WO2000074945A1 - Composition de resine destinee a une feuille d'enregistrement par jet d'encre et feuille realisee a l'aide de cette composition - Google Patents

Composition de resine destinee a une feuille d'enregistrement par jet d'encre et feuille realisee a l'aide de cette composition Download PDF

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Publication number
WO2000074945A1
WO2000074945A1 PCT/JP2000/003611 JP0003611W WO0074945A1 WO 2000074945 A1 WO2000074945 A1 WO 2000074945A1 JP 0003611 W JP0003611 W JP 0003611W WO 0074945 A1 WO0074945 A1 WO 0074945A1
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WIPO (PCT)
Prior art keywords
monomer
weight
group
resin composition
recording sheet
Prior art date
Application number
PCT/JP2000/003611
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English (en)
Japanese (ja)
Inventor
Katsuhiko Sumita
Kazuya Kataoka
Kenichi Kawai
Masaya Omura
Aika Iseki
Original Assignee
Daicel Chemical Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP11158814A external-priority patent/JP2000343811A/ja
Priority claimed from JP30578199A external-priority patent/JP2001121814A/ja
Priority claimed from JP30594399A external-priority patent/JP2001123075A/ja
Priority claimed from JP33051099A external-priority patent/JP2001146072A/ja
Priority claimed from JP33687699A external-priority patent/JP2001150804A/ja
Priority claimed from JP36001699A external-priority patent/JP2001171227A/ja
Priority claimed from JP2000028639A external-priority patent/JP2001213046A/ja
Priority claimed from JP2000033986A external-priority patent/JP2001219640A/ja
Application filed by Daicel Chemical Industries, Ltd. filed Critical Daicel Chemical Industries, Ltd.
Priority to EP00935535A priority Critical patent/EP1114734A1/fr
Publication of WO2000074945A1 publication Critical patent/WO2000074945A1/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
    • 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
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate layers
    • 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
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • 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
    • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
    • 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
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • B41M5/5272—Polyesters; Polycarbonates
    • 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
    • B41M5/5281—Polyurethanes or polyureas
    • 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
    • B41M5/529—Macromolecular coatings characterised by the use of fluorine- or silicon-containing organic compounds

Definitions

  • a resin composition used in an image receiving layer of an ink jet recording sheet having excellent ink absorbency, water resistance, and clearness of a recorded image, and an image receiving layer formed using the resin composition The present invention relates to an ink jet recording sheet having a layer.
  • the first aspect of the present invention is an ink jet recording comprising a crosslinkable group-containing cationic acrylic copolymer, a saponified vinyl acetate copolymer having a degree of polymerization of 200 to 100, and a modifier.
  • the sheet resin composition the recording sheet using it has high print quality, and even in an ink jet printing machine with a high printing speed, there is no beading and the ink absorbency such as sharpness and image uniformity, as well as water resistance. Its properties are highly improved, and it has the characteristic that water resistance and ink absorption, which are contradictory properties, can be compatible.
  • the second aspect of the present invention is, in particular, a crosslinkable group-containing cationic acrylic copolymer, a saponified vinyl acetate copolymer, an aqueous polyurethane resin, a polyurethane graft polymer mixture, and a polyester graft polymer.
  • a resin composition for an ink jet recording sheet comprising a mixture
  • a recording sheet using the same has a high clarity, a high degree of print image quality, and a high degree of improvement in water resistance in addition to ink absorption. It has the characteristic that both the water resistance and the ink absorptivity, which are contradictory properties, are compatible.
  • a second aspect of the present invention is a resin composition for an ink jet recording sheet comprising a crosslinkable group-containing cationic acrylic copolymer, a saponified vinyl acetate copolymer, an aqueous polyurethane resin composition, and a block isocyanate compound.
  • the recording sheet using it has the characteristic that the water resistance can be improved to a high degree while maintaining the ink absorption and the print quality.
  • the fourth aspect of the present invention is to copolymerize a monomer containing a polyalkylene oxide group, a monomer containing a hydrophilic group, a monomer containing a crosslinkable group, and a monomer containing a cationic monomer.
  • the ink-jet recording sheet resin composition comprising a cationic acrylic copolymer, a saponified vinyl acetate copolymer, and a modifier, the recording sheet using which is excellent in uniformity and bleeding Even in an environment where print quality is obtained and high resolution and high speed are required, water resistance, ink absorption and print quality are highly improved, and contradictory while improving print quality at the same level as photographic quality It has the characteristic of achieving both water resistance and ink absorption, which are characteristics.
  • the V of the present invention is obtained by copolymerizing a (meth) acrylate monomer containing a polyalkylene oxide group, a monomer containing a hydrophilic group, a monomer containing a crosslinkable group, and a cationic monomer.
  • the present invention relates to a resin composition for an ink jet recording sheet comprising a cationic (meth) acrylic copolymer, a saponified vinyl acetate copolymer, and a modifier. It has an excellent image-receiving layer that does not cause image defects such as high gloss and beading.
  • the VI of the present invention is particularly directed to a hydrolyzable compound obtained by copolymerizing a polymerizable unsaturated monomer having a hydrolyzable silyl group and a monomer containing a (meth) acrylate-based polymerizable unsaturated monomer.
  • a composition (P) comprising a silyl group-containing (meth) acrylate copolymer and inorganic compound-based fine particles, despite the use of a composition containing inorganic compound-based fine particles It has an image receiving layer excellent in glossiness and the like.
  • the invention W of the present invention comprises, in particular, a resin composition comprising a cellulose derivative and a good solvent for the cellulose derivative, an organic acid soluble in a good solvent or a poor solvent for the cellulose derivative, and optionally a poor solvent for the cellulose derivative.
  • a recording sheet using the same has excellent blocking resistance and forms an image receiving layer capable of improving the surface gloss of the image receiving layer, the sharpness of a recorded image, and the color reproducibility.
  • Ink-jet recording methods are inexpensive, easy to convert to full color, have low noise, and are excellent in print quality. First, it is widely used. Water-based inks are mainly used for ink-jet recording in terms of safety and recordability, and recording is performed by flying ink droplets from thin nozzles toward a recording sheet. For this reason, the recording sheet is required to quickly absorb the ink. In other words, on a recording sheet with low ink absorption, the ink remains on the surface of the recording sheet for a long time even after the recording is completed. The parts may be dirty. Also, in a high-density image area, a large amount of supplied ink is mixed and flows out without being absorbed, resulting in an unclear image.
  • JP-A-57-36692 discloses an ink jet recording sheet in which a basic latex polymer is applied in combination with a water-soluble polymer or a pigment in order to improve water resistance and resolution.
  • the technology relating to the network is disclosed.
  • Japanese Patent Application Laid-Open No. 63-115780 discloses an ink jet recording sheet in which a polymer containing a quaternary ammonium salt is applied to a recording sheet base material, and a synthetic silica is used in combination. It also describes that polyvinyl alcohol or the like is used in combination as a binder.
  • Japanese Patent Application Laid-Open No. 7-61113 discloses that an image receiving layer of ink is formed of polyvinyl acetate. There is disclosed an ink jet recording medium comprising a polyester resin and a cationic compound. Furthermore, Japanese Patent Application Laid-Open No. Hei 6-222711 discloses an ink jet recording sheet in which an image receiving layer of ink is composed of a pigment such as finely divided silica and an amphoteric ion latex.
  • Japanese Patent Application Laid-Open No. H11-174484 discloses a coating layer containing a pigment and a copolymer of a fatty acid vinyl ester such as vinyl acetate and a cationic monomer, and a pigment.
