CN101403850B - Multifunctional AA and NVP co-polymer argentic salt used for photothermography, and preparation method thereof - Google Patents
Multifunctional AA and NVP co-polymer argentic salt used for photothermography, and preparation method thereof Download PDFInfo
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- CN101403850B CN101403850B CN2008101531572A CN200810153157A CN101403850B CN 101403850 B CN101403850 B CN 101403850B CN 2008101531572 A CN2008101531572 A CN 2008101531572A CN 200810153157 A CN200810153157 A CN 200810153157A CN 101403850 B CN101403850 B CN 101403850B
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Abstract
The invention discloses a kind of AA for photosensitive heat display imaging and NVP copolymer silver salt and preparation method thereof. Structural unit shown in copolymer silver salt structural unit and B shown in A is constituted:
Preparation method includes following procedure: the copolymer of AA and NVP are prepared with liquid phase method; The pH value of reaction system is adjusted with sodium hydrate aqueous solution at room temperature; Silver nitrate is added in AA and NVP copolymer systems and the mixture of ethyl alcohol obtains AA and NVP copolymer silver salt. It is an advantage of the current invention that obtained AA and NVP copolymer silver salt, are used for photosensitive heat display imaging process, there is multifunctionality, preparation method process is simple, and product composition is easy to control, and reaction condition is mild.
Description
Technical field
The present invention relates to a kind of acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt and preparation method thereof that is used for photosensitive heat display imaging, belong to the technology of preparing of organic copolymer silver salt.
Background technology
Photosensitive heat display imaging material is the special photosensitive coating that is coated on the polyester film base, and numerous structures bases special, that function is single-minded such as main long chain organic acid silver, reductive agent, toner, polymer-matrix bonding agent and antifoggant by the ultra-fine silver halide particle of sensitization, non-sensitization, stabilizing agent, spectral sensitizer constitute.Whole photosensitive and the heat display imaging process is very complicated.From reaction mechanism that at present proposed, through having simplified, this photosensitive heat display imaging material is behind the process laser explosure, at first be on the ultra-fine silver halide particle of sensitization, to generate latent image centers, and then by thermal development processing processing, by the non-photosensitive silver of these latent image centers catalysis coexistences and the redox reaction between the weak reductant, generate nano level metallic silver particles, form visible black-and-white image on the final macroscopic view by these silver-colored particles.The used silver ion that wherein develops derives from the long chain organic acid derivant mountain Yu acid silver of non-sensitization; Bonding agent adopts Styrene-Butadiene or acryl resin, polyvinyl alcohol (PVA) carboxylic butyraldehyde etc., mainly is to provide a suitable reacting environment for the various components of adding in the image forming material; The transmission of silver ion and reduction process, the silver-colored particle grain size distribution that is generated and form and even final image tone, the toner that quality produces material impact are then selected phthalic acid, phthalazines, phthalimide etc.
Early stage photosensitive heat display imaging material is mainly used in fields such as microfilm, image fax, contactless printing.In recent years, along with the continuous development of modern digital medical diagnosis technology, photosensitive heat display imaging material has become the used topmost hard copy output medium of digitizing medical image.Nineteen ninety-five, in order to write down medical image easily, the subordinate's of Minnesota Mining and Manufacturing Company Imation company has released Dry View medical dry laser imaging system and the photosensitive heat display imaging film supporting with it, obtained and the same quality of image of conventional silver halide X-ray film, realized the dramatic change that medical diagnosis field no liquid is developed and processed, a large amount of dischargings of waste water and poisonous chemical process soup have not only been avoided, and it is efficient and convenient to have job operation, the process equipment cleaning, compact, the obvious advantage of the little grade that takes up room has fully satisfied the urgent requirement of modern society to efficient and environmental protection.
