and 694.8mg embodiment O in the 2-amino-1-naphthalene sulfonic aicd methyl esters of gained pack in the 100ml three-neck flask, stir with the adding of 56.5ml pyridine then, add the 1.53ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, by in 565ml ethanol, precipitating again and filtering and reclaim reaction product.Resulting polymers in 565ml purifies waste water agitator treating 5.5 hours, filtered and recycled, drying under reduced pressure, be dissolved among the 150mlTHF and stir with the adding of 150ml 1N hydrochloric acid.After 14 hours, steam THF in the liquid mixture, reclaim the polymkeric substance in the solution with evaporator.The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (Nicolet AVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 670cm
-1The new peak that causes.
1H-NMR has shown the transfer at the peak that naphthalene nucleus causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that comprises the unit of the following chemical formula of 6mol% (68) representative.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 31,000, and weight-average molecular weight Mw is 41,000.
Embodiment Q-1
Prepare three 2, the 000mL shaking flask.The many peptones of 0.5wt% (Wako Pure ChemicalCo. provides), 6.0mmol/L5-(phenyl sulfane (sulfanyl) base) valeric acid and 1mmol/L5-(4-ethenylphenyl) valeric acid are dissolved into 1, in the aforementioned M9 nutrient culture media of 000mL, pack into then each 2, in the 000mL shaking flasks, sterilization and be cooled to room temperature in autoclave sterilizer.Then with 11mL in advance in containing the M9 nutrient culture media of peptone more than 0.5% in 30 ℃ of shaken cultivation 8 hours Pseudomonas cichorii YN2 strain cultured solution be added in the nutrient culture media of being prepared, cultivated 38 hours in 30 ℃.After the cultivation, collect nutrient solution, adopt centrifugal filtration to reclaim bacterial cell, with washed with methanol and dry.After weighing, the bacterial cell of drying is stirred 25 hours with extracting polymer with chloroform at 35 ℃.Filter chloroform extract, in evaporator, concentrate and precipitate again to reclaim polymkeric substance with 0.45 μ m film filter at cold methanol.The drying under reduced pressure polymkeric substance that obtains expecting then.The dry weight of measuring resulting polymers in this embodiment is 1111mgPHA.
The mean molecular weight of resulting polymers is measured (GPC) (TosoHLC-8220 GPC, post: Toso TSK-GEL Super HM-H, solvent: chloroform, molecular weight are converted to polystyrene) with the colloidal sol permeation chromatography.As a result, gained number-average molecular weight Mn is 105,000, and weight-average molecular weight Mw is 130,000.
The structure determination of resulting polymers is used
1H-NMR carries out (FT-NMR:BrukerDPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent C DCl
3Measure temperature: room temperature).
As a result, confirmed a kind of polyhydroxy-alkanoates multipolymer, it comprises 3-hydroxyl-5-(phenyl sulfane base) valeric acid unit of following chemical formula (69) representative and 3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit as monomeric unit.
In addition, based on
1The H-NMR spectrogram has been determined the ratio of monomer: 70mol%3-hydroxyl-5-(phenyl sulfophenyl) valeric acid unit, 20mol%3-hydroxyl-ω-(4-ethenylphenyl) valeric acid unit and 10mol% other (with straight chain 3-hydroxyl alkane acid of 4～12 carbon atoms).
Embodiment Q-2
Pack into the polyhydroxy-alkanoates of gained among the 302mg embodiment Q-1 in the 200mL eggplant type flask and add the 20ml methylene chloride and make it dissolving.This solution is placed ice bath, add 3ml acetate and 1,103 milligram of also stirring of 18-hat-6-ether.Then, in ice bath, slowly add 877 milligrams of potassium permanganate and stirred 21 hours in room temperature.After the reaction, add 50ml water and 3,050 milligrams of sodium bisulfites.Use the hydrochloric acid of 1.0mol/L (1.0N) to make the pH=1 of liquid then.After in evaporator, the methylene chloride in the liquid mixture being steamed, reclaim the polymkeric substance in the solution.This polymkeric substance with 150ml purify waste water, with 150ml methyl alcohol, twice usefulness 150ml purifies waste water and finally uses the 50ml methanol wash then, obtains a kind of polymkeric substance thus, decompression is dry down, obtains the PHA of 342mg expectation.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR3 60FT-IR) mensuration.As a result, confirmed a kind of polyhydroxy-alkanoates multipolymer, it comprises 3-hydroxyl-5-(phenyl sulfonyl) valeric acid unit and 3-hydroxyl-ω-(4-carbonyl phenyl) valeric acid unit of following chemical formula (70) representative.
In addition, can adopt trimethyl silyl bisdiazo methane,, calculate the unit ratio of gained PHA by esterification to PHA side chain terminal carboxyl.
Pack into 30mg target P HA in the 100ml eggplant type flask and add the 2.1ml chloroform and 0.7ml methyl alcohol makes it dissolving.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane of 0.5ml 2mol/L, and at room temperature stirred 30 minutes.After the reaction, in evaporator, solvent is steamed to reclaim polymkeric substance.With 50ml methanol wash pinching compound back and forth.Drying under reduced pressure obtains 31mgPHA.
Analyze to carry out NMR with identical before mode.Based on
1The H-NMR spectrogram confirms to have ratio between the unit: 74mol%3-hydroxyl-5-(phenyl sulfonyl) valeric acid unit, 17mol%3-hydroxyl-ω-(4-carbonyl phenyl) valeric acid unit and 9mol% other (with straight chain 3-hydroxyl alkane acid of 4～12 carbon atoms).
In addition, with gel permeation chromatography (GPC:Toso, post: Polymer LaboratoriesPLgel 5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v), be converted to polystyrene) mean molecular weight of estimation PHA, this PHA is for making the carboxyl ester gained of aforementioned PHA side chain terminal with trimethyl silyl bisdiazo methane.As a result of, gained number-average molecular weight Mn is 85,000, and weight-average molecular weight Mw is 110,000.
Obtain 2gPHA by the scale that enlarges said method, be used for embodiment Q-3.
Embodiment Q-3
In the blanket of nitrogen, with gained among the 1.5003g embodiment Q-2 and comprise the polymkeric substance and 1 of 17mol%3-hydroxyl-ω-(4-carboxyl phenyl) valeric acid unit, 201mg 2-amino-1-naphthalene sulfonic aicd is packed in the 100ml three-neck flask, stir with the adding of 56.5ml pyridine then, add the 2.82ml triphenyl phosphite and 100 ℃ of heating 6 hours.After the reaction, reaction product is precipitated again in 565ml ethanol.Resulting polymers in 565ml purifies waste water agitator treating 5.5 hours, filtered and recycled, drying under reduced pressure, be dissolved among the 150mlTHF and stir with the adding of 150ml 1N hydrochloric acid.After 14 hours, steam THF in the liquid mixture, reclaim the polymkeric substance in the solution with evaporator.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) and fourier-transform infrared absorb (FT-IR) spectrometer (NicoletAVATAR360FT-IR) mensuration.