  • An ink jet recording sheet formed in accordance with the present invention is disclosed, wherein the cationic copolymer may be a copolymer with a nonionic monomer or a graft copolymer with polyvinyl alcohol. It is disclosed that a binder may be included.
  • Japanese Patent Application Laid-Open No. 62-83178 proposes an ink jet recording sheet provided with a coating layer containing finely powdered caic acid and a cationic polymer emulsion, and has a glass transition temperature of 0 °. It also describes that it is preferable to use a self-crosslinkable acrylemulsion of C or less as an adhesive.
  • JP-A-57-14091 and JP-A-61-19389 each disclose an ink jet recording sheet comprising co-idal silica and a water-soluble resin.
  • a water-soluble polymer is used for the binder.
  • JP-A-2-276670 and JP-A-3-281385 disclose an ink jet recording sheet formed from pseudo-boehmite fine particles. Although this recording sheet shows high ink absorption and water resistance, the ink receiving layer does not show sufficient gloss.
  • Japanese Patent Application Laid-Open Nos. 59-174,381 and 60-224,578 disclose starch, water-soluble cellulose derivatives, polyvinyl alcohol, etc. on a substrate. It has been proposed to use a water-philic polymer as an ink-receiving layer.However, even if the ink-absorbing property is satisfied, water resistance is poor, and the ink-receiving layer dissolves in water and the surface becomes sticky. When sheets are stacked, blocking occurs or there is a practical problem.
  • 3-72464 proposes a method comprising a combination of an ink-permeable surface layer and an ink-absorbing underlayer, wherein the ink is absorbed by the underlayer and blocking resistance is improved by the surface layer.
  • the ink passes through the surface layer and is absorbed by the underlayer, the ink has a deep penetrating effect on the recording sheet, so that the color density of the recorded portion is difficult to come out.
  • There are also problems such as delamination and low water resistance of the underlayer.
  • a porous layer is provided as an ink absorbing layer and ink is absorbed by a capillary phenomenon, as disclosed in Japanese Patent Application Laid-Open Nos.
  • the publication proposes a recording sheet in which fine particles such as silica are aggregated, and a porous layer having pores formed by voids between the particles is provided on a base material layer.
  • These inks have improved ink absorbency, but have the problem that the surface gloss is low due to light scattering of the particles and the ink absorption capacity is not sufficient.
  • Japanese Patent Application Laid-Open No. Sho 61-86062 proposes a recording sheet in which a porous plastic thin film layer is laminated on an ink absorbing layer, but the porous plastic thin film is made of a hydrophobic plastic such as polyethylene or polypropylene.
  • Ink jet recording in which water-based ink is mainly used, has insufficient ink permeability due to the formation, and holes are crushed or deformed because a porous plastic thin film is laminated by a thermocompression bonding method.
  • various proposals have been made regarding the ink image receiving layer of the ink jet recording sheet, but the ink adsorbability, water resistance, and glossiness of the ink jet recording sheet have been improved, but the degree of improvement is still small. However, the quality of printability and glossiness is still insufficient.
  • these recording sheets cannot improve ink fixability and water resistance to a high level.
  • it is difficult to thermally transfer a recorded image to an object to be transferred.
  • the washing resistance and durability are poor.
  • Japanese Patent Application Laid-Open No. 63-07784 describes that an ink absorption layer containing organic polymer fine particles that dissolve or swell in a solvent in an ink (particularly an oil-based ink) is formed on the surface of a support.
  • the disclosed ink jet recording sheet is disclosed.
  • Japanese Patent Application Laid-Open No. 7-251133 discloses that a spherical fine particle polymer having an average particle diameter of 5 to 15 nm is coated on at least one surface of a support formed of a polyolefin resin-coated paper or a polyester film, on a dry weight basis.
  • Ink jet recording sheets having an ink receiving layer formed at a ratio of 5 to 30 g / m 2 and having a thickness smaller than the average particle diameter of the spherical fine particle polymer are disclosed.
  • Japanese Unexamined Patent Publication No. Hei 8-322410 discloses a porous structure comprising a hot-melt resin (ethylene-vinyl acetate resin, polyester resin, rubber resin, etc.) on one side of a substrate.
  • An ink jet recording sheet having an ink receiving layer formed thereon is disclosed.
  • Japanese Unexamined Patent Publication No. Hei 8 (1995) -024 725 discloses that a hot melt resin (a water-soluble hot melt resin such as a saturated polyester resin in addition to a polyamide or polyester resin) and a hydrophilic material are provided on one surface of a base material.
  • An ink jet recording sheet is disclosed in which an ink receiving layer containing a hydrophilic resin (such as polyacrylamide, polyvinyl alcohol, and polyvinylpyrrolidone) is formed. This recording sheet can be bonded to a film or the like by heating.
  • the purpose of II is to provide a resin composition for an ink jet recording sheet that can highly improve ink absorption and water resistance.
  • the fourth object of the present invention is to improve the print quality, achieve both water resistance and ink absorbency, and prevent poor image quality such as beading even in a printing machine with a higher printing speed. Provide an ink jet recording sheet that does not generate.
  • a fifth object of the present invention is to obtain excellent printing characteristics, water resistance, and high glossiness, and to prevent traces of knurled by the printer from adhering to the recording paper when the printer discharges the recording paper.
  • a photographic ink jet recording sheet suitable for an ink jet recording system which does not impair the appearance of a printed image and enables high-quality printing with photographic quality even in high-speed ink jet printing.
  • a sixth object of the present invention is to provide an ink jet recording sheet having excellent gloss and excellent ink absorbency and water resistance.
  • the object of the seventh aspect of the present invention is to provide an ink having excellent ink absorption and blocking resistance, and Provide a recording resin composition for forming an image receiving layer capable of improving surface gloss of a layer, sharpness of a recorded image, water resistance, weather resistance and color reproducibility, and a recording sheet on which an image receiving layer made of the same is formed. I do.
  • the purpose of the coral of the present invention is to provide a heat transfer sheet useful for a heat transfer sheet excellent in ink absorbency, ink fixability, printability, water resistance of a recorded image, crack resistance, durability and washing resistance.
  • the present invention provides a resin composition for heat transfer and a thermal transfer sheet. Disclosure of the invention
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, have combined a saponified product of a crosslinkable group-containing cationic acryl copolymer and a vinyl acetate copolymer having a specific polymerization degree and a modifier. Or further, when combined with an aqueous polyurethane resin, a mixture of a polyurethane-based graft polymer and a mixture of a polyester-based graft polymer, or an aqueous-based polyurethane resin composition and a block isocyanate compound, water resistance, ink absorption and The present inventors have found that printing quality can be remarkably improved, and that a recording paper with excellent image quality can be obtained even in a high-speed printing machine. Thus, the present invention has completed the present invention.
  • the present inventors have proposed a cationic acrylic obtained by copolymerizing a monomer having an alkylene oxide group, a monomer having a hydrophilic group, a monomer having a crosslinkable group, and a cationic monomer.
  • copolymers (A-IV and AV) and saponified vinyl acetate copolymers (B), especially from saponified vinyl acetate copolymers with a specified degree of polymerization, and modifying agents (R) The resin composition of the present invention can remarkably improve water resistance, ink absorption and printing quality even in a high-resolution and high-speed printing machine, and can solve various problems such as adhesion of gizarol traces and high glossiness. The knowledge was obtained, and the IV and V of the present invention were completed.
  • the present inventors have found that, by constituting the image receiving layer with a specific copolymer and fine particles of an inorganic compound, it is possible to obtain excellent gloss and to obtain excellent ink absorption and water resistance.