In order to further develop the photosensitive heat display imaging technology, make up a succinctly and efficiently technology platform, to adapt to some general character requirements of following numerous different field, for good basis is established in photosensitive heat display imaging material widespread use in a wider context, just need research and development to have multi-functional material component, reduce the complicacy of existing system as far as possible, reduce the value volume and range of product that adds compound wherein.On the formation and function of present photosensitive heat display imaging material, as the long-chain fatty acid silver in silver-colored source, be chain or ring-type organism for various reactants provide the size of the adhesive component of environment and reaction platform, the silver-colored particle that can generate reduction and the toner that pattern exerts an influence, there is general character to a certain degree in the three and gets in touch on structure and composition, exist the possibility that it is incorporated in a single structure.Therefore adopt molecule design method, from some basic organic structures unit, establish reaction conditions, the synthetic simplification compound that has three kinds of functions concurrently, fundamentally simplifying and improving existing photosensitive heat display imaging system, become the fundamental guiding ideology of the following multi-functional copolymer silver salt technology of preparing research and development of addressing, also constituted particular content of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt and preparation method thereof that is used for photosensitive heat display imaging, described copolymer silver salt is used for the photosensitive heat display imaging process, has multifunctionality, the its preparation method process is simple, product is formed control easily, reaction conditions gentleness.
The present invention is realized by following technical proposals, a kind of acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt that is used for photosensitive heat display imaging, it is characterized in that this copolymer silver salt is made of structural unit shown in structural unit shown in the A and the B:
Wherein the molecular weight of multipolymer is 30,000~90,000, and viscosity is 150~400mpas.
The above-mentioned multi-functional acrylic acid (AA) of photosensitive heat display imaging and the preparation method of N-vinyl pyrrolidone (NVP) copolymer silver salt of being used for is characterized in that comprising following process:
1. the mass ratio 10: 7~17 by oil phase and water is in 1: 2~15 adding deionized waters with acrylic acid (AA) and N-vinyl pyrrolidone (NVP) in molar ratio, in solution, add 0.1~5% initiator ammonium persulfate, potassium persulfate or the sodium peroxydisulfate account for two kinds of monomer masses again, add 20~50% chain terminating agent isopropyl alcohol or the lauryl mercaptan account for two kinds of monomer masses, under agitation be warming up to 50~80 ℃ of reactions 2~5 hours, obtain acrylic acid (AA) and N-vinyl pyrrolidone (NVP) multipolymer.
2. under 20~30 ℃ of temperature, adding concentration in acrylic acid that makes in step 1 (AA) and N-vinyl pyrrolidone (NVP) multipolymer is the 0.15g/mL sodium hydrate aqueous solution, and the pH value of conditioned reaction system is 7~9.
3. silver nitrate is mixed with ethanol 1: 1 in molar ratio~4, the mol ratio 1: 1 of pressing the acrylic acid sodium salt in the silver nitrate and the prepared polymkeric substance of step 2 in the mixed liquor adds silver nitrate and alcohol mixeding liquid in the prepared multipolymer of step 2; Then, under 20~30 ℃ of temperature, stirring reaction 1~2 hour, obtaining molecular weight is 30,000~90,000, viscosity is the acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt of 150~400mpas.
The mass ratio of preferred oil phase and water is 10: 9~14; Acrylic acid and N-vinyl pyrrolidone mol ratio are 1: 3~10; Initiating agent is an ammonium persulfate, and the ammonium persulfate consumption is 0.5~3% of two kinds of monomer masses; Chain terminating agent is an isopropyl alcohol, and the isopropyl alcohol consumption is 25~40% of two kinds of monomer masses.
The invention has the advantages that, be used for photosensitive heat display imaging acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt, not only can be used as the silver-colored source of developing material, but also have on nanoscale formed silver-colored particle grain size distribution and form are controlled, participated in the effect of regulation system viscosity.Its preparation method process is simple, and product is formed control easily, reaction conditions gentleness.
Description of drawings
The nano silver particles transmission electron microscope photo that Fig. 1 obtains through the glucose reduction for embodiment 1 prepared acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt.
The nano silver particles transmission electron microscope photo that Fig. 2 obtains through the gallicin reduction for embodiment 2 prepared acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt.