Measure based on IR, by carboxylic acid 1,693cm
-1The peak that causes weakens, and observes by amide group 1 671cm
-1The new peak that causes.
1H-NMR has shown the transfer at the peak that naphthalene nucleus causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that comprises the unit of the following chemical formula of 15mol% (71) representative.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 76,000, and weight-average molecular weight Mw is 97,000.
Embodiment Q-4
The PHA of 1.0020g embodiment Q-3 gained is packed in the 300ml eggplant type flask, add 70ml chloroform and 17.5ml methyl alcohol then and make it dissolving, be cooled to 0 ℃.In this solution, add the hexane solution of the trimethyl silyl bisdiazo methane (Aldrich Inc. manufacturing) of 21.1ml 2mol/L, and stirred 4 hours.After the reaction, in evaporator, solvent is steamed to reclaim polymkeric substance.
Add 70ml chloroform and 17.5ml methyl alcohol polymkeric substance is dissolved again, in evaporator, steam solvent.Repeat this operation three times.
The down dry polymkeric substance that is reclaimed of decompression obtains 0.9057gPHA.
The structure of resulting polymers is used
1H-NMR (FT-NMR:Bruker DPX400;
1H resonant frequency: 400MHz; Measure atomic species:
1H; Solvent: deuterate DMSO; Measure temperature: room temperature) measure.
1The result of H-NMR shows the peak of 3～4ppm that methylmesylate causes, based on this result, confirms that gained PHA is the polyhydroxy-alkanoates multipolymer that contains the unit of the following chemical formula of 15mol% (72) representative.
Adopt the acid number titration of potentiometric titrimeter AT510 (Kyoto Denshi Co. manufacturing) also not show the peak that sulfonic acid causes, this shows that sulfonic acid has changed into methylmesylate.
Mean molecular weight with gel permeation chromatography (GPC:Toso, post: Polymer Laboratories PLgel5 μ MIXED-C, solvent: DMF/LiBr 0.1% (w/v) is converted to polystyrene) estimation gained PHA.As a result of, gained number-average molecular weight Mn is 79,000, and weight-average molecular weight Mw is 103,000.
Then, prepare various toners and it is estimated (embodiment 1～34) with charge control agent, described charge control agent prepares with the method that is selected from the inventive method.
In the 2L four neck flasks of being furnished with high speed agitator TK-homomixer, Na packs into
3PO
4Aqueous solution, to be adjusted at 10, the rotating speed of 000rpm is heated to 60 ℃.Tilt lenitively with CaCl then
2Aqueous solution adds, and comprises fine dispersion agent Ca with preparation
3(PO
4)
2Aqueous liquid dispersion, Ca
3(PO
4)
2Solubleness in water is low.
On the other hand, with following composition, and 10 mass parts release agents (ester type waxes) and 10 mass parts are by 2, and the polymerization initiator that 2 '-azo two (2, the 4-methyl pentane nitrile) constitutes disperseed 3 hours in bowl mill, obtained polymerizable monomer composition thus:
Styrene monomer 82 mass parts
Divinyl benzene monomer 0.1 mass parts
Cyano group colorant (C.I pigment blue 15) 6 mass parts
Oxidic polyethylene resin (molecular weight 3200, acid number 8) 5 mass parts
During the polymerizable monomer composition that will as above prepare is packed the aqueous liquid dispersion of preparing in advance into then,, carry out particle under the rotating speed of 000rpm and form 10.Subsequently, under the wing of paddle stirrer stirs, reacted 3 hours, react 6 hours to finish polyreaction at 80 ℃ then at 65 ℃.After the reaction,, add acid then to be dissolved in the low Ca of solubleness in the water with the suspending liquid cooling
3(PO
4)
2, filtering, wash also, drying obtains blue polymer particle (1).In the grain diameter measurement that carries out with Coulter Counter-Multisizer (Coulter Corp. manufacturing), gained blue polymer particle (1) has the weight average particle diameter of 6.9 μ m, and the micro mist amount of 5.3 quantity % (3.17 μ m or the littler ratio of particle in distributed number).
Mix the hydrophobic silica powder (BET:270m that 1.3 mass parts hexamethyldisilazanes was handled from the outside with the Henshel mixer by doing
2/ g) be added in the blue polymer particle (1) that 1 00 mass parts make like this as the flowable improver, obtain the blue toner (1) of the embodiment of the invention thus.And 7 mass parts blue toners (1) and 93 mass parts are scribbled the magnet carrier (mean grain size: 45 μ m) mix, obtain being used for the blue developer solution of 2-component of magnetic brush development of resin.
With embodiment compd A-2, C-1 and the C-2 replacement embodiment compd A-1, similar methods makes blue toner (2)～(4) of embodiment 2～4 among employing and the embodiment 1 except respectively.As among the embodiment 1, measure the characteristic of these toners, and be shown in Table 1.Equally also with embodiment 1 in the same these toners of handling, obtain blue developer solution (2)～(4) of bi-component of embodiment 2～4.
The comparative example 1
Except not adopting the embodiment compound, use with embodiment 1 in similar methods make comparative example 1 blue toner (5).As among the embodiment 1, measure the characteristic of this toner, and be shown in Table 1.Equally also with embodiment 1 in the same this toner of handling, obtain comparative example 1 the blue developer solution (5) of bi-component.
＜estimate
After stirring 10 seconds and 300 seconds, (25 ℃ of ambient temperature and moisture conditions, 60%RH) reach down (30 ℃ of hot and humid conditions, 80%RH), in blue developer solution (1)～(4) of the bi-component of previous embodiment and comparative example's 1 the bi-component blueness developer solution (5) each is carried out toner charge measurement amount with aforesaid quantity of electric charge measuring method.The measured value that bi-component is blown discharge capacity (blow-off change amount) is rounded up to a decimal, in order to following standard evaluation.Gained the results are summarized in the table 1:
[charged character]
E: excellent (20 μ C/g or lower)
A: good (19.9～-10.0 μ C/g)
B: can accept (9.9～-5.0 μ C/g) in the practice
C: unacceptable in the practice (4.9 μ C/g or higher).
