Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
  • C09B1/02—Hydroxy-anthraquinones; Ethers or esters thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes

Definitions

• the present invention relates to an image fading inhibitor, an image forming element using the same, a recording medium, an image forming method, and an image.
• a sublimable color material is used as a recording agent, and this is supported on a base material sheet such as a polyester film to form a thermal transfer sheet (ink sheet), and a transfer material that can be dyed with a sublimation color material,
• a base material sheet such as a polyester film
• a transfer material that can be dyed with a sublimation color material
• it is a method of forming various full-color images on an image receiving sheet (recording medium for thermal transfer) in which color material receiving portions are formed on paper or plastic film.
• the thermal head of Plink is used as the heating means, and a large number of color dots of three colors or envelopes are transferred to the image receiving sheet by heating for a very short time, and the multicolored color dots are used to transfer the original of the document. Reproduces a full-color image.
• Images formed in this way are obtained by using a dye as a sublimation colorant.
• the image obtained by using a dye is sharp, transparent, reproducible, and gradation of intermediate colors. It is possible to obtain a high-quality image comparable to a full-color silver salt photographic image.
• an image formed from a sublimation dye as an obtained image is generally inferior in light resistance as compared with a pigment image, and there is a problem that the image is fading or discolored quickly when exposed to direct sunlight. Also, if there is no direct light, for example, a room Among them, there is a problem that the color is changed (dark blue) even during binding of a file or book. These light fastness and dark blue problems have been improved to the extent that UV absorbers and antioxidants are added to the dye receiving layer of the image receiving sheet.
• the antioxidants and the like are uniformly distributed throughout the dye receiving layer, and on the other hand, most of the transferred dye is present near the surface of the receiving layer. Dye retention by dye is not performed efficiently, and there is a problem that prevention of discoloration is insufficient, and there is a demand for a technology that can effectively protect the transferred dye with an antioxidant or the like.
• inkjet recording has features such as low cost of the device itself, low running cost, and easy power recording, and has rapidly spread as a digital signal output device from computers, digital cameras, etc. ing.
• Recording inks used in ink jet printers are: 'inks in which a dye is dissolved in an aqueous or non-aqueous medium; or inks in which pigments are dispersed in an aqueous or oily medium;
• Various types of ink have been proposed.
• the current mainstream ink is one in which a dye is dissolved in an aqueous medium and has features such as beautiful coloring and high safety to the human body and the environment.
• the method is mainly based on the addition of antioxidants, UV absorbers, etc., and overcoat, and the type of additive, the method of addition, and the properties of the anti-aging agent have been proposed.
• coloring materials such as dyes used in sublimation thermal transfer recording and ink jet recording, but the following are generally considered.
• color materials such as dyes are brought into a triplet excited state by light, and excited singlet oxygen is generated by exchanging energy between the triplet state colorant and the ground state triplet oxygen.
• This singlet oxygen is highly active and has a relatively long life, and it is thought to react with coloring materials such as dyes to promote oxidation or decomposition and cause deterioration of the image.
• Patent Document 1 Japanese Patent Laid-Open No. 2000-226544
• Patent Document 2 Japanese Patent Laid-Open No. 2 Q 03-94797
• Inkujiwetto print recording liquid singlet oxygen quenching rate in Patent Document 1 contains a 1 X 10 6 dm 3 mo 1- 1 s- 1 or more compounds, ⁇ Pi Inkujetto printed recording sheet is disclosed.
• Patent Document 2 at least two kinds of antioxidants are contained, and the singlet oxygen quenching rate is 1 X 10 6 dm 3 mo 1 1 s 1 or more, 1 X 10 9 dm 3 mo 1 1 s 1
• An ink jet recording medium is disclosed in which a compound having 1 or less and a compound having a radical trap rate (K s ) of 1 or more and 10000 or less are used in combination.
• Patent Document 3 discloses an ultraviolet light dissipating energy absorber as an additive for improving the color fastness of a printed image, and a bound amine free radical inhibitor as another additive ( Hindered amine compounds) and reducing agents (such as hindered phenols) are disclosed.
• the singlet oxygen quenching rate k Q value is measured mainly in a non-aqueous solvent (insoluble in water or alcohol) (see Non-Patent Document 1).
• a non-aqueous solvent insoluble in water or alcohol
• singlet oxygen quenching rate k in water-soluble solvent (soluble in water and alcohol).
• the value of the singlet oxygen quenching rate k Q varies connexion by the measuring solvent, it is known that towards the value of an aqueous solvent is reduced.
• the singlet oxygen quenching rate value of DABCO (1,4-diazabicyclo [2.2.2] octane) described in the examples of Patent Document 1 is a non-aqueous solvent according to Non-Patent Document 1.
• a 2 X 1 O 7 dm 3 mo 1- 1 s- 1, 8. 1 X 1 O 6 dm 3 mo 1- is the aqueous solvent is a main Tano in one Honoré - 1 .
• Ink jet recording using a dye as a colorant results in an aqueous solvent environment, so it is essential to study the singlet oxygen quenching rate k Q in a water-soluble solvent.
• UV dissipating energy absorbers bound amine free radical inhibitors (hindered amine compounds), reducing agents (such as hindered phenols) as disclosed in Patent Document 3 are single-layered by a chemical reaction quenching mechanism (oxidation reaction mechanism). It extinguishes the term oxygen.
• the image fading inhibitor acts as a so-called sacrificial reagent, so a compound with a higher singlet oxygen quenching ability is a more unstable compound that is more susceptible to oxidization. It becomes a trade-off relationship with the sustainability of the effect.
• Patent Document 3 discloses an excited state hydrogen (proton) transfer of a benzotriazole-based ultraviolet absorber as an ultraviolet-absorbing energy absorber.
• proton transfer acts to develop an ultraviolet absorption function. For -singlet oxygen (cause of oxidation of the coloring material), it undergoes oxidative decomposition by singlet oxygen itself and absorbs ultraviolet rays. The ability to be lost.
• the present inventors have recognized that the image fading inhibitor is deactivated as a sacrificial reagent as described above as a first problem, and an image having a mechanism that maintains the effect for a long time with a smaller amount.
