Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
  • C08F2/10—Aqueous solvent
• • 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
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
• • 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
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
  • C08F226/04—Diallylamine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F6/00—Post-polymerisation treatments
  • C08F6/006—Removal of residual monomers by chemical reaction, e.g. scavenging
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F6/00—Post-polymerisation treatments
  • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
• • 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

Definitions

• the present invention relates to a method for producing a copolymer of diallyldialkylammonium salt and maleic acid, and more specifically, production of a copolymer of diallyldialkylammonium salt and maleic acid containing almost no residual monomer or residual peroxide ion. Regarding the method.
• the present invention also relates to a method for producing an ink jet recording medium using a copolymer of diallyldialkylammonium salt and maleic acid obtained by the above method.
• a copolymer of diallyldialkylammonium salt and maleic acid is obtained by using diallyldialkylammonium salt and maleic acid as monomers and copolymerizing them in an aqueous solution (see Patent Document 1).
• diallyldialkylammonium salt and maleic acid as monomers and copolymerizing them in an aqueous solution.
• Patent Document 2 there has been an interest in various uses such as papermaking aids (see Patent Document 2).
• Patent Document 1 a distillation distillation method
• Patent Document 2 an ion exchange membrane electrodialysis method
• the cationic monomer is a diallyldialkylammonium salt
• it is a non-volatile quaternary salt
• the object of the present invention is that the monomer and the polymerization initiator hardly remain, and as a result, the diallyldialkylammonium salt and maleic acid can stably exhibit excellent performance in various applications.
• Another object of the present invention is to provide a method for producing the copolymer.
• Another object of the present invention is a method for producing an ink jet recording medium having excellent light resistance even under extremely strong light intensity conditions, using a copolymer of diallyldialkylammonium salt obtained by the above method and maleic acid. Is to provide.
• the present inventors have found that a mixture comprising a diallyldialkylammonium salt and maleic acid in water or a polar solvent in the presence of a persulfate as a radical polymerization initiator.
• a copolymer of diallyldialkylammonium salt and maleic acid containing almost no residual monomer and residual polymerization initiator can be obtained and the diallyl obtained.
• the present invention (1) The following general formula (I) (Wherein R 1 and R 2 independently represent an alkyl group having 1 to 3 carbon atoms, and X ⁇ represents a counter ion) and the following formula (II)
• a monomer mixture containing maleic acid represented by the formula (1) is polymerized in water or a polar solvent in the presence of a persulfate as a radical polymerization initiator, and the radical polymerization initiator is decomposed after completion of the polymerization reaction.
• a method for producing a copolymer of a diallyldialkylammonium salt and maleic acid comprising producing a copolymer containing a maleic acid structural unit represented by: (2)
• the raw material monomer mixture comprises diallyldialkylammonium salt (I) and maleic acid (II), and the copolymer of the target product is diallyldialkylammonium salt structural unit (III) or (IV)
• the raw material monomer mixture comprises diallyldialkylammonium salt (I), maleic acid (II) and sulfur dioxide, and the copolymer of the target product is diallyldialkylammonium salt structural
• the molar ratio of the starting monomer diallyldialkylammonium salt (I) to maleic acid (II) is 1: (0.1-1), and the amount of raw material sulfur dioxide is The amount of persulfate is 3 mol% or more with respect to the total moles of all monomers, and the concentration of all the raw materials in the reaction solution is 45 to 70% with respect to the total moles.
• the polymerization reaction is carried out at a polymerization rate of 0 to 35 ° C.
• the method according to any one of (1) to (7) above, which is 20 ppm or less in terms of solids (9) A copolymer of diallyldialkylammonium salt and maleic acid is produced by the method according to any one of (1) to (8) above, and the obtained copolymer is directly or indirectly applied to a substrate.
• the present invention provides a method for producing an ink jet recording medium, characterized in that an ink jet recording medium is obtained by being present, and (10) an ink jet recording medium obtained by the method described in (9) above.
• the present invention it is possible to produce a copolymer of a diallyldialkylammonium salt and maleic acid, which hardly contains a monomer or a polymerization initiator and easily exhibits excellent performance in various applications.
• the monomer but also the polymerization initiator remains almost even when a polymerization reaction is carried out using a large amount of the polymerization initiator in order to reduce the residual monomer in the obtained copolymer.
• an ink jet recording medium excellent in light resistance of printing can be produced even under accelerated conditions with high light intensity.