Except adopting 2 mass parts embodiment compd As-1, A-2, C-1 and C-2 respectively, and replace beyond the cyano group colorant with yellow colorants (hansa yellow G), adopt with embodiment 1 in similar methods make Yellow toner (1)～(4) of embodiment 5～8.As among the embodiment 1, measure the characteristic of these toners, and be shown in Table 1.Equally also with embodiment 1 in the same these toners of handling, obtain yellow developer solution (1)～(4) of bi-component.
The comparative example 2
Except not adopting the embodiment compound and replacing the cyano group colorant with yellow colorants (hansa yellow G), use with embodiment 1 in similar methods make comparative example 1 blue toner (5).As among the embodiment 1, measure the characteristic of this toner, and be shown in Table 1.Equally also with embodiment 1 in the same this toner of handling, obtain comparative example 2 the blue developer solution (5) of bi-component.
＜estimate
After stirring 10 seconds and 300 seconds, (25 ℃ of ambient temperature and moisture conditions, 60%RH) reach down (30 ℃ of hot and humid conditions, 80%RH), in yellow developer solution (1)～(4) of the bi-component of embodiment 5～8 and comparative example's 2 the bi-component yellow developer solution (5) each is carried out toner charge measurement amount with aforesaid quantity of electric charge measuring method.The measured value that bi-component is blown discharge capacity is rounded up to a decimal, in order to following standard evaluation.Gained the results are summarized in the table 1:
[charged character]
E: excellent (20 μ C/g or lower)
A: good (19.9～-10.0 μ C/g)
B: can accept (9.9～-5.0 μ C/g) in the practice
C: unacceptable in the practice (4.9 μ C/g or higher).
Except adopting 2 mass parts embodiment compound F 17-hydroxy-corticosterones-1, G-1, H-1 and H-2 respectively, and (DBP oil uptake: 110mL/100g) beyond the replacement cyano group colorant, similar methods makes black toner (1)～(4) of embodiment 9～12 among employing and the embodiment 1 with carbon black.As among the embodiment 1, measure the characteristic of these toners, and be shown in Table 1.Equally also with embodiment 1 in the same these toners of handling, obtain bicomponent black developer solution (1)～(4).
The comparative example 3
Except do not adopt the embodiment compound and with carbon black (DBP oil uptake: 110mL/100g) replace the cyano group colorant, use with embodiment 1 in similar methods make comparative example 3 black toner (5).As among the embodiment 1, measure the characteristic of this toner, and be shown in Table 1.Equally also with embodiment 1 in the same this toner of handling, obtain comparative example 3 bicomponent black developer solution (5).
＜estimate
After stirring 10 seconds and 300 seconds, (25 ℃ of ambient temperature and moisture conditions, 60%RH) reach down (30 ℃ of hot and humid conditions, 80%RH), in bicomponent black developer solution (1)～(4) of embodiment 9～12 and comparative example's 3 the bicomponent black developer solution (5) each is carried out toner charge measurement amount with aforesaid quantity of electric charge measuring method.The measured value that bi-component is blown discharge capacity is rounded up to a decimal, in order to following standard evaluation.Gained the results are summarized in the table 1:
[charged character]
E: excellent (20 μ C/g or lower)
A: good (19.9～-10.0 μ C/g)
B: can accept (9.9～-5.0 μ C/g) in the practice
C: unacceptable in the practice (4.9 μ C/g or higher).
Styrene-propene butyl acrylate copolymer resin (glass transition temperature: 70 ℃) 100 mass parts
Magenta pigment (C.I. paratonere 114) 5 mass parts
Embodiment compound F 17-hydroxy-corticosterone-1 2
Mass parts
Mix and the molten above-mentioned composition of pinching with two bar extruders (L/D=30).After the cooling,, use the meticulous fragmentation of jet mill then, obtain magenta particles (1) with rough broken this potpourri of beater grinder.This magenta particles (1) weight average particle diameter is 7.5 μ m, micro mist amount 5.3 numerical value %.
Mix the hydrophobic silica powder (BET:250m that 1.5 mass parts hexamethyldisilazanes was handled from the outside with the Henshel mixer by doing
2/ g) be added in the magenta particles (1) that 100 mass parts make like this as the flowable improver, obtain magenta (redness) toner (1) of the embodiment of the invention thus.And 7 mass parts magenta (redness) toners (1) and 93 mass parts are scribbled the magnet carrier (mean grain size: 45 μ m) mix, obtain being used for 2-component magenta (redness) developer solution of magnetic brush development of resin.
With embodiment compound G-1, H-1 and the H-2 replacement embodiment compound F 17-hydroxy-corticosterone-1, similar methods makes magenta (redness) toner (2)～(4) of embodiment 14～16 among employing and the embodiment 1 except respectively.As among the embodiment 1, measure the characteristic of these toners, and be shown in Table 1.Equally also with embodiment 13 in the same these toners of handling, obtain bi-component magenta (redness) developer solution (2)～(4) of embodiment 14～16.
The comparative example 4
Except not adopting the embodiment compound, use with embodiment 13 in similar methods make comparative example 4 magenta (redness) toner (5).As among the embodiment 1, measure the characteristic of this toner, and be shown in Table 1.Equally also with embodiment 13 in the same this toner of handling, obtain comparative example 4 bi-component magenta (redness) developer solution (5).
＜estimate
After stirring 10 seconds and 300 seconds, (25 ℃ of ambient temperature and moisture conditions, 60%RH) reach down (30 ℃ of hot and humid conditions, 80%RH), in bi-component magenta (redness) developer solution (1)～(4) of embodiment 13～16 and comparative example's 4 bi-component magenta (redness) developer solution (5) each is carried out toner charge measurement amount with aforesaid quantity of electric charge measuring method.The measured value that bi-component is blown discharge capacity is rounded up to a decimal, in order to following standard evaluation.Gained the results are summarized in the table 1:
[charged character]
E: excellent (20 μ C/g or lower)
A: good (19.9～-10.0 μ C/g)
B: can accept (9.9～-5.0 μ C/g) in the practice
C: unacceptable in the practice (4.9 μ C/g or higher).
Except adopting 2 mass parts embodiment compd As-1, A-2, C-1 and C-2 respectively, and (DBP oil uptake: 110mL/100g) beyond the substitute red, similar methods makes black toner (1)～(4) of embodiment 17～20 among employing and the embodiment 13 with carbon black.As among the embodiment 1, measure the characteristic of these toners, and be shown in Table 1.Equally also with embodiment 13 in the same these toners of handling, obtain bicomponent black developer solution (6)～(9).