• the present invention relates to an image fading preventing agent that prevents discoloration and fading (referred to as “discoloration fading” in the present specification) of a formed image and can maintain image quality stably for a long period of time, and an image forming element using the same , Recording medium, image forming method, and image formed by them
• the purpose is to provide ⁇ images.
• the present inventors have a structure that causes intramolecular proton transfer as a singlet oxygen quenching mechanism of an image fading inhibitor contained in a recording medium, and electron transfer associated with the intramolecular proton transfer.
• the number of double bonds forming the pathway is 1 or more and 4 or less, and the image fading does not include ⁇ -electron system localized in the molecule.
• the inventors have found that fading can be prevented and that it is possible to maintain image quality stably for a long time, and the present invention has been completed. That is, the present invention includes the following matters.
• the present invention is an image fading-preventing homogeneous lj that is used in a site where an image is formed by a color material and has a functional group that causes intramolecular proton transfer in the molecule.
• the present invention is an image fading-preventing agent characterized in that singlet oxygen that causes an acid-rich reaction to a colorant is deactivated by an intramolecular proton transfer mechanism.
• the present invention is a recording medium having a base material and a color material receiving site formed on the base material, the image material fading preventing agent being contained in the color material receiving site. This is a characteristic recording medium.
• the present invention is an image forming method characterized in that an image is formed with a color material on the recording medium.
• the present invention is an image-forming element comprising a coloring material and a compound having a functional group that causes intramolecular proton transfer in the molecule.
• the present invention is an image having a colorant and a compound having a functional group that causes intramolecular proton transfer in the molecule.
• FIG. 1 is a diagram for explaining the dye deterioration preventing function of the image fading preventing agent in the present invention.
• FIG. 2 is a cross-sectional view showing the configuration of the recording medium of the present invention.
• the term “image fading inhibitor” refers to gas, light, etc. when present in the ink receiving layer of a recording medium together with the color of a dye or the like contained in the ink composition used for image formation. This is a compound that protects the color material from factors that cause it to deteriorate and prevents the image from fading.
• the image fading preventing agent having such a function a compound having a structure capable of intramolecular proton transfer is used in the present invention. This anti-fading agent has the effect of deactivating singlet oxygen that causes an oxidation reaction on the colorant by an intramolecular proton transfer mechanism.
• a compound having a hydrogen bond in the molecule undergoes an intramolecular proton transfer reaction represented by the following formulas (a) to (d) by light irradiation.
• the electron transfer path associated with intramolecular proton transfer at that time is indicated by a bold line.
• the wave function nodes in the excited state are shown by broken lines.
• intramolecular proton transfer means a phenomenon in which the intramolecular resonance equation is reversibly established even if a hydrogen atom moves in the molecule as shown in the above formulas (a) to (d). That means.
• the number of double bonds forming an electron transfer path associated with intramolecular proton transfer means that the molecule is accompanied by the above formula (a)
• a conjugated system with at least one double bond is necessary to complete resonances consistently within the molecule. The more double bonds, the longer the conjugated chain, and more energy and time for isomerization.
• the singlet oxygen quenching mechanism by the pentavalent phosphate ester compound will be described with reference to FIG.
• Excited singlet oxygen which causes image fading, is generated by the exchange of energy between the triplet excited state colorant and the ground state triplet oxygen when the coloring material such as dye becomes a triplet excited state by light.
• the generated singlet oxygen reacts with the dye as it is because of its high reaction activity, causing the dye to oxidize and produce a dye decomposition product (image fading phenomenon, dye deterioration).
• the pentavalent phosphate ester compound when the pentavalent phosphate ester compound is present together with the coloring material, the pentavalent phosphate compound interacts with the excited singlet oxygen faster than the rate at which the excited singlet oxygen reacts with the dye by a competitive reaction. However, it is thought that excited singlet oxygen is quenched into ground state triplet oxygen by intramolecular proton transfer reaction.
• the dye Since the dye is not easily oxidized by ground-state triplet oxygen, it is thus protected from oxidation leading to image fading. ,
• Such an image fading preventing agent that causes a preferred intramolecular proton transfer reaction in the present invention is the wave function in the excited state as indicated by the broken lines in the above formulas (a) to (d). This was achieved by considering the presence and the intramolecular conjugated electron system involved in the proton transfer reaction. That is, the anti-fading agent of the present invention has a structure that causes intramolecular proton transfer, and the number of double bonds forming an electron transfer path associated with the intramolecular proton transfer is 1 or more and 4 or less. And it does not include a localized ⁇ -electron system in the molecule.
• the number of double bonds forming the electron transfer path is 1 or more and 4 or less, the molecular resonance distance is short, the resonance route is limited, and proton transfer occurs efficiently and at low energy within the molecule. . As the molecular resonance distance becomes longer and there are multiple resonance routes, the proton transfer rate decreases and the singlet oxygen quenching ability decreases as the excitation energy increases. In the present invention, it is preferred that the number of double bonds forming the electron transfer path accompanying the intramolecular proton transfer is 2 or more and 4 or less. Sile,. In the present invention, the number of electron systems involved in the proton transfer reaction is
• Patent Document 3 discloses a benzotriazole-based compound as an ultraviolet absorber as a compound that functions as an image fading inhibitor by a mechanism based on intramolecular proton transfer. The resonance equation for the intramolecular proton transfer reaction of benzotriazole compounds is shown below. ,
• the number of double bonds forming the electron transfer path associated with intramolecular proton transfer is six, and the intramolecular resonance distance is long. Therefore, intramolecular resonance requires a larger excitation energy such as ultraviolet light than the compound having a short intramolecular resonance of the present invention.
• a compound with a long intramolecular resonance distance also has a slow intramolecular proton transfer reaction rate, and the singlet oxygen quenching mechanism due to the intramolecular proton transfer reaction and mechanism does not work.
• the energy excited by ultraviolet rays is converted into heat by proton transfer. It is only deactivated.
• Such compounds may be oxidized by heavy oxygen before quenching singlet oxygen.
• the proton transfer reaction is a reversible reaction that does not undergo an oxidation reaction reversibly.