  • a recording resin composition containing a cellulose derivative, a good solvent for the cellulose derivative, an organic acid soluble in the good solvent or the poor solvent for the cellulose derivative, and optionally a poor solvent for the cellulose derivative in a specific ratio. It has been found that the use thereof can greatly improve the surface gloss of the image receiving layer of the recording medium, the sharpness of the recorded image, and the like, and have completed the ⁇ of the present invention.
  • the durability of a transferred image can be improved.
  • cracking resistance can be significantly improved, and when copolymerized with a monomer containing a cationic functional group, ink absorption, ink fixing, and printing properties, as well as image durability and washing resistance, are further improved. They have found that they can do this and have completed the VI of the present invention. That is, the gist of the present invention is as follows.
  • 1 of the present invention is a resin composition for an ink jet recording sheet constituting an image receiving layer formed on at least one surface of a substrate for an ink jet recording sheet,
  • the crosslinkable group-containing cationic (meth) acrylic copolymer ( ⁇ ) is 2 to 80% by weight
  • modifier (R) is an aqueous polyurethane resin (C) ( ⁇ ⁇ 80) wt%, polyurethane graph Bok polymer mixture (D) ( ⁇ 2 ⁇ 60) wt%, [provided that the The mixture (D) is prepared by adding a hydrophilic radically polymerizable vinyl monomer (ds) to another aqueous solution or dispersion of a water-based polyurethane (d and a saponified vinyl acetate copolymer (d 2 )).
  • n 2 and n 3 are each 0 wt%, (n + n 2 + n 3) ⁇
  • the present invention provides the resin composition for an ink jet recording sheet according to 1 of the present invention, which satisfies the condition of 5% by weight.
  • the third aspect of the present invention is the second aspect of the second aspect , wherein the saponified products (d 2 ) and (e 2 ) of the vinyl acetate copolymer have a degree of saponification of 75 to 100% and a degree of polymerization of 200 to 5000, respectively. And a resin composition for an ink jet recording sheet.
  • the resin composition for an ink jet recording sheet according to the second aspect of the second aspect, wherein the aqueous polyester resin (C) is cationic.
  • 5 of the present invention provides the resin composition for an ink jet recording sheet according to 2 of the present invention, wherein the polyurethane graft polymer mixture (D) and the polyester graft polymer mixture (E) are cationic.
  • 6 of the present invention is a resin composition for an ink jet recording sheet constituting an image receiving layer formed on at least one surface of the substrate for an ink jet recording sheet,
  • An ink jet recording sheet comprising the block isocyanate compound (F) in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the saponified vinyl acetate copolymer (B).
  • a resin composition for use is provided.
  • the present invention is a cross-linkable group-containing cationic (meth) acrylic copolymer (A)
  • the present invention provides the resin composition for an ink jet recording sheet according to 1 or 6, which is a copolymer containing a monomer unit based on each of the following monomers (1) and (2).
  • Item 8 of the present invention provides the resin composition for an ink jet recording sheet according to item 1 or 6 of the present invention, wherein the saponification degree of the vinyl acetate copolymer (B) is 70 to 95%. .
  • the resin composition for an ink jet recording sheet according to the seventh aspect wherein the hydrophilic group-containing monomer is a (meth) acrylate ester containing an ester bond with a polyoxyalkylene.
  • the present invention is a cross-linkable group-containing cationic (meth) acrylic copolymer (A) wherein the monomer containing a tertiary amino group or a quaternary ammonium base is 0.1 to 50 mol%;
  • the present invention provides a resin composition for an ink jet recording sheet according to any one of (1), (6) and (7), which is a copolymer containing 0.1 to 25 mol% of a crosslinkable group-containing monomer.
  • 11 of the present invention is a resin composition constituting an image receiving layer formed on at least one surface of a substrate for an ink jet recording sheet, comprising a polyalkylene oxide group.
  • the present invention provides a resin composition for an ink jet recording sheet comprising 80% by weight (the total of these is 100% by weight).
  • 12 of the present invention comprises 5 to 80% by weight of a cationic (meth) acrylic copolymer (A-IV), 15 to 80% by weight of a saponified product of a vinyl acetate copolymer (B), and Agent
  • the cationic (meth) acrylic copolymer (A-IV) is Monomers having a sharp emission oxide groups (a 0. 1 to 40 wt%, the hydrophilic group-containing monomer dimer (a 2) 0. 1 ⁇ 50 wt%, crosslinkable group-containing monomer (a 3) 0.
  • cationic monomer a 1 to 40 wt%, Hadomonoma one (a 6) 10 ⁇ 6 0 wt%, soft monomer (a 7) 10 to 60 wt% (these totals 100 wt consists%), and 1 1 or 1 2 Inkujietsuto recording cationic acrylic copolymer (weight average molecular weight of a-IV) is a 0. 2 X 1 0 4 ⁇ 1 0 0 X 1 0 4 present invention Provided is a resin composition for a sheet.
  • a resin composition constituting an image receiving layer formed on at least one surface of a substrate for an ink jet recording sheet, wherein at least a (meth) acrylate monomer containing a polyalkylene oxide group (a) A cationic (meth) acrylic copolymer obtained by copolymerizing a hydrophilic group-containing monomer (a 2 ), a crosslinking group-containing monomer (a 3 ) and a cationic monomer (a 4) (A-V) 70 to 100% by weight, saponified vinyl acetate copolymer (B) 0 to 30% by weight (the total of these is 100% by weight) and
  • a resin composition for an ink jet recording sheet comprising 0 to 15 parts by weight of a modifier (R) based on 100 parts by weight of the total of (A-V) and (B).
  • a cationic (meth) acrylic copolymer A-V
  • a polyalkylene oxide group-containing (meth) acrylate polymer a, a hydrophilic group-containing monomer (a 2 )
  • Ink jet recording according to item 14 of the present invention which is a copolymer obtained by copolymerizing a crosslinkable group-containing monomer (a 3 ), a cationic monomer (a 4 ) and a nonionic monomer (a 5 ).
  • a resin composition for a sheet A-V
  • 16 is a cationic (meth) acrylic copolymer (A-V) 75 to 95% by weight, a saponified vinyl acetate copolymer (B) 5 to 25% by weight (the total of these is 100%). (% By weight) and 0.5 to 5 parts by weight of a modifier (R) based on 100 parts by weight of the total of (AV) and (B). Offer things.
  • the 17 of the present invention is a cationic (meth) acrylic copolymer (A-V) 75 to 95% by weight, a vinyl acetate copolymer genide (B) 5 to 25% by weight (the total of these is 100% by weight) and 0.5 to 3 parts by weight of the modifier (R) with respect to 100 parts by weight of the total of (A-V) and (B).
  • a fat composition is provided.
  • the cationic (meth) acrylic copolymer (A-V) may have a polyalkylene oxide group-containing (meth) acrylate monomer (a 6 ) of 8 to 40% by weight, body (a 2) 1-30 wt.%, the crosslinkable group-containing 0.2 to 10 wt% of the monomer (a 3), cationic monomer (a 4) 10 to 50% by weight and nonionic sexual single-mer (a 5) 10 to 80 wt% that provides 14 to 17 either Inkujietsuto recording sheet resin composition of (their sum is 100 wt%) the invention containing.
  • 19 of the present invention is a structure wherein the polyalkylene oxide group of the polyalkylene oxide group-containing (meth) acrylate monomer (a) is represented by the general formula: [(CHR 1 ) !-0] m-R 2
  • the present invention provides a resin composition for an ink jet recording sheet according to any one of 11, 13, 14, 15 and 18.