The nano silver particles transmission electron microscope photo that Fig. 3 obtains through the reduction of gallic acid n-propyl for embodiment 3 prepared acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt.
Embodiment
What below provide utilizes embodiments of the invention, describe technology of the present invention and characteristics in detail, yet, present embodiment is not to be used to limit the present invention, anyly be familiar with this operator, without departing from the spirit and scope of the present invention, can do various changes and retouching within the scope of the appended claims.
Embodiment 1
In the glass reactor that a 250mL band stirs, add reaction mass, it consists of: acrylic acid 1mL, N-vinyl pyrrolidone 10mL, deionized water 10mL, ammonium persulfate 0.06g, isopropyl alcohol 4mL.Starting and stir, is under the 300r/min at rotating speed, is heated to 80 ℃ with water-bath, reacts to obtain acrylic acid and N-vinylpyrrolidone copolymers after 3 hours.Naturally cool to 20~30 ℃, adding concentration is that the NaOH of 0.15g/mL is neutralized to pH7~8 with reaction system; The silver nitrate aqueous solution 50mL that gets concentration and be 2mol/L with join in the prepared multipolymer after the ethanol of 24mL mixes; 25 ℃ of following stirring reactions 1 hour, obtain molecular weight and be 60,000~65,000 acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt, recording this copolymer silver salt viscosity through rotary viscosimeter is 300mpas.
Get in the glass reactor of above-mentioned acrylic acid that makes (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt solution 10mL to 200mL, start behind the adding deionized water 80mL and stir, adding reductive agent glucose 2.50g under 80 ℃.The Nano silver grain that generates is shaped as the class sphere, and particle size is 10~30nm.
Embodiment 2
In the glass reactor that a 250mL band stirs, add reaction mass, it consists of: acrylic acid 1mL, N-vinyl pyrrolidone 5mL, deionized water 6mL, ammonium persulfate 0.06g, isopropyl alcohol 2mL.Starting and stir, is under the 250r/min at rotating speed, is heated to 70 ℃ with water-bath, reacts to obtain acrylic acid and N-vinylpyrrolidone copolymers in 4 hours.Naturally cool to 20~30 ℃, adding concentration is that the NaOH of 0.15g/mL is neutralized to pH7~8 with system; The silver nitrate aqueous solution 50mL that gets concentration and be 2mol/L with join in the prepared multipolymer after the ethanol of 12mL mixes; 25 ℃ of following stirring reactions 1.5 hours, obtain molecular weight and be 50,000~55,000 acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt, recording its viscosity is 280mpas.
Get in the glass reactor of above-mentioned acrylic acid that makes (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt solution 10mL to 200mL, start behind the adding 80mL deionized water and stir, adding reductive agent gallicin 3.10g under 40 ℃.The Nano silver grain that generates is shaped as the class sphere, and particle size is 20~40nm.
Embodiment 3
In the glass reactor that a 250mL band stirs, add reaction mass, it consists of: acrylic acid 1mL, N-vinyl pyrrolidone 15mL, deionized water 24mL, potassium persulfate 0.23g, isopropyl alcohol 6mL starts and stirs, at rotating speed is under the 200r/min, be heated to 60 ℃ with water-bath, reacted 5 hours, obtain acrylic acid and N-vinylpyrrolidone copolymers.Naturally cool to 20~30 ℃, adding concentration is that 0.15g/mL NaOH is neutralized to pH7~8 with reaction system; The silver nitrate aqueous solution 50mL that gets concentration and be 2mol/L joins in the prepared multipolymer with after the ethanol of 6mL mixes; 25 ℃ of following stirring reactions 2 hours, promptly obtain molecular weight and be 30,000~35,000 acrylic acid (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt, recording its viscosity is 220mpas.
Get in the glass reactor of above-mentioned acrylic acid that makes (AA) and N-vinyl pyrrolidone (NVP) copolymer silver salt solution 10mL to 200mL, start behind the adding deionized water 80mL and stir, at 25 ℃ of following adding reductive agent gallic acid n-propyl 2.50g.The Nano silver grain that generates is shaped as the class sphere, and particle size is 10~20nm.