The comparative example 5
Except do not adopt the embodiment compound and with carbon black (DBP oil uptake: 110mL/100g) the substitute red, use with embodiment 13 in similar methods make comparative example 5 black toner (10).As among the embodiment 1, measure the characteristic of this toner, and be shown in Table 1.Equally also with embodiment 13 in the same this toner of handling, obtain comparative example 5 bicomponent black developer solution (10).
＜estimate
After stirring 10 seconds and 300 seconds, (25 ℃ of ambient temperature and moisture conditions, 60%RH) reach down (30 ℃ of hot and humid conditions, 80%RH), in bicomponent black developer solution (6)～(9) of embodiment 17～20 and comparative example's 5 the bicomponent black developer solution (10) each is carried out toner charge measurement amount with aforesaid quantity of electric charge measuring method.The measured value that bi-component is blown discharge capacity is rounded up to a decimal, in order to following standard evaluation.Gained the results are summarized in the table 1:
[charged character]
E: excellent (20 μ C/g or lower)
A: good (19.9～-10.0 μ C/g)
B: can accept (9.9～-5.0 μ C/g) in the practice
C: unacceptable in the practice (4.9 μ C/g or higher).
Embodiment 21
Vibrin 100 mass parts
Carbon black (DBP oil uptake: 110mL/100g) 5 mass parts
Synthesizing polyester resin as follows.As catalyzer, make the addition compound product of 751 parts of bisphenol-As and 2 moles of epoxypropane, 104 parts of terephthalic acid (TPA)s and 167 part of three polyanhydride polycondensation with 2 parts of dibutyl tin oxides, obtain softening point and be 125 ℃ vibrin.
Mix the hydrophobic silica powder (BET:250m that 1.5 mass parts hexamethyldisilazanes was handled from the outside with the Henshel mixer by doing
2/ g) be added in the black particle (11) that 100 mass parts make like this as the flowable improver, obtain the black toner (11) of the embodiment of the invention thus.And 7 mass parts black toners (11) and 93 mass parts are scribbled the magnet carrier (mean grain size: 45 μ m) mix, obtain being used for the 2-component black developer solution of magnetic brush development of resin.
Embodiment 22～24
With embodiment compd A-2, C-1 and the C-2 replacement embodiment compd A-1, similar methods makes black toner (11)～(14) of embodiment 22～24 among employing and the embodiment 21 except respectively.As among the embodiment 1, measure the characteristic of these toners, and be shown in Table 1.Equally also with embodiment 21 in the same these toners of handling, obtain bicomponent black developer solution (11)～(14) of embodiment 22～24.
The comparative example 6
Except not adopting the embodiment compound, use with embodiment 21 in similar methods make comparative example 6 black toner (15).As among the embodiment 1, measure the characteristic of this toner, and be shown in Table 1.Equally also with embodiment 21 in the same this toner of handling, obtain comparative example 6 bicomponent black developer solution (15).
＜estimate
After stirring 10 seconds and 300 seconds, (25 ℃ of ambient temperature and moisture conditions, 60%RH) reach down (30 ℃ of hot and humid conditions, 80%RH), in bicomponent black developer solution (11)～(14) of embodiment 21～24 and comparative example's 6 the bicomponent black developer solution (15) each is carried out toner charge measurement amount with aforesaid quantity of electric charge measuring method.The measured value that bi-component is blown discharge capacity is rounded up to a decimal, in order to following standard evaluation.Gained the results are summarized in the table 1:
[charged character]
E: excellent (20 μ C/g or lower)
A: good (19.9～-10.0 μ C/g)
B: can accept (9.9～-5.0 μ C/g) in the practice
C: unacceptable in the practice (4.9 μ C/g or higher).
Table 1
| Embodiment | Embodiment compound sequence number | The toner sequence number | Size distribution | Charged character | ||||
| Mean grain size (μ m) | Micro mist amount (%) | Ambient temperature and moisture (Q/M) | Hot and humid (Q/M) | |||||
| 10 seconds | 300 seconds | 10 seconds | 300 seconds | |||||
| 1 | A-1 | Blue 1 | 6.9 | 5.3 | E | E | E | E |
| 2 | A-2 | Blue 2 | 7.1 | 4.9 | E | E | E | E |
| 3 | C-1 | Blue 3 | 7.3 | 4.9 | E | E | E | E |
| 4 | C-2 | Blue 4 | 7.2 | 5.1 | E | E | E | E |
| 5 | A-1 | Yellow 1 | 7.1 | 5.4 | E | E | E | E |
| 6 | A-2 | Yellow 2 | 7.2 | 5.3 | E | E | E | E |
| 7 | C-1 | Yellow 3 | 7.5 | 5.3 | E | E | E | E |
| 8 | C-2 | Yellow 4 | 7.3 | 5.1 | E | E | E | E |
| 9 | F-1 | Black 1 | 6.9 | 5.3 | E | E | E | E |
| 10 | G-1 | Black 2 | 7.2 | 5.2 | E | E | E | E |
| 11 | H-1 | Black 3 | 7.3 | 5.1 | E | E | E | E |
| 12 | H-2 | Black 4 | 7.1 | 5.3 | E | E | E | E |
| 13 | F-1 | Red 1 | 7.5 | 5.3 | E | E | E | E |
| 14 | G-1 | Red 2 | 7.4 | 5.2 | E | E | E | E |
| 15 | H-1 | Red 3 | 7.6 | 5.5 | E | E | E | E |
| 16 | H-2 | Red 4 | 7.7 | 5.4 | E | E | E | E |
| 17 | A-1 | Black 6 | 7.5 | 5.8 | E | E | E | E |
| 18 | A-2 | Black 7 | 7.4 | 5.5 | E | E | E | E |
| 19 | C-1 | Black 8 | 7.5 | 5.3 | E | E | E | E |
| 20 | C-2 | Black 9 | 7.4 | 5.5 | E | E | E | E |
| 21 | A-1 | Black 11 | 7.3 | 4.9 | E | E | E | E |
| 22 | A-2 | Black 12 | 7.6 | 5.1 | E | E | E | E |
| 23 | C-1 | Black 13 | 7.7 | 4.8 | E | E | E | E |
| 24 | C-2 | Black 14 | 7.5 | 4.9 | E | E | E | E |
| The comparative example 1 | - | Blue 5 | 7.1 | 5.2 | C | C | C | C |
| 2 | - | Yellow 5 | 7.3 | 5.4 | C | C | C | C |
| 3 | - | Black 5 | 7.1 | 5.1 | C | B | C | B |
| 4 | - | Red 5 | 7.5 | 5.6 | C | B | C | B |
| 5 | - | Black 10 | 7.6 | 5.7 | C | B | C | C |
| 6 | - | Black 15 | 7.6 | 4.9 | C | B | C | B |
(for the purpose of convenient, yellow and magenta being expressed as Huang Hehong)
Embodiment 25～30 and comparative example 7～12
At first with used image processing system in illustrated embodiments 25～30 and comparative example's 7～12 the image forming method.Fig. 1 is a kind of cross sectional representation of image processing system, and this device is used to implement the embodiment of the invention and comparative example's image forming method.Photosensitive rotary drum 1 shown in Fig. 1 has the photosensitive layer 1a that contains organic photosensitive semiconductor on substrate 1b, and is configured to rotate with direction shown in the arrow; Give its surface charging with charging roller 2, surface voltage is about-600V, this charging roller is made of charge member, contacts rotation with photosensitive drum.As shown in fig. 1, charging roller 2 is made of the metal-cored 2b that covers conductive elastic layer 2a.