  • R in equation represents a hydrogen atom, a methyl group or a hydroxyl group
  • R 2 represents a hydrogen atom or a methyl radical
  • n is 1 to 5
  • m is an integer of 1-20, respectively
  • n, m R 1 s may be the same or different from each other.
  • the hydrophilic group of the hydrophilic group-containing monomer (a 2 ) is selected from a carboxyl group or a salt thereof, an acid anhydride group, a hydroxyl group, a sulfonic acid group or a salt thereof, an amide group, and an ether group.
  • the resin composition for an ink jet recording sheet according to any one of 7, 11, 13, 14, 15, and 18 of the present invention is provided.
  • the crosslinkable group-containing monomer (a 3) of the present invention is a monomer having a hydrolyzable condensing group 7, 1 1, 13, 14, 1 5 or 18 either Provided is a resin composition for an ink jet recording sheet.
  • the ink jet according to any one of 7, 11, 13, 14, 15, and 18 of the present invention wherein the crosslinkable group-containing monomer (a 3 ) is a monomer having an alkoxysilyl group.
  • the crosslinkable group-containing monomer (a 3 ) is a monomer having an alkoxysilyl group.
  • the cationic monomer (a 4 ) is preferably any of a tertiary amino group-containing monomer, a tertiary amine acid salt-containing monomer and a quaternary ammonium base-containing monomer.
  • the present invention also provides a resin composition for an ink jet recording sheet according to any one of 7, 11, 13, 13 to 15, and 18 of the present invention.
  • the 24 of the present invention is a nonionic monomer (a 5 ) which is any one of 15 or 18 of the present invention, which is any of S (meth) acrylates, aromatic vinyls and vinyl esters.
  • the present invention provides a resin composition for an ink jet recording sheet.
  • the present invention provides a resin composition for an ink jet recording sheet according to any one of (16) and (17).
  • the ink jet recording sheet according to any one of 1, 11 or 16 of the present invention, wherein the modifier (R) contains an aqueous polyurethane resin (C) and Z or an aqueous polyester resin (e!).
  • the modifier (R) contains an aqueous polyurethane resin (C) and Z or an aqueous polyester resin (e!).
  • a resin composition for use is provided.
  • the ink image receiving layer formed on at least one surface of the base material for an ink jet recording sheet comprises a polymerizable unsaturated monomer having a hydrolyzable silyl group (a 8 ).
  • Hydrolyzable silyl group-containing (meth) acrylate copolymer (A-VI) obtained by copolymerizing a monomer containing a (meth) acrylate polymerizable unsaturated monomer (a 9 ) and an inorganic compound
  • An ink jet recording sheet comprising a composition (P) containing fine particles (G).
  • Item 28 of the present invention provides the ink jet recording sheet of item 27, wherein an ink fixing layer is provided between the base material for an ink jet recording sheet and the ink image receiving layer.
  • the 29 of the present invention provides the ink jet recording sheet of 27 of the present invention, wherein the hydrolyzable silyl group-containing (meth) acrylate copolymer (A-VI) is an aqueous copolymer.
  • the present invention is the weight ratio of the monomer unit based on each of (a 8 ) and (a 9 ) contained in the hydrolyzable silyl group-containing (meth) acrylate copolymer (A-VI).
  • Item 31 of the present invention provides the ink jet recording sheet of item 27, which is a beaded colloidal silica in which inorganic compound-based fine particles (G) are dispersed in water.
  • the ink fixing layer is at least selected from the group consisting of a cationic group-containing resin or a saponified product of the cationic group-containing resin and a vinyl acetate copolymer, an aqueous polyester resin, and an aqueous polyurethane resin.
  • An ink jet recording sheet according to 27 of the present invention comprising a resin composition containing a compound with 1 resin.
  • the cationic group-containing resin is a polymerizable unsaturated monomer having a hydrolyzable silyl group, a polymerizable unsaturated monomer having a tertiary amino group and / or a quaternary ammonium group, and 33.
  • An ink jet recording sheet according to claim 33 which is a cationic group-containing copolymer obtained by copolymerizing a monomer containing an acrylate-based polymerizable unsaturated monomer.
  • 35 of the present invention is a recording resin composition for forming an ink recording layer
  • a recording resin composition consisting of 70 to 99% by weight (I) of a good solvent for the cellulose derivative (100% by weight of both), and (3) a good solvent (I) or poor 0.1 to 20 parts by weight of an organic acid (J) soluble in a solvent (K) and optionally (4) a poor solvent (K) of a cellulose derivative in a ratio of 0 to 150 parts by weight.
  • a recording resin composition is provided.
  • 36 of the present invention provides the recording resin composition of 35 of the present invention, wherein the cellulose derivative (H) is cellulose acetate. 37.
  • the present invention provides the recording resin composition according to the present invention, wherein the recording resin composition has a boiling point of 35 ° C to 160 ° C.
  • Item 39 of the present invention provides the recording resin composition 35 of the present invention, wherein the melting point of the organic acid (J) is 60 ° C or more.
  • a poor solvent (K) power of a cellulose derivative at least one selected from esters, alcohols, ketones and ethers, and having a boiling point of 100 to 300 ° C. 35 or 37 of the present invention is provided.
  • good solvent of a cellulose derivative (I) is, d-5 dialkyl ketones, acetate d-4 alkyl esters, cyclic or linear C 4 - 6 ether, d-4 Arukirusero cellosolve, and d-4 alkyl Serosorubuasete at least one selected from a preparative, a poor solvent for the cellulose derivative (K), formic acid C 5-8 alkyl esters, Ahn Ikikosan d-4 alkyl esters, C 4 - 8 cycloalk force Nord , C 6- ! . Jarkirketon and C? ⁇ . 35.
  • a recording resin composition according to the present invention characterized in that it is at least one selected from ether.
  • the difference in boiling point between the good solvent (I) and the poor solvent (K) of the cellulose derivative (TK-TI) is 10 ° C ⁇ (TK-T I) ⁇ 200 ° C. 35 or 41 of the recording resin composition of the present invention.
  • the recording resin composition of 35 or 39 of the present invention provides the recording resin composition of 35 or 39 of the present invention, wherein the solubility of the organic acid (J) in water at 20 ° C. is 2 g / 100 ml or less. I do.
  • 44 of the present invention relates to the use of the resin composition for an ink jet recording sheet according to any one of 1 to 43 of the present invention, wherein an image receiving layer is formed on at least one surface of a substrate.
  • An ink jet recording sheet is provided.
  • a resin composition for a thermal transfer sheet comprising a polymer (L) containing a monomer unit represented by the following formula (14) and a hot melt adhesive resin (M). Equation (14)
  • R 2 — H, one CHa or one hundred H
  • n 1 to 5 m is 1 to 20
  • a plurality of R 2 may be the same or different from each other, and m (CHR 2) ⁇ - may be random or bonded to a block.
  • a resin composition for a thermal transfer sheet according to 46 of the present invention comprising a copolymer with at least one kind of monomer.
  • a resin composition for thermal transfer sheet according to 47 of the present invention which is at least one selected from a monomer having a group or an al
  • the proportion of the hot melt adhesive resin (M) is 10 to 150 parts by weight relative to 100 parts by weight of the polymer (L).
  • a resin composition for a thermal transfer sheet is provided.
  • 53 of the present invention is a sheet having at least one surface of a substrate on which an ink receiving layer releasable from the substrate is formed, wherein the ink receiving layer is 46 to 52 of the present invention.
  • a thermal transfer sheet comprising any one of the resin compositions for thermal transfer sheets.