• a monomer containing maleic acid represented by is polymerized in water or a polar solvent in the presence of a persulfate as a radical polymerization initiator, and the radical polymerization initiator is decomposed after the completion of the polymerization reaction.
• R 1 and R 2 each independently represents an alkyl group having 1 to 3 carbon atoms, and X ⁇ represents a counter ion
• V a structural unit represented by the following formula (V):
• the copolymer containing the maleic acid structural unit represented by these is manufactured.
• diallyldialkylammonium salt used as a raw material monomer is represented by the following general formula (I) It is represented by
• R 1 and R 2 independently represent an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
• X ⁇ represents a counter ion, and examples thereof include chlorine ion, bromine ion and iodine ion. Chlorine ions are preferred because of their availability and monomer stability.
• diallyldialkylammonium salt used in the present invention include diallyldialkylammonium chloride, diallyldialkylammonium bromide, and diallyldialkylammonium iodide.
• the raw material maleic acid used in the present invention is represented by the following formula (II) It is represented by
• the molar ratio of the starting diallyldialkylammonium salt (I) and maleic acid (II) is preferably 1: (0.1 to 1.0), and 1: (0.15 to 1.0). Is more preferable, and 1: (0.2 to 1.0) is more preferable. If the amount of maleic acid (II) is small, the properties of the amphoteric copolymer are difficult to be obtained, and even if the amount of maleic acid (II) is too large, the number of diallyldialkylammonium salt units contained in the copolymer is small.
• the amount of maleic acid (II) per mole of diallyldialkylammonium salt (I) is limited to 0.1 to 1.0 mole.
• a third monomer such as sulfur dioxide is included in addition to the monomer of general formula (I) and the monomer of formula (II) in order to change the properties of the resulting copolymer. Can be polymerized.
• the amount of the third monomer is preferably 0.1 to 30 mol%, more preferably 0.1 to 15 mol%, based on the total monomers of the raw material.
• 0.1 to 7 mol% is more preferable.
• a persulfate is used as a radical polymerization initiator (in this specification, sometimes referred to as a polymerization initiator or an initiator).
• examples of the persulfate include ammonium persulfate, sodium persulfate, and potassium persulfate.
• polymerization is carried out so that the residual monomer in the copolymer is 5 mol% or less, preferably 2 mol% or less, more preferably 1 mol% or less with respect to the monomer structural unit in the copolymer. It is preferably used when the amount of initiator used in the reaction is increased. If the initiator is too small, the polymerization conversion rate tends to be low, and if it is too large, it takes time to decompose the initiator.
• the amount of initiator is, for example, preferably 3 mol% or more, more preferably 4 to 60 mol%, still more preferably 5 to 50 mol%, more preferably 6 to 40 mol% is particularly preferable, and 7 to 30 mol% is most preferable.
• the initiator addition method is preferably divided addition in order to thoroughly reduce the residual monomer in the polymerization reaction solution, and is preferably added 3 times or more, more preferably 5 times or more. preferable. In the present invention, when the residual monomer in the polymerization reaction solution does not fall below the target value, it is preferable to add an initiator further to thoroughly reduce the residual monomer.
• water or a polar solvent is used as a solvent used in the polymerization reaction.
• a polar solvent methanol, ethanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), or the like can be used.
• DMSO dimethyl sulfoxide
• DMF dimethylformamide
• water is particularly preferable from the viewpoints of polymerization reactivity and safety.
• the copolymer solution is preferably diluted with a solvent such as water or a polar solvent, if necessary, before decomposing the initiator. It is necessary to appropriately adjust the amount of the solvent for dilution depending on the copolymer to be produced.
• the initiator decomposition reaction is preferably carried out at a copolymer concentration of 5 to 40% by mass. At this time, if the copolymer concentration is too thin, it is necessary to carry out a vacuum concentration operation as a post-treatment, which is troublesome. On the other hand, if the copolymer concentration is too high, an excessive polymerization reaction may react with the initiator decomposition reaction, the molecular weight may change, or gelation may occur.
• the decomposition of the initiator after completion of the polymerization reaction is preferably performed by heat treatment at 65 to 80 ° C.
• the temperature is lower than 65 ° C, the initiator tends to take longer to decompose.
• the temperature exceeds 80 ° C, the molecular weight may change, and further, gelation may occur and it may be difficult to obtain a water-soluble copolymer.
• the heat treatment for decomposing the initiator can be performed under normal pressure.
• the amount of initiator activity after decomposing the initiator is preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 30 ppm or less, and particularly preferably 20 ppm or less in terms of solids.