According to digital image information, open or close the irradiation 3 on the photosensitive drum 1 that is applied to surface charging, form the electrostatic charge image of band exposure electromotive force-100V and half-light electromotive force-600V by polygon mirror.Cause the electrostatic charge image on the photosensitive drum 1 visual with multiple developing apparatus 4-1,4-2,4-3 and 4-4 by counter-rotating, on photosensitive drum 1, form toner image thus.In this operation, adopt the 2-component developer solution of gained among embodiment 3～8 and the comparative example 1～6, form the toner image of Yellow toner, pinkish red toner, cyano group toner or black toner.Fig. 2 represents the sectional view that the part of each developing apparatus 4 is amplified, and this device is used for the used bi-component developer solution of this operation.
Then the toner image on the photosensitive drum 1 is transferred on the intermediate transfer element 5 that contacts rotation with photosensitive drum.As a result, on photosensitive drum, form four look lamination visual images.Transfer printing and the transfer printing residual toner that is retained in photosensitive drum 1 are not recovered to and used in the toner container 9 with cleaning element 8.
As shown in fig. 1, intermediate transfer element 5 is made of metal-cored 5b that constitutes substrate and lamination elastic layer 5a thereon.Among the present invention, adopt by apply the intermediate transfer element that nitrile rubber (NBR) forms on tubular metal core 5b, carbon black fully disperses in described rubber as the material that electric conductivity is provided.It is 30 ° that the hardness of elastic layer 5b is surveyed according to JIS K6301, and volume resistance is 1.0 * 10
9Ω cm.By providing+the 500V power supply for metal-cored 5b, obtain the transfer printing electric current of the 5 μ As required from photosensitive drum 1 to the transfer printing of intermediate transfer element.
By transfer roll 7, the four look lamination toner images that form on the intermediate transfer element 5 are transferred on transfer materials such as the paper, with after heating-fixing apparatus H fix.Transfer roll 7 is made of the metal-cored 7b of external diameter 10mm and the foam element elastic layer 7a of ternary ethylene-propylene copolymer (EPDM), and carbon fully disperses in described ternary ethylene-propylene copolymer as the material that electric conductivity is provided.It is 35 ° that elastic layer 7b adopts hardness to survey according to JIS K6301, and volume resistance is 1.0 * 10
6The material of Ω cm.Equally voltage is applied to the transfer printing electric current that 15 μ A are provided on the transfer roll 7.
Device shown in Fig. 1 adopts hot-rolling type heating-fixing apparatus, and does not have the oiling station shown in Fig. 5 and 6.Top roll and lower roll all have the fluoride resin superficial layer.Roller diameter is 60mm.During fixing operation, adopt the roller of 160 ℃ fixed temperature and 7mm wide.The fixedly residual toner that reclaims from photosensitive drum through cleaning is transported to developing apparatus by re-use device and reuses.
＜estimate
(25 ℃ of aforementioned ambient temperature and moistures, 60%RH) or hot and humid (30 ℃, 80%RH) under the condition of environment, with 8 pages (A4 sizes)/minute printout speed, with replenish respectively by embodiment 1,5,9,13, the bi-component developer solution of 17 and 21 toner preparation and by the bi-component developer solution of comparative example 1～6 toner preparation, (make developing apparatus after each printout, suspend 10 seconds with monochromatic intermittent mode, and the primary operation of the deterioration of toner when restarting accelerated), print the output test, estimate the following of gained printout image.Evaluation result is summarized in the table 2.
[evaluation of printout image]
1. image density
Plain copying paper (75g/m in routine
2) on carry out the printout of predetermined number, the image density level that the end with respect to the initial pictures printing is kept is estimated.With Macbeth reflection densitometer (Macbeth Inc. manufacturing) measurement image density, to estimate the corresponding initial density 0.00 of this white portion with respect to the relative density of printout image in the white portion.
E: excellent (whole image density 1.40 or higher)
A: good (whole image density be equal to or higher than 1.35 but be lower than 1.40)
B: general (whole image density be equal to or higher than 1.00 but be lower than 1.35)
C: inferior (whole image density is less than 1.00)
2. image is tied mist
Plain copying paper (75g/m in routine
2) on carry out the printout of predetermined number, the solid white image at the end of printing is estimated.Particularly, estimate in the following manner.With reflection densitometer (Reflectometer Odel TC-6DS, Tokyo Denshoku Co., Ltd. make), measure the poorest reflection density Ds that prints the back white portion and print before the average emitted emission density Dr of paper, with the knot mist amount of following standard evaluation by (Ds-Dr) definition:
E: excellent (knot mist amount is equal to or higher than 0% and still is lower than 1.5%)
A: good (knot mist amount is equal to or higher than 1.5% and still is lower than 3.0%)
B: general (knot mist amount is equal to or higher than 3.0% and still is lower than 5.0%)
C: inferior (knot mist amount is equal to or higher than 5.0%).
3. transfer properties
Plain copying paper (75g/m in routine
2) on carry out the printout of predetermined number, visualization Image blank amount is also estimated according to following standard:
E: excellent (rareness)
A: good (small)
B: can accept in the practice
C: unacceptable in the practice.
In addition, in embodiment 25～30 and comparative example 7～12, the generation that spot on visual valuation 5,000 image prints output back photosensitive drum and the intermediate transfer element, residual toner adhere to and to printing the influence (with the coupling of image processing system) of output image.In the system of the bi-component developer solution that adopts embodiment 25～30, can not observe the spot on photosensitive drum and the intermediate transfer element and the adhesion of residual toner, very satisfactory with the coupling of image processing system.On the other hand, in the system of the bi-component developer solution that adopts comparative example 7～12, all observe the adhesion of toner on photosensitive drum under all scenario.In addition, in the system of the bi-component developer solution that adopts embodiment 25～30, unsatisfactory with the coupling of image processing system, the toner that for example forms on the intermediate transfer element adheres to and surperficial spot, and the longitudinal stripe image deflects that form on image.