  • 54 of the present invention provides the thermal transfer sheet of 53 of the present invention, wherein the ink receiving layer is formed on the substrate via a protective layer that can be peeled off from the substrate.
  • the thermal transfer sheet of 54 of the present invention provides the thermal transfer sheet of 54 of the present invention, wherein the protective layer is composed of at least one selected from a thermoplastic resin, a thermosetting resin, and an elastomer.
  • 56 of the present invention provides the thermal transfer sheet of 53 or 54 of the present invention, wherein the ink receiving layer contains at least one component of a dye fixing agent and a plasticizer.
  • 57 of the present invention is a method for producing a sheet wherein at least an ink receiving layer is formed by applying a material solution for forming an ink receiving layer releasable from the substrate on one surface of the substrate, Provided is a method for producing a thermal transfer sheet, wherein the receiving layer is composed of any one of the resin compositions of 46 to 56 of the present invention.
  • the present invention relates to a novel resin composition for an ink jet recording sheet and an ink jet recording sheet using the same to form an image receiving layer on the surface of the substrate for the sheet.
  • the recording sheet according to the present invention includes a base material and an image receiving layer, and at least one surface of the base material has an image receiving layer formed of the resin composition of the present invention.
  • the material of the base material for an ink jet recording sheet (hereinafter sometimes referred to as “base material for recording sheet” or simply “base material”) is not particularly limited, and a usual material using a natural fiber is used.
  • base material for recording sheet or simply “base material”
  • base material coated paper using the paper, non-woven fabric, plastic film, synthetic paper (including fiber, as well as plastic film) in which natural fibers or synthetic fibers are used alone or in combination.
  • plastic films and synthetic papers are particularly preferred.
  • polystyrene resin examples include polyolefin such as polyethylene and polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and poly (meth) acrylic acid.
  • Polyester polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose derivatives such as cellulose acetate, polyester (polyalkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate, polyethylene naphthate, polybutylene) Polyalkylene naphthenate such as naphthalate, etc.), polycarbonate, polyamide (nylon 6, nylon 66, nylon 6Z10, nylon 6Z12, etc.), polyesteramide, polyether, polyimide, polyamideimide, polyether Esters, etc., and their copolymers, blends, and cross-linked products can also be used as appropriate.
  • polyolefins particularly, polypropylene
  • polyolefins and the like are usually used.
  • Esters especially polyethylene terephthalate
  • polyamides are particularly preferably used
  • polyesters especially polyethylene terephthalate
  • the transparency of the ink jet recording sheet substrate according to the present invention is not particularly limited, and opaque, translucent, or transparent materials are appropriately used depending on the application.
  • opaque, translucent, or transparent materials are appropriately used depending on the application.
  • ⁇ HP overhead projector
  • a transparent one is preferred.
  • paper and coated paper for example, high-quality paper, art paper, RC paper, and the like can be used.
  • the thickness of the substrate is also not particularly limited and is appropriately selected depending on the application, but is usually from 5 to 500 x m, and more preferably from about 10 to 300 m.
  • additives such as sizing agents, antioxidants, ultraviolet absorbers, heat stabilizers, lubricants, and pigments may be added to the plastic film or synthetic paper used as the base material. Is also good.
  • a film and a synthetic paper having excellent water resistance are preferably used.
  • the surface of the base material is subjected to a corona discharge treatment or an undercoat treatment in advance.
  • the image-receiving layer according to the first aspect of the present invention comprises a cross-linkable group-containing cationic acrylic copolymer (A-I), a vinyl acetate-based copolymer having a specific polymerization degree (B), and a modifier (R). To form an image receiving layer.
  • A-I cross-linkable group-containing cationic acrylic copolymer
  • B vinyl acetate-based copolymer having a specific polymerization degree
  • R modifier
  • the image-receiving layer according to the first aspect of the present invention comprises a composition comprising a crosslinkable group-containing cationic acrylyl copolymer ( ⁇ - ⁇ ) and a saponified vinyl acetate copolymer (B), and an aqueous polyurea compound. It is made of resin (C), polyurethane-based graft polymer mixture (D) and Z or polyester-based graft polymer mixture (E).
  • the image receiving layer according to the m-th embodiment of the present invention comprises a composition comprising a crosslinkable group-containing cationic acrylic copolymer ( ⁇ - ⁇ ) and a saponified vinyl acetate copolymer (B), It is formed of resin (C), polyurethane graft polymer mixture (D) and Z or polyester graft polymer mixture (E).
  • the image receiving layer according to the first aspect of the present invention comprises a crosslinked group-containing cationic acrylic copolymer ( ⁇ - ⁇ ) and a saponified vinyl acetate copolymer (B), and an aqueous polyurethane resin composition. (C) and a block isocyanate compound (F).
  • the image-receiving layers according to the fourth and fifth aspects of the present invention comprise a (meth) acrylate monomer (a) having a specific polyalkylene oxide group, a hydrophilic group-containing monomer (a 2 ), Cationic (meth) acrylic copolymer (A-IV or AV) obtained by copolymerizing a group-containing monomer (a 3 ) and a cationic monomer (a 4 ), vinyl acetate It is formed of a resin composition for a recording sheet comprising a saponified copolymer (B) and a modifier (R).
  • the image receiving layer according to the VI of the present invention comprises a monomer containing a polymerizable unsaturated monomer having a hydrolyzable silyl group (a 8 ) and a (meth) acrylate polymerizable unsaturated monomer (a 9 ).
  • Sheet comprising a composition (P) containing a hydrolyzable silyl group-containing (meth) acrylate copolymer (A-VI) obtained by copolymerizing a polymer and inorganic compound-based fine particles (G) It is formed of a resin composition for use.
  • the image-receiving layer according to the seventh embodiment of the present invention comprises a resin composition comprising a cellulose derivative (H) and a good solvent (I) of a cellulose derivative, and a good solvent (I) or a poor solvent (K) of a cellulose derivative. It is formed of a resin composition for a recording sheet comprising a soluble organic acid (J) and, optionally, a poor solvent (K) for a cellulose derivative.
  • the method for forming the image receiving layer is not particularly limited, and various known means can be applied. The details will be described later.
  • the resin composition for forming the image receiving layer formed on at least one surface of the substrate for an ink jet recording sheet according to the present invention (hereinafter, may be simply referred to as “recording resin composition”) will be sequentially described below. It is composed of a recording resin composition.
  • the recording resin composition according to the first and second aspects of the present invention contains a crosslinkable group-containing cationic acryl copolymer (AI XttA-n) in an amount of 2 to 80% by weight, preferably 5 to 50% by weight, and a degree of polymerization.
  • AI XttA-n crosslinkable group-containing cationic acryl copolymer
  • the composition ratio of each component is represented by solid content conversion.
  • the components of the modifier according to I and ⁇ of the present invention (R), an aqueous polyurethane Tan resin (C) (I!, ⁇ 80) % by weight, polyurethane graft polymer mixture (D) (n 2 ⁇ 60) wt%,
  • the mixture (D) is a mixed aqueous solution or dispersion of the graph Bok aqueous polyurethane (d vinyl acetate copolymer saponified (d 2), the hydrophilic radical polymerizable vinyl-single Monomer (d 3 ) and another radical polymerizable vinyl monomer (d 4 ) in an amount of 100 to 60% by weight.
  • the mixture (E) is prepared by adding a hydrophilic radical polymerizable vinyl monomer to a mixed aqueous solution or aqueous dispersion of an aqueous polyester resin (e!) For grafting and a saponified product (e 2 ) of a vinyl acetate copolymer.