• diallyldialkylammonium salt (I) of the monomer used and maleic acid (II) diallyldialkylammonium salt (I) of the monomer used and maleic acid (
• the molar ratio with II) is preferably 1: (0.1 to 1), and the amount of persulfate used is preferably 3 mol% or more based on the total mol of all monomers.
• the concentration of all the monomers for the polymerization reaction in the reaction solution is preferably 20 to 70% by mass, more preferably 23 to 65% by mass, and further preferably 25 to 60% by mass.
• the temperature during the polymerization reaction is preferably 30 to 62 ° C, more preferably 35 to 61 ° C, and further preferably 40 to 60 ° C.
• the concentration of the total polymer in the reaction solution for the initiator decomposition reaction after the polymerization reaction is preferably 5% by mass or more and less than 20% by mass, more preferably 10 to 18% by mass, and still more preferably 13 to 17% by mass. It is. At this time, it is preferable to perform the initiator decomposition reaction by diluting with water or a polar solvent as necessary.
• the molar ratio of the diallyldialkylammonium salt (I) of the monomer used to maleic acid is preferably 1: (0.1-1), and the amount of sulfur dioxide used is The amount of persulfate used is preferably 0.1 to 30% by mole based on the total moles of monomers, and the amount of persulfate used is preferably 3% by mole or more based on the total moles of all monomers.
• the concentration of all monomers for the polymerization reaction in the reaction solution is preferably 45 to 70% by mass, more preferably 47 to 68% by mass, and even more preferably 48 to 65% by mass.
• the temperature during the polymerization reaction is preferably from 0 to 35 ° C, more preferably from 5 to 30 ° C, and even more preferably from 10 to 25 ° C.
• the concentration of the polymer in the reaction solution for the initiator decomposition reaction after the polymerization reaction is preferably 5 to 40% by mass, more preferably 15 to 35% by mass, and further preferably 20 to 30% by mass. At this time, it is preferable to perform the initiator decomposition reaction by diluting with water or a polar solvent as necessary.
• this method includes the following embodiments (1) to (5).
• a copolymer of diallyldialkylammonium salt and maleic acid is made into an aqueous solution having a concentration of 0.03 to 5 W / V%, and if necessary, mixed with a commonly used binder such as oxidized starch, polyvinyl alcohol, etc.
• a binder containing a pigment having a high ink absorption capability (for example, synthetic silica, synthetic alumina, calcium carbonate, etc.) is applied to the base paper, and an air naphtho coater or spray is applied to the surface of the formed binder coat layer.
• a copolymer of diallyldialkylammonium salt and maleic acid is applied by, for example.
• a coating liquid obtained by adding a copolymer of diallyldialkylammonium salt and maleic acid to a pigment and a binder is directly applied to paper as a base material.
• synthetic pulp or synthetic fiber may be used together with the raw material pulp.
• whiteness pigments such as titanium oxide, calcium carbide, and zeolite can be internally added together with the copolymer of the present invention to improve the whiteness of the paper.
• a copolymer of diallyldialkylammonium salt and maleic acid can be used in combination with other coating agents.
• cation-modified starch, oxidized starch, polyvinyl alcohol, polyacrylamide for surface coating, etc., or a mixed solution with a surface sizing agent can be applied.
• the coating pigment include synthetic amorphous silica, clay, talc, diatomaceous earth, calcium carbonate, barium sulfate, titanium oxide, zinc oxide, satin white, and aluminum silicate.
• Other additives such as surface sizing agents, anti-slip agents, antiseptics, antifoaming agents, viscosity modifiers, and dyes may be used in combination. *
• the coating amount of the copolymer of diallyldialkylammonium salt and maleic acid is usually 0.05 to 10 g / m 2 , preferably 0.2 to 5 g / m 2 .
• Inkjet recording can be performed by attaching droplets of aqueous ink containing a dye to an inkjet recording medium obtained by allowing a copolymer of diallyldialkylammonium salt and maleic acid to be present in the inkjet recording medium.
• a water-based ink any water-based ink that is usually used for ink jet recording including a dye such as a direct dye, an acid dye, or a reactive dye can be used.
• Ink jet recording can be performed by generating fine droplets of water-based ink using a commonly used apparatus, etc., and making it fly and adhere to the recording medium.
• the ink jet recording method of the present invention can be widely applied to facsimiles, printers, computer terminals and the like.