Table 2
| Embodiment | 2-component developer solution | Ambient temperature and moisture | Hot and humid | |||||
| Image density | Image knot mist | Transfer properties | Image density | Image knot | Transfer properties | |||
| 1 | Blue 1 | E | E | E | | E | E | |
| 5 | Yellow 1 | E | E | E | | E | E | |
| 9 | Black 1 | E | E | E | | E | E | |
| 13 | Red 1 | E | E | E | | E | E | |
| 17 | Black 6 | E | E | E | E | E | E | |
| 21 | Black 11 | E | E | E | E | E | E | |
| The comparative example 7 | Blue 5 | C | C | C | | C | C | |
| 8 | Yellow 5 | C | C | C | | C | C | |
| 9 | Black 5 | B | B | C | | C | C | |
| 10 | Red 5 | B | B | C | | C | C | |
| 11 | Black 10 | B | B | C | | C | C | |
| 12 | Black 15 | B | B | C | B | C | C | |
In embodiment 31～33 and comparative example's 13～15 image forming method, for developer solution, adopt embodiment 1,5 and 9 and comparative example 1～3 in made toner.In addition, in image forming device spare, adopt a kind of as shown in Figure 3 pass through the image processing system that re-use device is transformed go up to be installed being purchased laser printer LBP-EX (Canon Inc. manufacturing).Dispose a kind of system for the image processing system shown in Fig. 3, wherein use the elastic doctor blade 22 of clearer 21 after transfer operation, clearer 21 keeps in touch with photosensitive drum 20, strikes off the not transfer printing toner that is retained on the photosensitive drum 20; Send into clearer 21 inside with clearer then, return developing apparatus 26, utilize the toner that reclaims at this thus by supply pipe 24 and the loading hopper 25 that utilizes clearer 23 again, is furnished with worm conveyor.
In image processing system shown in Figure 3, elementary charging roller 27 is given the surface charging of photosensitive drum 20.Elementary charging roller 27 by rubber rollers constitute (diameter: 12mm, contact pressure: 50gf/cm), this rubber rollers scribbles the nylon resin that is dispersed with conductive carbon in it; And on the electrostatic latent image load-carrying unit, form the electrostatic latent image of half-light voltage VD=-700V and light voltage VL=-200V by laser explosure (600dpi, not shown).For the toner load-carrying unit, adopt development roller shell 28, it is 1.1 that its surface scribbles the resin and the skin hardness Ra that are dispersed with carbon black in it.
Fig. 4 is the sectional view that the part of used developing apparatus among embodiment 31～33 and the comparative example 13～15 is amplified, and this device is used for single component development liquid.For making latent electrostatic image developing, the speed of setting development roller shell 28 is 1.1 times of translational speed of photosensitive drum 20 opposite faces, and the gap α (S-D) that sets between photosensitive drum 20 and the development roller shell 28 is 270 μ m.And urethane rubber scraping blade 29 is contacted, with it as the element that is used to regulate the toner bed thickness.And the temperature that will be used for fixing the heating-fixing apparatus of toner image is set at 160 ℃.For stationary installation, adopt a kind of device shown in Fig. 5 and Fig. 6.Among Fig. 6, numeral 32 expression tension-free states.
(25 ℃ of ambient temperature and moistures, 60%RH) or hot and humid (30 ℃, in environment 80%RH), with 8 pages (A4 sizes)/minute printout speed, with the continuous mode of continuous supplementation toner (operating period developing apparatus do not have time-out quicken the pattern that toner consumes thus), carry out 30,000 printouts, image density and the following standard of foundation measured on the gained printout image are estimated its permanance.And observe the 10th, 000 figure, image knot mist is estimated according to following standard.In addition, after durability test, observe state that composing images forms each device of device, estimate the coupling between each device and the every kind of aforementioned toner.Evaluation result is summarized in the table 3.
[variation of image density in the durability test]
Plain copying paper (75g/m in routine
2) on carry out the printout of predetermined number, the image density that the end of printing is kept is estimated with respect to the level of initial pictures.With Macbeth reflection densitometer (Macbeth Inc. manufacturing) measurement image density, to estimate the corresponding initial density 0.00 of this white portion with respect to the relative density of printout image in the white portion.
E: excellent (whole image density 1.40 or higher)
A: good (whole image density be equal to or higher than 1.35 but be lower than 1.40)
B: can accept in the practice (whole image density be equal to or higher than 1.00 but be lower than 1.35)
C: unacceptable in the practice (whole image density is less than 1.00)
[image knot mist]
Plain copying paper (75g/m in routine
2) on carry out the printout of predetermined number, the solid white image at the end of printing is estimated.Particularly, estimate in the following manner.With reflection densitometer (Reflectometer Odel TC-6DS, Tokyo Denshoku Co., Ltd. make), measure the poorest reflection density Ds that prints the back white portion and print before the average emitted emission density Dr of paper, with the knot mist amount of following standard evaluation by (Ds-Dr) definition:
E: excellent (knot mist amount is equal to or higher than 0% and still is lower than 1.5%)
A: good (knot mist amount is equal to or higher than 1.5% and still is lower than 3.0%)
B: general (knot mist amount is equal to or higher than 3.0% and still is lower than 5.0%)
C: inferior (knot mist amount is equal to or higher than 5.0%).
[estimating coupling] with image processing system
1. overlap the coupling of roller with development
After the printing test, the visual valuation residual toner on the cover roller that develops coherent condition and to printing the influence of output image.
E: excellent (not existing)
A: good (pettiness existence)
B: can accept (existence adheres to but be little to the image influence) in the practice
C: unacceptable in the practice (it is inhomogeneous that frequently adhesion causes image).
2. with the coupling of photosensitive drum
The situation that scratch generates on the visual valuation photosensitive drum, the adhesion that residual toner puts at developer roll, and to printing the influence of output image
E: excellent (not generating)
A: good (slight scratch but image is not had influence)
B: can accept in the practice (have adhesion and scratch but little) to image influence
C: unacceptable in the practice (the frequent image deflects that cause longitudinal stripe that adhere to).
3. with the coupling of stationary installation
Observe the fixedly surface state of film, estimate its permanance by the adhesion of comprehensive evaluation surface state and residual toner.