Claims (3)
1. an acrylic acid and N-vinylpyrrolidone copolymer silver salt that is used for photosensitive heat display imaging is characterized in that this copolymer silver salt is made of structural unit shown in structural unit shown in the A and the B:
Wherein the molecular weight of copolymer silver salt is 30,000~90,000, and viscosity is 150~400mpas.
2. one kind prepares the described method that is used for the acrylic acid and the N-vinylpyrrolidone copolymer silver salt of photosensitive heat display imaging of claim 1, it is characterized in that comprising following process:
(1) be 1.15,1.04 or 0.69 to be 0.16,0.31 or 0.1 to add in the deionized water in molar ratio by the mass ratio of oil phase and water with acrylic acid and N-vinyl pyrrolidone, the initiating agent that in solution, adds the ammonium persulfate, potassium persulfate or the sodium peroxydisulfate that account for two kinds of monomer gross masses 0.1~5% again, and adding accounts for the isopropyl alcohol of two kinds of monomer gross masses 20~50% or the chain terminating agent of lauryl mercaptan, under agitation be warming up to 50~80 ℃ of reactions 2~5 hours, obtain acrylic acid and N-vinylpyrrolidone copolymer;
(2) under 20~30 ℃ of temperature, adding concentration in acrylic acid that makes in step (1) and the N-vinylpyrrolidone copolymer is 0.15g/mL NaOH, and the conditioned reaction system pH is 7~9;
(3) mol ratio 1: 1~4 of pressing silver nitrate and ethanol is mixed it, presses in the mixed liquor the acrylic acid mol ratio in the silver nitrate and the prepared polymkeric substance of step (2) 1: 1 silver nitrate and alcohol mixeding liquid are added in the prepared multipolymer of step (2); Then, under 20~30 ℃ of temperature, stirring reaction 1~2 hour, obtaining molecular weight is 30,000~90,000, the acrylic acid of viscosity 150~400mpas and N-vinylpyrrolidone copolymer silver salt.
3. by the described preparation method who is used for the acrylic acid and the N-vinylpyrrolidone copolymer silver salt of photosensitive heat display imaging of claim 2, it is characterized in that: initiating agent is an ammonium persulfate, and the ammonium persulfate consumption is 0.5~3% of two kinds of monomer total amounts; Chain terminating agent is an isopropyl alcohol, and the isopropyl alcohol consumption is 25~40% of two kinds of monomer total amounts.
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Citations (4)
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US5240809A (en) * | 1992-04-20 | 1993-08-31 | Minnesota Mining And Manufacturing Company | Imageable articles having dye selective interlayers |
CN1393737A (en) * | 2001-06-26 | 2003-01-29 | 柯尼卡株式会社 | Heat developing photo sensitive material |
CN1407395A (en) * | 2001-08-20 | 2003-04-02 | 柯尼卡株式会社 | Silver thermal photographic dry image materials, image recording method and forming method |
CN1474232A (en) * | 2002-07-30 | 2004-02-11 | 伊斯曼柯达公司 | Novel silver compound and composition, thermal developing material comtaining it and preparing method |
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Publication number | Priority date | Publication date | Assignee | Title |
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US5240809A (en) * | 1992-04-20 | 1993-08-31 | Minnesota Mining And Manufacturing Company | Imageable articles having dye selective interlayers |
CN1393737A (en) * | 2001-06-26 | 2003-01-29 | 柯尼卡株式会社 | Heat developing photo sensitive material |
CN1407395A (en) * | 2001-08-20 | 2003-04-02 | 柯尼卡株式会社 | Silver thermal photographic dry image materials, image recording method and forming method |
CN1474232A (en) * | 2002-07-30 | 2004-02-11 | 伊斯曼柯达公司 | Novel silver compound and composition, thermal developing material comtaining it and preparing method |
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JP特开2004-170997A 2004.06.17 |
JP特开2007-225937A 2007.09.06 |
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