• a compound deprived of energy from singlet oxygen undergoes proton transfer and thermally deactivates its energy due to the difference in stability between each other, returning it to its original state. It is considered 'back'. Therefore, image fading prevention using proton transfer mechanism The agent is considered to maintain its effect semi-permanently. .
• the anti-fading agent according to the present invention is a compound having a structure capable of intramolecular proton transfer as described above, and the structure capable of intramolecular proton transfer removes energy from oxygen to singlet by proton transfer. Has the ability to quench oxygen. From such a point of view, it is preferable that it is in a dissolved state in the recording medium, or is dissolved when water enters the recording medium so that energy can be captured from singlet oxygen.
• the image fading inhibitor is preferably a colorless or white compound.
• a compound with a large conjugation such as / 3 carotene has a double bond in its molecule that is easily oxidized by singlet oxygen with its low acid potential (sacrificial reagent ability)
• J3 carotene is described as having a singlet oxygen quenching rate of 1.0 X 1 OW d mSmol -1 s- 1 ).
• the singlet oxygen quenching mechanism is not due to intramolecular proton transfer, but is a chemical quenching mechanism in which the localized double bond of the self oxidatively degrades, and there are places that function as a chemical quenching mechanism. The fact that there is one, the compound itself is therefore very unstable.
• the white compound means that the compound does not have a molecular orbital system that absorbs the visible light region.
• the colorless compound means a compound whose compound molecule size is less than or equal to the wavelength of visible light in a liquid state or a dispersed state.
• Image fading inhibitor When the image fading inhibitor is permanently insoluble or alcohol insoluble, it cannot be directly prevented from being deteriorated by singlet oxygen because it is dispersed by a surfactant or the like and added to the ink receiving layer coating solution. In addition, there is a possibility that the proton transfer mechanism is hindered by the interaction with the surfactant and the singlet oxygen quenching ability is not sufficiently exhibited. Image fading inhibitor is water insoluble or alcohol insoluble Even so, it is possible to directly prevent deterioration of the coloring material due to singlet oxygen by overcoating the solution of the image fading inhibitor dissolved in the solvent after providing the ink receiving layer. In this case, the singlet oxygen quenching ability may be reduced, which increases the number of manufacturing processes, and is not very ambitious from the viewpoint of environmental impact.
• the anti-fading agent is water-soluble or alcohol-soluble, it can be added directly to the coating solution of the ink-receiving layer, so that deterioration of the coloring material due to singlet oxygen can be prevented directly.
• the image fading inhibitor is more preferably water-soluble or alcohol-soluble.
• Water-soluble or alcohol-soluble means a compound having a solubility of 0.1% by mass or more with respect to water or alcohol.
• the singlet oxygen quenching rate (k Q1 ) of the anti-fading agent measured by the competitive reaction method in ethanol is 3.0 X 1 O 8 dm 3 mo 1— — 1 or more, 9.0 X 10 It is preferably 10 dm 3 mo — 1 or less.
• An image fading preventing agent having such a singlet oxygen quenching rate can effectively prevent discoloration and fading of an image formed on a recording medium.
• 3. 0 X 1 O 8 dm 3 sufficient image fading preventing effect is less than mo 1-IS -1 becomes difficult to obtain, 9. 0 X 10 10 dm 3 mo 1 - a 1 .s- 1 If it exceeds, it becomes difficult to obtain sufficient stability of the compound.
• the singlet oxygen quenching rate (k Q dm 3 m0 1 s— represents the number of molecules of singlet oxygen that a solution of concentration lmo 1/1 quenches per second.
• the singlet oxygen quenching mechanism that has been actively studied so far is mainly singlet oxygen by oxidation reaction (electron extraction).
• a quenching mechanism in this regard until the oxidation reaction or electron transfer model as singlet oxygen erasing mechanism, for example, H arry H. Wa sse rma n s Ro bert W. fifth Mu Rray Author of SI NGLET oXYGEN (1979) Chapter Q uenchingof S inglet ⁇
• Some measurement methods in literature such as xygen Law and theory are published. Many of these methods perform measurements in non-aqueous solvents.
• the singlet oxygen quenching rate k Q measured in a non-aqueous solvent is becoming difficult to reflect the function in the actual recorded matter, particularly in ink jet recording using a dye as a coloring material. Therefore, it is important to carry out in an aqueous solution or an alcohol solution such as ethanol.
• the singlet oxygen quenching rate (k Q ) of the singlet oxygen quencher is a method described in page 22 of the 22nd Annual Meeting of the Oxidation Reaction (Ehime Univ., Mukai, Dai et al. '). Specifically, it was synthesized according to the method described by Inoue et al. In Te trahedron L et t., 41, 21 77-2181 (1985), etc.
• the singlet oxygen quenching mechanism includes a chemical quenching rate (k r ) in which a quenching compound reacts with singlet oxygen to quench it as an oxide, and singlet oxygen is converted into triplet oxygen without reacting.
• k r chemical quenching rate
• k q physical quenching rate
• singlet oxygen quenching rate (kg) usually includes both quenching rates. .
• the anti-fading agent of the present invention has a singlet oxygen quenching mechanism, from singlet oxygen to energy. Only a physical quenching mechanism that deprives Luge and quenches singlet oxygen by proton transfer is exhibited. This eliminates the trade-off relationship with the sustainability of the effect that the more highly effective compound is an unstable compound that is more susceptible to oxidization by itself, and exhibits high image fading prevention function stably over the long term. As a result, a recording medium capable of maintaining the image quality, an image fading preventing agent used therefor, and an image forming method have been completed.
• the chemical quenching rate (k r2 ) is dominant as the singlet oxygen quenching rate (k Q2 ) of the color material in order to prevent the color material contained in the ink from fading.
• Color materials are not a preferred form. This is because the chemical quenching rate ⁇ k r2 ) may be deviated from the purpose of the present invention because the colorant itself is deteriorated by an oxidation reaction, that is, accompanied by a change in molecular structure that causes discoloration. It is.