  • n is the minimum value of n 2 and n 3 are each 0 wt%, (r ⁇ + ns + ns) ⁇ 5% by weight.
  • the water-based polyurethane resin (C) has a force ⁇ , ⁇ 0) weight%
  • the polyurethane-based graft polymer mixture (D) has ( ⁇ 2 -50) weight%
  • the polyester-based graft polymer mixture ( ⁇ ) has (%). ⁇ 3 to 60)% by weight and (r ⁇ + ns + n ⁇ l 0% by weight).
  • the modifier (R) is a resin composition of the water-based polyurethane resin (C) or the polyester-based graft mixture (E).
  • the recording resin composition according to the m-th invention comprises a crosslinked group-containing cationic (meth) acrylic copolymer ( ⁇ - ⁇ ) in an amount of 2 to 80% by weight, a saponified vinyl acetate copolymer (B ) Is 5 to 60% by weight, the aqueous polyurethane resin composition (C1) is 0 to 80% by weight,
  • the crosslinkable group-containing cationic acrylic copolymer ( ⁇ - ⁇ ) is 10 to 60% by weight
  • the saponified vinyl acetate copolymer (B) is 15 to 50% by weight
  • the aqueous polyurethane resin composition ( C 1) is 5 to 60% by weight
  • the block isocyanate compound (F) is 0.3 to 5 parts by weight based on the (B) part by weight.
  • composition ratio of each component expressed in terms of solid content is a range that gives excellent properties such as ink absorbency, water resistance, and print image quality in ink jet recording. It is appropriately selected from the boxes.
  • the crosslinkable group-containing cationic acrylic copolymer ((A-I) to (A-positive)) and the content thereof determine the ink fixing property, water resistance, and print image quality.
  • the ink absorption is affected, and the degree of polymerization affects print quality such as beading.
  • the modifier (R) improves properties such as water resistance and adhesion to a substrate.
  • the water-based polyurethane resin (C) affects water resistance and adhesion to the substrate, and the polyurethane-based graft polymer mixture (D) and the polyester-based graft polymer mixture (E) mainly affect ink absorption. Depends.
  • ⁇ - ⁇ is not particularly limited as long as it is a cationic acrylic copolymer having a crosslinkable group, but as an embodiment, it is based on each monomer of (1) or (2) below.
  • a copolymer containing a cationic monomer unit and a crosslinkable group-containing monomer unit (1) A copolymer containing a cationic monomer unit and a crosslinkable group-containing monomer unit.
  • Examples of the cationic monomer include various monomers having a tertiary amino group or a salt thereof, and various monomers having a quaternary ammonium base or capable of forming a quaternary ammonium base.
  • Examples thereof include (meth) acrylates and salts thereof, and further, di (: alkylamino-C 2 -alkyl group-substituted aromatic biels or salts thereof.
  • the above salts include hydrohalides (hydrochlorides, hydrobromides, etc.), sulfates, alkyl sulfates (methyl sulfate, ethyl sulfate, etc.), alkyl sulfonates, aryl sulfones
  • quaternary ammonium bases can be prepared by reacting a tertiary amino group with an alkylating agent (epichlorohydrin, methyl chloride, benzyl chloride, etc.). A generation method may be adopted.
  • crosslinkable group-containing monomer examples include monomers having various functions having a self-crosslinkable or reactive functional group. Specifically, glycidyl (meth) methacrylate, (meth) a Containing epoxy groups such as rylglycidyl ether, 1-aryloxy-3,4_epoxybutane, 11- (3-butenyloxy) 1-2,3-epoxypropane, 4_vinyl-1_cyclohexene-1,2-epoxide monomer, N- methylol (meth) acrylamide, N- methoxymethyl (meth) N one 4 alkoxymethyl, such as acrylamide (meth) acrylamide, N- Puchiroru (meth) methylol group-containing monomers such as ⁇ click Riruamido or Derivatives, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethoxydimethylsilane, vinyl Ethoxy di
  • the crosslinkable group-containing monomer include a hydrolytic condensable group, particularly an alkoxysilyl group (and Specifically, it is a crosslinkable monomer having a hydrolytic condensable group such as a methoxysilyl group or an alkoxysilyl group such as an ethoxysilyl group.
  • crosslinkable group-containing monomers can be used alone or in combination of two or more.
  • Hydrophilic group-containing monomer component Hydrophilic group-containing monomer component
  • Amide group-containing monomers such as styrene sulfonic acid and vinyl sulfonic acid, vinyl methyl ether, vinyl ethyl Ether group-containing monomers to which vinyl ethers such as ether and vinyl isobutyl ether belong, polyoxyethylenes such as diethylene diol glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate Le Killen group-containing monomers and the like can be exemplified.
  • carboxyl group-containing monomers such as (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate,
  • Hydroxyl group-containing monomers such as (meth) hydroxypropyl acrylate, and polyoxyalkylene esters such as jeti-lendlycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate Monomers.
  • hydrophilic group-containing monomers can be used alone or in combination of two or more. You.
  • cationic monomers crosslinkable group-containing monomers or hydrophilic group-containing monomers are usually used in combination with the following nonionic monomers in order to adjust film formability and film properties. Is done.
  • the nonionic monomers mentioned here include, for example, methyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, N-Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethyl (meth) acrylate 8-alkyl esters of (meth) acrylic acid such as xyl, lauryl (meth) acrylate, and stearyl (meth) acrylate; cycloalkyl esters such as cyclohexyl (meth) acrylate; and (meth) acrylic Aryl esters such as phenyl acrylate, aralkyl esters such as benzyl (me
  • Non-ionic monomers are usually C 8 alkyl esters of (meth) acrylic acid, especially C 2 of acrylic acid.
  • aromatic vinyls, especially styrene, or vinyl esters, especially vinyl acetate, are used.
  • nonionic monomers can be used alone or in combination of two or more.
  • the amount of use of the cationic monomer and the monomer having a crosslinkable group, or the amount of use when a monomer having a hydrophilic group is further combined, does not impair water resistance and ink absorption.
  • the amount of the cationic monomer used is 0.1 to 50 mol% (for example, 1 to 45 mol%) of the whole monomer, and preferably 0.1 to 50 mol%. It is about 5 to 40 mol% (for example, 2 to 35 mol%), more preferably about 1 to 30 mol% (for example, 3 to 25 mol%), and usually about 2 to 25 mol%.
  • the amount of the crosslinkable group-containing monomer is, for example, about 0.1 to 25 mol%, preferably about 0.2 to 20 mol%, and more preferably about 0.5 to 15 mol% of the whole monomer. Usually, it is about 0.3 to 10 mol%.
  • the amount of the hydrophilic group-containing monomer used is 0 to 50 mol%, preferably 0 to 45 mol% (0.5 to 45 mol%), more preferably 0 to 40 mol% of the whole monomer. Mol% (1 to 35 mol%), usually about 1 to 20 mol%.
  • the total is adjusted to 100% by mole, but when less than 100% by mole, the remainder is usually the above-mentioned nonionic property. It is composed of monomers.
  • a copolymer containing 0.1 to 50 mol% of a monomer containing a tertiary amino group or a quaternary ammonium base, and 0.1 to 25 mol% of a monomer containing a crosslinkable group The first of the present invention! It is preferably used as the crosslinkable group-containing cationic acrylic copolymer (A-I-A- ⁇ ) according to (1).