(1) surface state
Fixedly state is cut in lip-deep scratch of film and wiping afterwards for visualization and evaluation printout test.
E: excellent (not existing)
A: good (pettiness existence)
B: can accept in the practice
C: unacceptable in the practice.
(2) coherent condition of residual toner
Visualization and estimate after the printout test coherent condition of residual toner on the fixing film surface.
E: excellent (not existing)
A: good (pettiness existence)
B: can accept in the practice
C: unacceptable in the practice.
Table 3
| Embodiment | Toner | The printout picture appraisal | Coupling is estimated | ||||||||
| Variable density in the durability test | Image knot mist 10000 | The cover roller develops | Photosensitive drum | Stationary installation | |||||||
| During beginning | 1000 | 10000 | 30000 | Surface state | Toner adheres to | ||||||
| 31 | Blue 1 | E | E | E | E | E | E | | E | E | |
| 32 | Yellow 1 | E | E | E | E | E | E | | E | E | |
| 33 | Black 1 | E | E | E | E | E | E | E | E | E | |
| The comparative example 13 | Blue 5 | B | C | C | C | C | C | | C | C | |
| 14 | Yellow 5 | B | C | C | C | C | C | | C | C | |
| 15 | Black 5 | A | B | C | C | C | C | C | C | C | |
Except with the toner re-use device from image processing system removal shown in Figure 3, printout speed become 16 pages (A4 sizes)/minute, adopt continuous mode (operating period developing apparatus do not have time-out quicken the pattern that toner consumes thus) and adopt the blue toner (1) of embodiment 1 of continuous supplementation, with with embodiment 31 in identical mode print the output test, for embodiment 31～33 and comparative example 13～15 in identical every evaluation gained printout image and with the coupling of used image processing system.As a result, in all, all obtain gratifying result.
Claims (23)
1. polyhydroxy-alkanoates comprises the unit of at least a chemical formula (1) representative in its molecule:
R wherein
1Represent OH, halogen atom, ONa, OK or OR
1aA
1The phenyl of representing 2-methyl-propyl, unsubstituted phenyl or naphthyl, methyl or methoxy to replace, R
1aRepresent hydrogen, methyl and phenyl; The m representative is selected from 0～7 integer; And when having multiple unit, to every kind of unit R
1, A
1, R
1aHas aforementioned implication independently with m.
2. according to the polyhydroxy-alkanoates of claim 1, substituting group-A wherein
1SO
2R
1Represent by following chemical formula (6 '):
R wherein
1Be OH, halogen atom, ONa, OK or OR
6b, R wherein
6bRepresent methylidene; And when having multiple unit, R
6bEvery kind of unit had aforementioned implication independently.
3. according to the polyhydroxy-alkanoates of claim 1, A wherein
1Be to phenylene.
4. according to the polyhydroxy-alkanoates of claim 1, A wherein
1It is adjacent phenylene.
5. according to the polyhydroxy-alkanoates of claim 1, substituting group-A wherein
1SO
2R
1Be the group of chemical formula (9 ') representative:
6. according to the polyhydroxy-alkanoates of claim 1, substituting group-A wherein
1SO
2R
1Be the group of chemical formula (10 ') representative:
7. according to the polyhydroxy-alkanoates of claim 1, substituting group-A wherein
1SO
2R
1Be the group of chemical formula (52 ') representative:
8. in the polyhydroxy-alkanoates according to claim 1, A
1Be 1, the 8-naphthylene.
9. according to the polyhydroxy-alkanoates of claim 1, except the unit that comprises chemical formula (1) representative, also comprise at least a in the following two class unit: the alkanoic acid unit of the 3-hydroxyl-ω-replacement of chemical formula (11) representative:
Wherein n is selected from 1～8 integer, R
11Expression phenyl or tolyl, and when having multiple unit, n and R
11Every kind of unit had aforementioned implication independently.
10. according to the polyhydroxy-alkanoates of claim 9, R wherein
11Represent any of chemical formula (13), (16), (22) and (23), and when having multiple unit, this unit has aforementioned implication independently to every kind of cell cube:
R wherein
13Represent H, halogen atom, CH
3, C
2H
5, COOR
13a, R wherein
13aRepresent H, Na or K; And when having multiple unit, this unit has aforementioned implication independently to every kind of cell cube;
R wherein
16Represent H; And when having multiple unit, this unit has aforementioned implication independently to every kind of unit;
R wherein
22Represent H; And when having multiple unit, this unit has aforementioned implication independently to every kind of unit;
11. according to the polyhydroxy-alkanoates of claim 1, wherein number-average molecular weight is 1,000～1, in 000,000 scope.
12. a method for preparing polyhydroxy-alkanoates comprises:
Preparation comprises polyhydroxy-alkanoates, and the step of the amines of at least a chemical formula (25) representative of the unit of chemical formula (24) representative; With
Make this polyhydroxy-alkanoates and amines carry out the step of condensation reaction, thereby obtain comprising the polyhydroxy-alkanoates of the unit of chemical formula (1) representative:
Wherein the p representative is selected from 0～7 integer; R
24Represent H, Na or K; When having multiple unit, to every kind of unit p and R
24Has aforementioned implication independently;
H
2N-A
1-SO
2R
1 (25)
R wherein
1Represent OH, halogen atom, ONa, OK or OR
1aA
1The phenyl of representing 2-methyl-propyl, unsubstituted phenyl or naphthyl, methyl or methoxy to replace, R
1aRepresent hydrogen, methyl and phenyl;
R wherein
1Represent OH, halogen atom, ONa, OK or OR
1aA
1The phenyl of representing 2-methyl-propyl, unsubstituted phenyl or naphthyl, methyl or methoxy to replace, R
1aRepresent hydrogen, methyl and phenyl; The m representative is selected from 0～7 integer; And when having multiple unit, to every kind of unit R
1, A
1, R
1aHas aforementioned implication independently with m.
13. according to the preparation method of claim 12, wherein said condensation reaction is the reaction that forms amido link with condensation agent.
14. according to the preparation method of claim 13, wherein said condensation agent is that to be selected from phosphoric acid be that condensation agent, carbodiimide are that condensation agent and acid chloride are at least a in the condensation agent.
15. according to the preparation method of claim 12, it is that condensation agent is as condensation agent that thionyl (two) chlorine is adopted in wherein said condensation reaction.