• the singlet oxygen quenching rate (k Q2 ) is as close as possible to the physical quenching rate (k q2 ). If the ratio of the chemical quenching rate (k r2 ) to the singlet oxygen quenching rate (k Q2 ) of the colorant is 10% or less, the image storability is improved, but it is greater than 10%. In this case, the contribution of chemical quenching is large, and the color material itself has a large oxidation reaction, which may cause a problem as the degree of image fading.
• the present invention relates to a recording medium containing an image fading inhibitor having a singlet oxygen quenching rate (k Q1 ) larger than the singlet oxygen quenching rate (k Q2 ) of the color material.
• the image fading prevention agent is preferentially acidified by singlet oxygen, so it is possible to prevent the color material from fading, and the singlet oxygen quenching rate of the color material (k Q2 )
• the chemical quenching rate (k r2 ) becomes dominant, the color material is oxidized regardless of the value of the singlet oxygen quenching rate (k Q1 ) of the anti-fading agent. May occur.
• any agent having a functional group that causes intramolecular proton transfer in the molecule may be used.
• an anthraquinone derivative examples include pentavalent phosphate compounds, unsaturated cyclic alkyl compounds, and unsaturated aliphatic compounds.
• pentavalent phosphate compounds and anthraquinone derivatives are preferred. Since the pentavalent phosphate compound and the anthraquinone derivative have a large singlet oxygen quenching rate (k Q1 ) —, the effect of the present invention is great.
• the pentavalent phosphate ester compound used as the image fading preventing agent of the present invention is preferably selected from compounds having the structure described in the following formula (1) or (2).
• 1 ⁇ to 1 3 are each independently a hydrogen atom, an aliphatic alkyl group, a Fang aromatic alkyl group or a (meth) Atari Roy Ruo alkoxyalkyl group.
• R 1 to R 3 are hydrogen atoms.
• One of the compounds of the hydrogen atom of the Ri ⁇ R 3, i.e. pentavalent phosphoric acid ester compound having one free OH is Shi preferred Rere. L,
• R 4 to R 7 are each independently a hydrogen atom, an aliphatic alkyl group, an aromatic alkyl group, or a (meth) ataryloxyalkyl group.
• 1 to 3 of R 4 to R 7 are hydrogen atoms.
• a compound in which one or two of R 4 to R 7 are hydrogen atoms is preferred.
• a compound in which one of R 4 and R 5 is a hydrogen atom and one of R 6 and R 7 is a hydrogen atom is preferable.
• an aliphatic alkyl group that can be suitably selected from the above formula (1) or formula (2), Includes an alkyl group having 1 to 24 carbon atoms such as a methyl group, an ethyl group, and a propyl group, and examples of the aromatic alkyl group include a phenyl group, a phenylmethyl group, a tolyl group, a naphthyl group, and a naphthylmethyl group.
• the (meth) ataryloxyalkyl group include an alkyl group having an acryloyloxy group or a methacryloyloxy group. These groups may be linear or branched.
• Specific examples of the pentavalent phosphate ester compound represented by the formula (1) include the following.
• N is 1 or 2.
• pentavalent phosphate compound represented by the formula (2) include the following.
• the anthraquinone derivative used as the image fading preventing agent of the present invention has a great effect of this effort.
• the anthraquinone derivative used as the image fading preventing agent of the present invention is preferably selected from compounds having the structures described in the following formulas (3) and (4).
• Formula (3) ' is a structural formula that has one structure that causes proton transfer in the molecule. It is.
• 1 ⁇ to 17 are preferably each independently a hydrogen atom, an aliphatic alkyl group, or an aromatic alkyl group. Since these substituents affect the basicity of the substituted ketone or the balance of the acidity of the hydroxyl group, they affect the proton transfer reaction rate, and hence the singlet oxygen quenching rate. Therefore, it is necessary to take a look at it and make an appropriate selection.
• an ester group and a hydroxyl group can be substituted independently at the positions of R 4 and R 5 , respectively. It is more preferable to be a compound that simultaneously produces two types of proton transfer reactions of type 1 and ester monohydroxyl type. ⁇
• Equation (4) is a structural formula having two structures that cause proton transfer in the molecule.
• R 1 to R 6 are preferably each independently a hydrogen atom, an aliphatic alkyl group, or an aromatic alkyl group. Since these substituents affect the basicity of the substituted ketone or the balance of hydroxyl acidity, they affect the rate of proton transfer reaction and thus the rate of singlet oxygen quenching. Therefore, it is necessary to select appropriately in view of that.
• the recording medium of the present invention has a base material 2 and an ink receiving layer 1 formed on the base material 2 as a color material receiving site.
• the ink receiving layer 1 contains the aforementioned image fading preventing agent of the present invention.
• Base material 2 includes chemical pulp such as LBKP and NBKP, wood pulp such as GP, P GW, RMP, TMP, mechanical pulp such as C TMP, CMP, and CGP, waste paper pulp such as DIP, polyethylene fiber, etc.
• """various additives that are usually used in papermaking, if necessary, Base paper produced by various devices such as a long net paper machine, a circular net paper machine, and a twin wire paper machine can be used.
• this base paper is a processed paper with a size press or anchor coat layer, such as starch or polybulol alcohol, or art paper, coated paper, cast coat paper, etc., with a coat layer on top of them. Coated paper is also included.
• the ink receiving layer 1 may be provided as it is on such paper, and the smoothness of the surface of the substrate 2 is improved in order to obtain good recording characteristics and glossiness for inkjet recording and paper.
• a calendar device such as a machine calendar, a TG calendar, a soft calendar, etc. may be used in the stage prior to the application of one ink receiving layer.
• the base material 2 may be one obtained by providing a resin layer on the above paper, and the resin layer may be a synthetic resin such as polyethylene, polypropylene, polyester ⁇ /, nylon, rayon, polyurethane, or a mixture thereof.
• a film material, or a sheet formed by molding the above synthetic resin into a fiber, can also be used.
• the ink receiving layer 1 formed on the substrate 2 contains the image fading inhibitor of the invention described above.
• One type of image fading inhibitor may be used, or two or more types may be used in combination.