  • the glass transition temperature of the crosslinkable group-containing cationic acrylic copolymer ( ⁇ - ⁇ to ⁇ - ⁇ ) can be selected within a range that does not impair the film-forming property, and is preferably from 20 to 50 ° C, 40 ° C is more preferable, and more preferably about 0 ° C to 30 ° C.
  • a copolymer having such a glass transition temperature can be prepared by combining the cationic monomer and the crosslinkable group-containing monomer, and if necessary, further combining a hydrophilic group-containing monomer.
  • a monomer capable of forming a homopolymer having a glass transition temperature of 80 to 120 ° (:, preferably 90 to 105 ° C) such as a hard monomer such as methyl (meth) acrylate, styrene and the like.
  • Monomer and soft monomer for example, Cs-i of acrylic acid, glass transition temperature of 85 ° C ⁇ -10 It is used in combination with a monomer capable of forming a homopolymer at a temperature of preferably 85 ° C to 120 ° C and copolymerized.
  • the proportion of each monomer used is not particularly limited. Can be.
  • the weight average molecular weight of the crosslinkable group-containing cationic acrylic copolymer ( ⁇ - ⁇ to ⁇ -m) is not particularly limited, but is preferably from 0.2 ⁇ 10 4 to 100 ⁇ 10 4, and more preferably from 1 ⁇ 10 4 A range of about 50 ⁇ 10 4 is more preferable.
  • the form of the crosslinkable group-containing cationic acrylic copolymer (A-II-III-II) may be an aqueous solution in addition to an organic solvent solution, but a cationic emulsion (particularly an aqueous emulsion) is usually preferred.
  • the surface potential ( ⁇ potential) of the polymer particles contained in the emulsion is +10 to +6 OmV, preferably +12 to +55 mV, more preferably +20 to +55 mV, and particularly preferably. Is about +15 to +55 mV.
  • the surface potential of the polymer particles can be measured, for example, with the following apparatus and conditions.
  • Measuring device Electrophoretic light scattering photometer (ELS-800) manufactured by Otsuka Electronics Co., Ltd. Measurement temperature: 25 ° C.
  • Concentration Dilute the emulsion with distilled water to a solids concentration of 0.01 to 0.05% by weight. Distance between electrodes: 32 mm
  • the average particle size of the polymer particles in the cationic emulsion is from 1 to 200 nm, preferably from 3 to 100 11111, and more preferably from about 5 to 50 nm.
  • Cationic emulsions containing a crosslinkable group-containing cationic acrylic copolymer can be prepared by a conventional method, for example, emulsion polymerization containing a nonionic surfactant and a Z or cation surfactant.
  • a method of emulsion-polymerizing the above two or three kinds of monomers in a system, or a method of forming a tertiary amine salt or a quaternary ammonium salt after copolymerizing the monomers to form an aqueous emulsion. Can be obtained.
  • the resin composition for an ink jet recording sheet comprises a hydrophilic polymer compound (a water-soluble polymer compound or a water-insoluble polymer compound having water absorbency) and other components. When combined, water resistance and print quality can be improved without significantly impairing the ink absorbency.
  • a hydrophilic polymer compound a water-soluble polymer compound or a water-insoluble polymer compound having water absorbency
  • saponified vinyl acetate copolymers (B) are used as the above and below-mentioned hydrophilic polymer compounds.
  • the saponified polymers may be used alone, and a plurality of kinds of vinyl acetate copolymers may be used.
  • a combined saponified product may be used in combination, and further another hydrophilic polymer compound may be used in combination.
  • hydrophilic polymer compounds examples include hydrophilic natural polymers or derivatives thereof (starch, corn starch, sodium alginate, gum arabic, gelatin, casein, dextrin, etc.), cellulose derivatives (methylcellulose, ethylcellulose, hydroxylase).
  • the other hydrophilic polymer compound is preferably a cellulose derivative (particularly, hydroxyethyl cellulose, etc.), a vinyl alcohol polymer, a vinyl ester polymer, polyvinyl pyrrolidone, or the like.
  • a hydrophilic polymer having at least one functional group selected from a polyoxyalkylene group, an acetoacetyl group, a propyloxyl group, an acid anhydride group and an amino group is also preferably used.
  • the saponified product (B) of the above-mentioned vinyl acetate copolymer according to the first to VI aspects of the present invention is a partially saponified product of a vinyl acetate homopolymer or a copolymer of vinyl acetate and another copolymerizable monomer. Or completely saponified, but preferably has a degree of genification of 70 to 95%, and More preferably, it is 75 to 92%, and still more preferably, it is 79 to 89%. However, in the second invention, 70 to 100%, more preferably 75 to 95%, and still more preferably 79 to 95%
  • a saponified vinyl acetate copolymer having a degree of polymerization of 200 to 100, preferably 300 to 800 is used. If the degree of polymerization of the polymer is less than 200, the effect of improving water resistance may not appear,
  • Preferred as the other copolymerizable monomers are hydrophilic groups (for example, carboxyl groups and salts thereof, sulfonic acid groups and salts thereof, acid anhydride groups, amide groups, hydroxyl groups, ether groups, etc.).
  • a vinyl monomer such as a (meth) acrylate diaryl ether having an ether group, especially an oxyalkylene group, in which case the number of units (addition moles) of the alkylene oxide is It is preferably from 1 to 100, more preferably from 2 to 80, still more preferably from 5 to 70.
  • Examples of the vinyl monomer having an oxyalkylene group include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, and triethylene glycol mono (meth) acrylate.
  • preferred monomers are (meth) acrylates, which are vinyl monomers in which the oxyalkylene group is an oxyethylene group, especially polyoxyalkylene.
  • aryl ethers (among others, polyoxyethylene aryl ethers) are included. These vinyl monomers can be used alone or in combination of two or more.
  • the ratio of the copolymerizable monomer copolymerized with vinyl acetate for obtaining the saponified product (B) of the vinyl acetate copolymer according to the first to VI aspects of the present invention depends on the sharpness of the image, the water resistance, and the like. Although it can be freely selected within a range not to impair, it is preferably 0.1 to 50 mol% of the whole monomer, more preferably 1 to 30 mol%, and 2.5 to 25 mol% (for example, 3 to 20 wt%). %) Is more preferred.
  • a copolymer of vinyl acetate and a vinyl monomer having a polyoxyalkylene group is available from Nippon Kasei Chemical Co., Ltd. under the trade name “OKS-7 158 G”. And so on.
  • the hydrophilic polymer which can be used in combination with the saponified vinyl acetate copolymer (B) includes the reactive functional group of the crosslinkable group-containing cationic acrylic copolymer.
  • hydrophilic polymer compound having a functional group reactive to an epoxy group such as a glycidyl group, an alkoxysilyl group, etc.
  • an epoxy group such as a glycidyl group, an alkoxysilyl group, etc.
  • Examples of the modifier according to the present invention include water-based polyurethane resin (C), urethane-based graft polymer mixture (D), and polyester-based graft polymer mixture.
  • At least one component selected from (E) and the block isocyanate compound (F) is preferably used.
  • a resin comprising an aqueous polyurethane resin (C) and Z or a polyester-based graft polymer mixture (E) is used.
  • a composition is used.
  • the water-based polyurethane resin (C) refers to a polyol component, a polyisocyanate component, and a low-molecular-weight resin containing at least two hydrogen atoms in the molecule that reacts with the polyisocyanate component. It is obtained by dissolving or dispersing a polyurethane resin synthesized from a chain extender having a molecular weight in water and synthesized by a known method.
  • the polyisocyanate component used in the production of the water-based polyurethane resin (C) includes aromatic polyisocyanates (for example, m-phenylene diisocyanate, p-foot, 2,4-tolylene diisocyanate).