• Example 1 Example of production of 1: 1 binary copolymer of diallyldimethylammonium chloride and maleic acid by the method of the present invention
• a 300 mL four-necked separable flask equipped with a stirrer, a condenser and a thermometer Then, 61.7 g (0.3 mol) of 65 mass% diallyldimethylammonium chloride aqueous solution, 34.8 g (0.3 mol) maleic acid, and 153.2 g of water were dissolved, and the internal temperature was raised to 50 ° C. .
• ammonium persulfate after the decomposition treatment was simply measured with a semi-quantitative ion test paper (Quantofix (registered trademark) Peroxid, MACHEREY-NAGEL) as residual peroxide ions, and was confirmed to be 15 ppm in terms of solids.
• Comparative Example 1 Example of production of a 1: 1 copolymer of diallyldimethylammonium chloride and maleic acid without any decomposition of the initiator Examples except for not performing the decomposition of the initiator after completion of the polymerization
• a 2: 1 copolymer of diallyldimethylammonium chloride and sulfur dioxide was produced.
• the residual peroxide ions were simply measured by the semi-quantitative ion test method and confirmed to be 150 ppm in terms of solids.
• Example 2 Example of production of 20: 9: 1 terpolymer of diallyldimethylammonium chloride, maleic acid and sulfur dioxide by the method of the present invention
• Four 300 mL units equipped with stirrer, condenser and thermometer In a mouth-separable flask, 298.5 g (1.2 mol) of 65% by weight diallyldimethylammonium chloride aqueous solution, 63.3 g (0.54 mol) maleic acid, 3.8 g (0.06 mol) sulfur dioxide, water
• 41.1 g (0.18 mol) of ammonium persulfate was added in 9 portions, and polymerization was carried out at 18 ° C.
• Example 3 Preparation of inkjet recording paper and light resistance test Synthetic amorphous silica (trade name: Fine Seal X-37B, manufactured by Tokuyama Corporation) as an inorganic pigment, 10.8 parts by weight, polyvinyl alcohol as a binder (Product name: PVA-235, manufactured by Kuraray Co., Ltd.) 2.9 parts by weight, 1.2 parts by weight of the copolymer obtained in Examples 1 and 2 or Comparative Examples 1 and 2 as a fixing agent (in terms of solid) Then, 0.1 part by weight of boric acid as a hardener was uniformly mixed to prepare an ink receiving layer coating solution having a solid content concentration of 15% by mass. The prepared coating liquid was applied onto marshmallow paper (trade name: OK Marshmallow CoC, manufactured by Oji Paper Co., Ltd.) and dried to prepare an ink jet recording paper.
• marshmallow paper trade name: OK Marshmallow CoC, manufactured by Oji Paper Co., Ltd.
• an ink jet recording medium obtained by producing a copolymer by the method of the present invention and coating the obtained copolymer on paper as a base material by the method of the present invention has a light intensity. It was revealed that the light resistance of printing (magenta, yellow) was improved under strong acceleration conditions. In addition, when the light resistance test was conducted using a carbon arc fade meter under a low light intensity condition, no discoloration was observed even when any of the polymers of Examples 1 and 2 and Comparative Examples 1 and 2 was used. It was.
• a monomer or a polymerization initiator activity hardly remains, and as a result, a copolymer of a diallyldialkylammonium salt and maleic acid that easily exhibits excellent performance in various applications can be produced.
• the polymerization initiator not only the monomer but also the polymerization initiator hardly remains even when a polymerization reaction is performed using a large amount of the polymerization initiator in order to reduce the residual monomer in the obtained copolymer.
• a copolymer of diallyldialkylammonium salt and maleic acid such as a binary copolymer of diallyldialkylammonium salt and maleic acid, a terpolymer of diallyldialkylammonium salt, maleic acid and sulfur dioxide, etc.
• a copolymer of diallyldialkylammonium salt and maleic acid such as a binary copolymer of diallyldialkylammonium salt and maleic acid, a terpolymer of diallyldialkylammonium salt, maleic acid and sulfur dioxide, etc.
• the obtained copolymer hardly retains a monomer and a polymerization initiator, it is used for applications such as an aggregating agent, a deodorizing agent, and a papermaking aid, and particularly for producing an ink jet recording medium excellent in light resistance of printing. Preferably used.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
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• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
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• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Polymerisation Methods In General (AREA)
• Polymerization Catalysts (AREA)

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• 2009
  • 2009-07-10 JP JP2009163820A patent/JP5464409B2/ja active Active
• 2010
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  • 2010-02-23 EP EP20100755573 patent/EP2412736B1/en active Active
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