• the content of the image fading inhibitor in the ink receiving layer 1 is preferably within a range of 0.1% by mass or more and 10.0% by mass or less with respect to the total solid content of the ink receiving layer 1. If it is less than 0.1% by mass, sufficient weather resistance may not be obtained. On the other hand, if it exceeds 10.0 mass%, there may be a problem in image recording characteristics such as a decrease in OD and a decrease in ink absorption in the halftone and secondary color portions.
• Items that can be considered as an effect on the image recording characteristics due to the addition of the anti-fading agent here are graininess, image density, and color saturation. For example, it is a blur and fine line blur. 'An even more preferable range of the content of the image fading inhibitor is 2.5% by mass or more and 6.0% by mass or less, and within this range, the balance of weather resistance and image recording characteristics is more excellent. Therefore, it is very satisfactory because the image recording characteristics are hardly affected by the addition of the image fading inhibitor while providing sufficient weather resistance.
• the image fading preventing agent contained in the ink-receiving layer 1 the content per unit area of the recording medium, 1. 0 0 X 1 0- 4 mo 1 Zm 2 or more, 1. OO mol Zm 2 below It is preferable to adjust so that.
• the content of the image fading inhibitor per unit area within this range, sufficient weather resistance can be obtained, and OD is lowered, and ink absorption is reduced in the halftone and secondary color areas. Excellent image recording characteristics can be obtained. More preferably, 5 X 1 0 - 4 mo 1 / m 2 or more, 1 X 1 0 - is 2 mo 1 / m 2 or less.
• the image fading preventing agent is present in a state where the image fading preventing agent can function so that energy can be captured from singlet oxygen in the recording medium, that is, in a state where energy can be taken from singlet oxygen. It is preferable.
• the image fading inhibitor is present as a solid or a crystal, it is present as a microcapsule containing the image fading inhibitor dissolved in an oily substance, and various other than these. Can exist in a state.
• energy may not be efficiently captured from singlet oxygen simply by including an image fading inhibitor in the recording medium.
• the image fading preventing agent in order for the image fading preventing agent to be in a fully functioning state, it is dissolved in the recording medium or dissolved by entering into the recording medium, and singlet ' Those capable of capturing energy from oxygen are preferred.
• the ink composition which is a coloring material
• the recording medium is filled with an ink liquid mainly composed of water, it is in a dissolved state, The energy can be efficiently captured from singlet oxygen.
• the ink receiving layer 1 usually contains a pigment and a binder in addition to the image fading inhibitor.
• the pigment used here is preferably composed mainly of alumina hydrate in terms of dye fixing property, transparency, printing density, color developability, and gloss / rawness, but the following pigments are used.
• inorganic pigments include light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica force, alumina, hydric magnesium hydroxide, etc. It is done.
• organic pigments include styrene particles, microcapsule particles, urea resin particles, and melamine resin particles. Select one of these, or use a combination of two or more if necessary. ,
• a fine particle pigment having an average particle diameter of 1 / m or less is preferably used as a main component, and particularly preferable are fine particles such as silica-based and aluminum oxide-based particles.
• Preferred as the silica-based fine particles are silica fine particles typified by colloidal silica available from the market.
• Particularly preferable examples of the silica-based fine particles include those disclosed in Japanese Patent Nos. 2 80 3 1 3 4 and 2 8 8 1 8 4 7.
• a preferable example of the acid-hyaluminum fine particles is alumina hydrate fine particles.
• the alumina hydrate is represented by the following general formula, for example.
• n represents any of 0, 1, 2 or 3
• m represents a value in the range of 0 to 10, preferably 0 to 5.
• MH 2 0 often represents a detachable aqueous phase that is not involved in the formation of the crystal lattice, so m can be an integer or non-integer value.
• Alumina hydrate is generally produced by hydrolysis of aluminum alkoxide or sodium aluminate (USP 4, 2 4 2, 2 71, 4, 2 0 2, 8 7 0), It can be produced by a known method such as a method of neutralizing by adding an aqueous solution of aluminum sulfate, aluminum chloride or the like to an aqueous solution of sodium aluminate (Japanese Patent Publication No. 5 7-4 4 7 0 5 '). '
• the alumina hydrate suitable for the present invention shows a boehmite structure or an amorphous state by analysis by X-ray diffraction method, and particularly, disclosed in JP-A-7-2 3 2 4 7 3 Alumina hydrates described in JP-A-8-1 3 2 731, JP-A-9 6 6 664, JP-A-9-7 6 6 28 and the like are preferred.
• the ink-receiving layer 1 is formed by drying again and is subjected to a casting process in many cases. It is preferable to use a plate-like alumina hydrate that has a low tendency to be oriented when the receptor layer 1 is formed and has good water absorption. That is, since the plate-like alumina hydrate has good moisture absorption, the re-wetting liquid (moisture) is easy to permeate, so that the ink receiving layer 1 is likely to swell and the alumina hydrate particles are easily rearranged. . Therefore, high gloss can be obtained in the casting process. In addition, since the rewetting liquid penetrates efficiently, the production efficiency in the casting process is also increased.
• the pigment content in the ink receiving layer 1 is 55.0 mass based on the total solid content of the ink receiving layer 1. / 0 or more, 94.0 mass. / Within the range of 0 or less is preferable.
• binders include polyvinyl alcohol, modified polyvinyl alcohol, starch or modified product thereof, gelatin or modified product thereof, casein or modified product thereof, gum arabic, canolepoxymethylsenololose, hydroxyethinore Cellulose derivatives such as senocellulose and hydroxypropylmethylcellulose; Conjugated copolymer latexes such as SBR latex, NBR latex and methyl methacrylate-butadiene copolymer; functional group-modified polymer latex; Conventionally known binders such as vinyl copolymer latex such as tylene monoacetate butyl copolymer; polyvinyl pyrrolidone, maleic anhydride or copolymer thereof, and acrylate ester copolymer can be used.
• polybulal alcohol as a binder
• a conventionally known binder in combination with polyvinyl alcohol.
• the amount of binder to be combined is 5 masses with respect to the pigment. It is preferable that the amount be 20% by mass or more.