16. a method for preparing polyhydroxy-alkanoates comprises:
The step for preparing the polyhydroxy-alkanoates of the unit that comprises chemical formula (26) representative;
R wherein
26Represent OH, halogen atom, ONa or OK; A
26The phenyl of representing 2-methyl-propyl, unsubstituted phenyl or naphthyl, methyl or methoxy to replace; The m representative is selected from 0～7 integer; And when having multiple unit, R
26, A
26With m every kind of unit had aforementioned implication independently; And
Make the step of described polyhydroxy-alkanoates and trimethyl silyl bisdiazo methane reaction, thereby obtain comprising the polyhydroxy-alkanoates of the unit of chemical formula (27) representative:
A wherein
27The phenyl of representing the bright base of 2-methyl, unsubstituted phenyl or naphthyl, methyl or methoxy to replace; The m representative is selected from 0～7 integer; And when having multiple unit, A
27With m every kind of unit had aforementioned implication independently.
17. an improved charge control agent, in order to the state of charge of control dusty material, wherein improvement comprises:
Comprise at least a unit in the unit of chemical formula (1) representative:
R wherein
1Represent OH, halogen atom, ONa, OK or OR
1aA
1The phenyl of representing the bright base of 2-methyl, unsubstituted phenyl or naphthyl, methyl or methoxy to replace, R
1aRepresent hydrogen, methyl and phenyl; The m representative is selected from 0～7 integer; And when having multiple unit, to every kind of unit R
1, A
1, R
1aHas aforementioned implication independently with m.
18. according to the charge control agent of claim 17, wherein said dusty material is the developing electrostatic charge image toner.
19. a developing electrostatic charge image toner comprises at least a adhesive resin, a kind of colorant and a kind of charge control agent according to claim 17.
20. an image forming method comprises: give the step of charge member impressed voltage, give the charging of electrostatic latent image load-carrying unit thus; On the electrostatic latent image load-carrying unit that has charged, form the step of electrostatic charge image; Development step makes developing electrostatic charge image with the developing electrostatic charge image toner, forms toner image thus on the electrostatic latent image load bearing unit; Transfer step is transferred to the toner image on the electrostatic latent image load bearing unit on the recording materials; And fixing step, the toner image heating is fixed on the recording materials; This method comprises the developing electrostatic charge image toner of use according to claim 19.
21. according to the image forming method of claim 20, wherein said transfer step comprises: first transfer step is transferred to the toner image on the electrostatic latent image load-carrying unit on the intermediate transfer element; And second transfer step, the toner image on the intermediate transfer element is transferred on the recording materials.
22. an image processing system, thereby comprise the device that impressed voltage is given the charging of electrostatic latent image load-carrying unit to the charge member; On the electrostatic latent image load-carrying unit that has charged, form the device of electrostatic charge image; Make developing electrostatic charge image on the electrostatic latent image load bearing unit, form the developing device of toner image thus with the developing electrostatic charge image toner; Toner image on the electrostatic latent image load bearing unit is transferred to transfer printing device on the recording materials; And toner image heating is fixed to immobilising device on the recording materials; This device comprises the developing electrostatic charge image toner of use according to claim 19.
23. according to the image processing system of claim 22, wherein said transfer printing device comprises: the first transfer printing device is transferred to the toner image on the electrostatic latent image load-carrying unit on the intermediate transfer element; And the second transfer printing device, the toner image on the intermediate transfer element is transferred on the recording materials.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002382254 | 2002-12-27 | ||
| JP382254/2002 | 2002-12-27 | ||
| JP367057/2003 | 2003-10-28 | ||
| JP418774/2003 | 2003-12-16 |
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|---|---|
| CN1732414A CN1732414A (en) | 2006-02-08 |
| CN100370365C true CN100370365C (en) | 2008-02-20 |
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| JP4535112B2 (en) | 2007-10-04 | 2010-09-01 | 富士ゼロックス株式会社 | Image forming system, image processing apparatus, and program |
| CN113416411B (en) * | 2021-07-21 | 2022-08-12 | 贵州森远增材制造科技有限公司 | Selective laser printing method for recycling and reusing four-stage nylon 12 residual powder |
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|---|---|---|---|---|
| US4837394A (en) * | 1988-08-05 | 1989-06-06 | Eastman Kodak Company | electrostatographic toner particle comprising a polyester containing a covalently bound quaternary phosphonium salt |
| US4855396A (en) * | 1988-08-05 | 1989-08-08 | Eastman Kodak Company | Polyesters containing covalently bound quaternary phosphonium salts |
| EP1236755A2 (en) * | 2001-03-01 | 2002-09-04 | Canon Kabushiki Kaisha | Novel polyhydroxyalkanoate containing unit phenylsulfanyl structure in the side cahin, process for its production, charge control agent, toner binder and toner which contain novel polyhydroxyalkanoate, and imageforming apparatus which make use of the toner |
| EP1245605A2 (en) * | 2001-03-27 | 2002-10-02 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate containing unit with thienyl structure in the side chain, process for its production, charge control agent, toner binder and toner which contain this polyhydroxyalkanoate, and image-forming method and image-forming apparatus which make use of the toner |
| EP1254918A2 (en) * | 2001-04-27 | 2002-11-06 | Canon Kabushiki Kaisha | Novel polyhydroxyalkanoate, producing method therefor, charge control agent containing such polyhydroxyalkanoate, toner containing such charge control agent and image forming method and image forming apparatus utilizing such toner |
-
2003
- 2003-12-26 CN CNB2003801075715A patent/CN100370365C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4837394A (en) * | 1988-08-05 | 1989-06-06 | Eastman Kodak Company | electrostatographic toner particle comprising a polyester containing a covalently bound quaternary phosphonium salt |
| US4855396A (en) * | 1988-08-05 | 1989-08-08 | Eastman Kodak Company | Polyesters containing covalently bound quaternary phosphonium salts |
| EP1236755A2 (en) * | 2001-03-01 | 2002-09-04 | Canon Kabushiki Kaisha | Novel polyhydroxyalkanoate containing unit phenylsulfanyl structure in the side cahin, process for its production, charge control agent, toner binder and toner which contain novel polyhydroxyalkanoate, and imageforming apparatus which make use of the toner |
| EP1245605A2 (en) * | 2001-03-27 | 2002-10-02 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate containing unit with thienyl structure in the side chain, process for its production, charge control agent, toner binder and toner which contain this polyhydroxyalkanoate, and image-forming method and image-forming apparatus which make use of the toner |
| EP1254918A2 (en) * | 2001-04-27 | 2002-11-06 | Canon Kabushiki Kaisha | Novel polyhydroxyalkanoate, producing method therefor, charge control agent containing such polyhydroxyalkanoate, toner containing such charge control agent and image forming method and image forming apparatus utilizing such toner |
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