• the ink receiving layer 1 It is very effective for forming the ink receiving layer 1 to contain one or more oxalic acid compounds as a crosslinking agent in the raw material for forming the ink receiving layer 1 formed as described above.
• boric acid compounds that can be used in this case, not only orthoboric acid (H 3 B 0 3 ) but also metaboric acid and hypoboric acid can be used, and salts thereof can also be used.
• the borate is preferably a water-soluble salt of boric acid, specifically, for example, a sodium salt of boric acid.
• Alkali metal salts such as strong Rium salt (K 2 B 4 0 7 ⁇ 5 H 2 0, KB 0 2 etc.), ammonium salt of boric acid ( ⁇ 4 ⁇ 4 0 9 ⁇ 3 ⁇ 2 0, ⁇ ⁇ 4 ⁇ 2 etc.), alkaline earth metal salts such as magnesium salt and calcium salt of boric acid, and the like.
• Orthofluoric acid or a salt thereof is preferably used from the viewpoints of the stability over time of the coating liquid and the effect of suppressing the occurrence of cracks.
• the ink receiving layer 1 may contain other additives as required.
• Other additives include dispersants, thickeners, pH modifiers, lubricants, fluidity modifiers, surfactants, antifoaming agents, release agents, fluorescent brighteners, ultraviolet absorbers, and antioxidants. An agent etc. can be mentioned.
• an image fading inhibitor solution obtained by dissolving the image fading inhibitor in an organic solvent or the like is used as a component other than the image fading inhibitor.
• the method of coating on the ink-receiving layer 1 formed in advance is simple. By doing so, it is possible to include a large amount of image fading inhibitor on the surface side of the ink receiving layer 1.
• the organic solvent that can be used to prepare the image fading inhibitor solution is not particularly limited.
• esters such as ethyl acetate and butyl acetate, and ketones such as methyl isobutyl ketone, methyl ethyl ketone, and aceton.
• Ethers such as jetyl ether and ethyl ether, and alcohols such as isopropanol, methanol and ethanol are preferred.
• the image fading inhibitor is water-soluble, water, preferably deionized water, can be used as a solvent.
• An image fading inhibitor concentration in the image fading inhibitor solution is preferably 0.5 to 30% by mass because coating is easy.
• the coating method of the image fading inhibitor is a non-contact coating method with respect to one surface of the ink receiving layer using a die coater, air knife coater, spray, etc.
• a contact-type coating method such as a roll coater, a bar coater, or a gravure coater can also be used.
• an image fading preventing agent may be added to the raw material coating solution for the ink receiving layer 1 and coated as a coating solution containing all components.
• the dry coating amount of the ink receiving layer 1 is preferably 30 g / m 2 ′ or more, and more preferably 60 g / m 2 or less. That's right. If less than 3 0 g / m 2, in particular, cyan, magenta, ink of three colors of yellow, other black ink, when used in flop links such as multiple light color ink is added, sufficient Ink absorption may not be obtained, that is, ink overflow may occur and bleeding may occur, or ink dye may spread to the substrate 2 and print density may decrease. On the other hand, if it exceeds 60 g Zm 2 , cracks may not be completely suppressed.
• the ink receiving layer 1 exhibiting sufficient ink absorption even in a high temperature and high humidity environment can be obtained, which is preferable, and the dry coating amount is preferably 60 g Zm 2.
• the dry coating amount is preferably 60 g Zm 2. The following is more preferable because uneven coating of the ink receiving layer 1 is further less likely to occur, and the ink receiving layer 1 having a stable thickness can be produced.
• the ink receiving layer 1 formed as described above preferably has the pore properties satisfying the following conditions in order to achieve the purpose and effect such as high ink absorbability and high fixability. .
• the pore volume of the ink-receiving layer 1, 0. Lcm 3 Z g or more, 1. O cm is preferably in the 3 / g within the range. In other words, if the pore volume is less than the above range, sufficient ink absorption performance cannot be obtained, resulting in an ink receiving layer 1 with poor ink absorbability. There is a risk of bleeding. On the other hand, when the above range is exceeded, the ink receiving layer 1 tends to be easily cracked or fallen.
• the BET specific surface area of the ink receiving layer 1 is preferably 2 O m 2 Z .g or more and 4 50 m 2 / g or less. If the above range is not satisfied, sufficient luster 1 "may not be obtained, and haze may increase.
• the image may appear to have a “white haze”. Further, this case is not preferred because it may cause a decrease in the adsorptivity of the dye in the ink. On the other hand, if the above range is exceeded, cracks are likely to occur in the ink receiving layer 1, which is not preferable.
• the pore volume and BET specific surface area values are obtained by the nitrogen adsorption / desorption method.
• a glossy surface can be formed on the surface of the ink receiving layer 1 by a casting method.
• the casting method is a method in which the ink receiving layer 1 in a wet state or in a plastic state is pressed against a heated mirror-like drum (cast drum) surface, and dried in the pressure-bonded state.
• the ink receiving layer 1 is copied onto the surface, and there are three representative methods: the direct method, the rewetting method (indirect method) and the coagulation method.
• any of these casting methods can be used.
• the rewetting casting method is particularly preferable. According to the above, it is preferable because the surface of the ink jet recording medium can be obtained.
• the image forming method of the present invention is a method of forming an image with a color material on the recording medium described above.
• the image forming method it is possible to prevent discoloration of the image formed on the recording medium and to maintain the image quality stably for a long period of time.
• it is suitable for an image forming method using an inkjet recording method.
• an ink composition that can be suitably used in the image forming method of the present invention will be described.
• the ink assembly as an ink used in the image forming method of the present invention contains a color material, and as a preferred form, a color material, water, a water-soluble organic solvent, Ink yarn composition containing
• the color material contained in the ink composition is not particularly limited, but it is preferable to use a water-soluble dye.
• a color index, an acid dye, a direct dye, a catalyst dye, a reactive dye examples of dyes are classified into dyes, sulfur dyes, and food dyes.
• azo, anthraquinone and anthrapyridone can be used.
• the content of the coloring material in the ink composition is preferably 0.1% by mass or more and 20% by mass or less, and 1% by mass or more and 5% by mass. / 0 or less is more preferable.
• the image fastness of the obtained image is significantly improved.
• the heavy oxygen quenching rate of the colorant is, 1 0 X 1 O 8 dm 3 mo 1- more, 3 0 X 1 0 10 dm 3 mo 1- -.. Is preferably 1 or less.
• High singlet oxygen quenching ability is achieved by substituting the molecular structure, the electronic state in the molecule, the quenching mechanism due to energy relaxation by proton transfer, and the oxidized site having an antioxidant function.
• the relationship between the colorant contained in the ink composition used for recording, the image fading inhibitor contained in the recording medium, and the singlet oxygen quenching rate will be described.
• the image fading inhibitor is given priority.
• the color fading prevention function of the color material is easily exhibited.
• the image fading inhibitor in the recording medium is evenly distributed, and in the case of inkjet recording, whether or not the color material in the ink composition is uniformly fixed in the ink receiving layer, etc. Therefore, it is considered that there are complicated factors that cannot be easily quantified.
• the singlet oxygen quenching rate of the plurality of image fading inhibitors satisfies the above formula. Further, when a plurality of color materials are driven into the recording medium, the one having the maximum singlet oxygen quenching speed of the plurality of color materials may be satisfied.
• water-soluble organic solvent a water-soluble high boiling point low-volatile organic solvent is preferably used.
• preferable water-soluble high-boiling and low-volatile organic solvents include polyhydric alcohols and polyhydric alcohol lower alkyl ethers, and more specifically, ethylene glycol, diethylene glycol / res, Alkylene glycols such as triethyleneglycol and propylene glycol; glycerin; polyalkylene glycols such as polyethylene glycol and polypropylene daricol; ethylene glycol.
• (Or ethyl) ether triethylene glycol monomethyl Or lower monoalkyl ethers of polyhydric alcohols such as ether; and polyhydric lower alkyl dialkyl ethers such as triethylene glycol dimethyl (or ethyl) ether.
• the alkylene group is preferably an alkylene group having 2 to 6 carbon atoms.
• These organic solvents can be used alone or in combination of two or more. The amount of these water-soluble, low-boiling, low-volatile organic solvents may be appropriately determined.
• the content in the ink composition is preferably 5 to 35% by mass. Les. The reason is that these solvents remaining in the printed material may absorb moisture in the air and cause bleeding of images during storage.
• amides such as dimethylformamide and .dimethylacetamide
• ketones or ketone alcohols such as acetone and diaceton alcohol
• tetrahydrofuran dioxane Ethers such as methyl alcohol, ethyl alcohol,
• the ink composition of the present invention can contain acetylene glycol as the water-soluble organic solvent.
• acetylene glycol commercially available products can be used.
• Surfynol 8 2, 10 4, 4 4 0, 4 6 5, TG, Orphine STG above trade name, manufacturer: A ir Propandand Chemicals Inc. (Seller: Nissin Chemical Industry Co., Ltd.) can be used.
• the amount of acetylene glycol added may be appropriately determined.
• the content in the ink thread and the composition is 0.3% by mass or more, 1.8% by mass. The following degree is preferable. '.
• a polyhydric alcohol lower alkyl etherol and acetylene glycol can be used in combination.
• the content of the water-soluble organic solvent is preferably in the range of 1% by mass to 40% by mass of the total ink composition, more preferably in the range of 3% by mass to 30% by mass.
• the colorant dye has good solubility in the ink composition, has a viscosity for stable ink composition discharge, and The water content in the
• a range of 30% by mass or more and 95% by mass or less is preferable.
• each ink composition used in the present invention includes, in addition to the above-mentioned components, a surfactant, a pH-adjusting antifungal agent, an antiseptic, an antifungal agent, an antioxidant, a reduced P method It may contain various additives such as stopper, evaporation promotion, clean H glaze, and water-soluble polymer.
• a moisture retaining solid such as urea, urea derivative, trimethylolpropane, etc. is also used as a component of the ink composition. Also good.
• the amount of humectant added, such as urea, urea derivatives, trimethylolpropane, etc. is preferably in the range of 1 to 30% by mass, more preferably in the range of 3% by mass to 20% by mass.
• the addition amount of the surfactant is preferably in the range of 0.01 to: L 0% by mass, and more preferably in the range of 0.05 to 3% by mass.
• Preferred physical properties of the ink composition are as follows in terms of viscosity, surface tension and pH (deviation is 25 ° C). Viscosity ranges from 1.5 cps to 10 cps Is preferable, and more preferably in the range of 1.8 cps or more and 5.0 cps or less.
• the surface tension is preferably 25 dyn / cm or more and 45 dy nZ cm or less.
• the pH is preferably 4 or more and 10 or less, more preferably 6 or more and 9 or less.
• a rain image forming element having a coloring material and a compound having a functional group that causes intramolecular proton transfer in the molecule is obtained. Then, an image formed by them is obtained.
• the singlet oxygen quenching rate of the coloring material and the image fading inhibitor was measured under the following conditions by the competitive exhaustion method described above.
• 1 X 10- 3 singlet was adjusted to M oxygen generator [3- (1, 4-E positive O cyclohexyl - 4-methyl-1, 4-dihydro-1 one-naphthyl) propionate (EP)]
• the reference substance [2 quenching speed was adjusted to IX 10- 3 M, 5-Jifuwe two Lou 3, 4- Ben Zofran (DPBFs)]
• a solution in which the measurement substance (coloring material or 'image fading inhibitor) coexists was prepared.
• coloring materials A and B having the following structures are used.
• the reaction reagent for the acylation uses an acid anhydride or ester, and the cyclization reaction is a dehydration reaction in the presence of alkali at high temperature and high pressure (120 ° C or higher, 160 ° C or lower, '2 atmospheres or higher). It was.
• Ink compositions A and B used in Examples and Comparative Examples were prepared as follows.
• Color material (Color material A or B)
• Ink-jet recording ink containing colorant A or B after mixing with 78 parts by mass of ion-exchanged water and pressure-filtering the resulting mixture through a membrane filter with a pore size of 0.2 microns.
• Compositions A and B were obtained, respectively.
• image fading preventing agents A, B, C, D and E were prepared as image fading preventing agents used in Examples and Comparative Examples.
• Image fading inhibitor A (Molecular weight: 299)
• Image fading inhibitor B (Molecular weight: 31 3)
• 5-valent phosphate ester compound (Johoku Chemical Co., Ltd., trade name: J ⁇ — 5 0 6) (with a structure that allows intramolecular migration of molecules, liquid at room temperature, easily soluble in water)
• Trivalent phosphate ester compound Triphenyl phosphate ester
• a substrate was prepared as follows. Freeness 450 ml l CS F (Canadian Standarad Freeness) hardwood B West kraft pulp (LBPK) 80 parts by weight, freeness 480 m 1 CSF softwood bleached kraft pulp (NB PK) In a pulp slurry consisting of 20 parts by mass, cationized starch (manufactured by Yamato Chemical Co., Ltd., trade name: Soldine CP-1 3D) 0.60 parts by mass, heavy calcium carbonate 10 Parts by weight, light calcium carbonate 15 parts by weight, alkyl ketene dimer (manufactured by Arakawa Chemical Industries, Ltd., trade name: Size Pine K903) 0.1 parts by weight, cationic polyacrylamide (manufactured by Arakawa Chemical Industries, Ltd.) Product name: POLYSTRON 6 1 9) 0.0 3 parts by mass and sulfuric acid band (manufactured by Showa Chemical Industry Co., Ltd.) 0.4.
• cationized starch manufactured by
• the coating liquid used for forming the undercoat layer is composed of kaolin (trade name: Ultrawhite 90, manufactured by Engelhard), Zinc oxide / aluminum hydroxide (mass ratio 6 5/1 0/2 5).
• an aqueous tetraborate solution (dissolved in pure water and adjusted to a solid content concentration of 5.0% by mass) ) was applied to a solid content of 0.5 g / m 2 , and the ink receiving layer was formed immediately after the coating solution was impregnated in the undercoat layer.
• the coating liquid and coating method used to form the ink receiving layer at that time are as follows.
• Sodium aluminate was added to a 4% by mass aqueous solution of aluminum chloride to adjust the pH to 4. Thereafter, the temperature was raised to 90 ° C while stirring, and stirring was continued for a while. Thereafter, re-poured sodium aluminate was added to adjust the pH to 10 and a aging reaction was carried out for 40 hours while maintaining the temperature. Thereafter, the temperature was returned to room temperature, and the pH was adjusted to 7 or more and 8 or less with acetic acid. 'The dispersion was desalted and then peptized with oxalic acid to obtain a colloidal sol. The colloidal sol of alumina hydrate was concentrated to obtain a solution having a solid content of 17% by mass.
• polyvinyl alcohol (trade name: PVA 1 17; manufactured by Kurarene soil) was dissolved in pure water to obtain a 9% by mass solution.
• the above-mentioned alumina hydrate co-hydral sol and polyvinyl alcohol solution were mixed and stirred so that the solid content of alumina hydrate and the solid content of polybutyl alcohol was 10: 1, thereby obtaining a dispersion.
• This was coated with a die coater at a rate of 30 m / min so that the dry coating amount was 35 g / m 2 . And then, 1 7 0. (: Was dried to form an ink receiving layer, and thus a recording medium 1 for ink jet was obtained.
• the average pore radius of the recording medium 1 at this time was 8.5 nm, and the pore volume was 0.65 ml Zg.
• An ink jet recording medium 9 was prepared in the same manner as the ink jet recording medium 1 except that the composition of the coating liquid for forming the ink receiving layer was changed.
• the preparation of a coating solution for forming the ink receiving layer is described below.
• Sodium aluminate was added to a 4 mass% aqueous solution of aluminum chloride to adjust the pH to 4. After that, the temperature was raised to 90 ° C while stirring, and stirring was continued for a while. Sodium hydroxide was added to adjust pH to 10 and the aging reaction was carried out for 40 hours while maintaining the temperature, and then returned to room temperature, and pH was adjusted to 7 to 8 with acetic acid.
• the colloidal sol was obtained by demineralization treatment with acetic acid and then peptized with acetic acid, and the colloidal sol of this alumina hydrate was concentrated to obtain a solution with a solid content of 17% by mass.
• polybulal alcohol (trade name: P VA 1 17, manufactured by Kuraray Co., Ltd.) was dissolved in pure water to obtain a 9% by mass solution.
• Polybula alcohol solution, alumina hydrate solids and polybulal The mixture was stirred and mixed so that the solid content of the mixture was 10: 1 by mass, and further the image fading inhibitor was adjusted to 4.4% by mass with respect to the total solid content of this dispersion of 100.
• a dispersion was obtained by adding C. This was coated with a die coater at a rate of 30 m / min so that the dry coating amount was 35 g Zm 2 and at 170 ° C.
• the ink-receiving layer was formed by drying, thus obtaining a recording medium 9 for ink jet recording, and the average pore radius of the recording medium 9 for ink-jet recording at this time was 8.6 11 ⁇ 1 from BET measurement.
• the pore volume was 0.67 ml / g, and the coating amount of the image fading inhibitor C added to the ink receiving layer of the recording medium 9 for ink jet recording was 1.00 X 1 0 1 2 mo 1 / m 2
• ink jet recording was performed with an ink jet printer (commercial product: iP86600, manufactured by Canon Inc.).
• the recording medium for the ink jet used was for the ink jet produced above. Recording medium 1-9, size 1. O cmX l. 0 cm area was printed. OD was controlled to 1.0 by controlling Duty, and used as a sample for fluorescent lamp test. This and can exhaled Inku weight of 19. 5 g / m 2, since the dye concentration is 0 wt% 6.
• the dye solids 1. 1 7 g / m 2 the discharged it become. 'Also, the combinations of the ink composition and the recording medium for the ink jet used are shown in Table 2.
• image fading preventing agent image forming element, recording medium, image forming method, and image of the present invention
• image forming technique such as a sublimation thermal transfer method, an electrophotographic method, and offset printing. It can be used widely.

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