  • the polyisocyanate component is an adduct having a polyisocyanate group added to a polyhydric alcohol and having an isocyanate group at a terminal, a cyanurate, a dimer, or a trimer generated by a Burette reaction. There may be.
  • the polyisocyanate component can be used alone or in combination of two or more.
  • the polyester polyol is a polyester having a hydroxyl group, which is obtained by reacting a polyhydric alcohol with a polycarboxylic acid or a lower alkyl ester or an acid anhydride thereof, and may be derived from a lactone.
  • a diol component eg, polyesterdiol
  • the polyol component can be used alone or in combination of two or more.
  • Polyhydric alcohols for preparing the polyester polyol as the polyol component include aliphatic polyhydric alcohols (eg, ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, tetramethylene glycol, C 2 as methylene glycol, neopentyl glycol - 1 0 alkylene diol, diethylene glycol, poly Okishi one C 2 4 alkylene glycol such as triethylene glycol, trimethylolpropane, pen evening erythritol Alicyclic polyhydric alcohols (e.g., 1,4-cyclohexandimethylol, alicyclic diols such as hydrogenated bisphenol A), aromatic polyhydric alcohols [e.g., Aromatic diols of 2-bis (2-hydroxyethylphenyl) propane, etc.] are included, but aliphatic polyols are usually used as polyhydric alcohols.
  • aliphatic polyhydric alcohols
  • the polyhydric alcohols can be used alone or in combination of two or more.
  • polyhydric carboxylic acids for preparing the polyester polyol include aliphatic polycarboxylic acids (for example, saturated aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and maleic acid).
  • aliphatic polycarboxylic acids for example, saturated aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and maleic acid.
  • Unsaturated aliphatic dicarboxylic acids such as acids
  • alicyclic polycarboxylic acids for example, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid
  • aromatic polycarboxylic acids for example, Examples thereof include phthalic acid, terephthalic acid, isophthalic acid, aromatic dicarboxylic acids such as 1,5-naphthylene dicarboxylic acid, and aromatic polycarboxylic acids such as trimellitic acid.
  • Polycarboxylic acids can be used alone or in combination of two or more.
  • polyester polyol can be derived from a lactone, and the lactone includes butyrolactone, norellolactone, and force prolactone, and these may be used alone or in combination of two or more.
  • a short-chain polyol for example, the above-mentioned aliphatic polyhydric alcohol or the like
  • aliphatic polyhydric alcohol for example, the above-mentioned aliphatic polyhydric alcohol or the like
  • the chain extender used in the production of the aqueous polyurethane resin (C) includes a polyamine component.
  • the polyamine include ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, Examples thereof include diamines such as 7-diaminohexane, 1,8-diaminooctane, xylylenediamine, 1,4-diaminocyclohexaneisophoronediamine and phenylenediamine, and polyamines such as triaminopropane.
  • One of the polyurethane resins obtained by such a raw material and the production method may be used alone, or a plurality of polyurethane resins may be used in combination.
  • the polyurethane resin composition (C1) used in the first aspect of the present invention includes, in addition to the above-mentioned aqueous polyurethane resin (C), a polyurethane graft polymer mixture (D) and / or A composition containing the polyester-based graft polymer mixture (E) may be used.
  • a polyurethane graft polymer mixture (D) may be used.
  • the grafting aqueous polyurethane (d,), grafting acid vinyl Le copolymer saponified (d 2) and a hydrophilic Raj Cal polymerizable vinyl monomer in the mixed aqueous solution or dispersion in ( d 3) copolymerizable with the radical-polymerizable vinyl monomer (d 4) composition obtained by polymerizing the like.
  • the water-based polyurethane resin (C) exemplified in the description of the water-based polyurethane resin can be preferably used.
  • the saponified product (d 2 ) of the vinyl acetate-based copolymer for grafting the saponified product (B) of the vinyl acetate-based copolymer exemplified in the description of the saponified product of the vinyl acetate-based copolymer is preferable. Can be used.
  • hydrophilic radical polymerizable vinyl monomer (d 3 ) include the polyalkylene oxide side chains exemplified in the description of the cationic acryl copolymer and a hydrophilic group containing a crosslinkable group. Monomers can be preferably used.
  • the nonionic monomers exemplified in the description of the cationic acrylic copolymer can be preferably used.
  • the ratio of the saponified product of the water-based polyurethane (di) and the vinyl acetate-based copolymer (d 2 ) to the radically polymerizable vinyl monomers (d 3 ) and (d 4 ) is not particularly limited.
  • the saponified product (d 2 ) of the vinyl acetate copolymer is preferably 10 to 500 parts by weight, more preferably 20 to 30 parts by weight, based on the aqueous polyurethane (d 100 parts by weight) in terms of the fraction.
  • the radical polymerizable vinyl monomer (d 3 ) preferably has a total of two kinds (d 3 ) + (d 4 ) of 10 to 500 parts by weight, more preferably 20 to 500 parts by weight.
  • the amount of the saponified product (d 2 ) of the vinyl acetate copolymer is less than 100 parts by weight, the sharpness of the image and the ink absorption are insufficient, and the weight is 500 parts by weight.
  • the polyurethane graft polymer mixture (D) is a radical polymerizable vinyl monomer (d 3 ) 100 hydrophilic to the saponified product (d 2 ) of the above-mentioned aqueous polyurethane (di) and vinyl acetate copolymer.
  • d4 radical polymerizable vinyl monomer
  • copolymerizable at 0 to 40 % by weight preferably 95 to 60: 5 to 40 % by weight. It is obtained by graft polymerization.
  • the content of the hydrophilic pinyl monomer (d 3 ) is less than 60% by weight, the absorbability of the aqueous ink becomes poor.
  • the hydrophilic radically polymerizable vinyl monomer (d 3 ) is graft-polymerized to an aqueous polyurethane ((h) and a saponified product (d 2 ) of a vinyl acetate copolymer
  • the graft polymer mixture (D) has excellent water-absorbent ink absorbency and has the characteristics of polyurethane resin such as adhesion, water resistance, transparency, and toughness.
  • polymerization initiator examples include general radical polymerization initiators, for example, azo compounds [azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), azobiscyanovaleric acid, 2, 2-azobis (2-amidinopropane) hydrochloride, 2,2-azobis (2-amidinopropane) acetate, etc.), inorganic peroxides (persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, etc.) Hydrogen peroxide), organic peroxides (benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, di (2-ethoxysulfyl) peroxy succinate), and redox catalysts (sulfite or bisulfite (Al Metal salts, ammonium salts, etc.), reducing agents such as L-ascorbic acid, erythorbic acid, etc. And oxidizing agents such as
  • the polyurethane graft polymer mixture (D) obtained as described above may contain epoxy resin, amino resin, acrylic resin, polyurethane resin, polyester resin, starch, polyamine resin, etc.
  • Conventionally known additives such as agents, thickeners, leveling agents, antiblocking agents, antistatic agents, ultraviolet absorbers, and antioxidants can be added.
  • the aqueous polyester resin composition (E1) used in the present invention can be obtained by subjecting a dicarboxylic acid and a diol to polycondensation esterification (or transesterification) by a known production technique.
  • the production method is not limited at all.
  • the dicarboxylic acid component it is preferable to mainly use an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, or naphthophosphorus dicarboxylic acid or an ester thereof.
  • aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, or naphthophosphorus dicarboxylic acid or an ester thereof.
  • an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, or naphthophosphorus dicarboxylic acid or an ester thereof.
  • an aromatic nucleus of the aromatic dicarboxylic acid has a high affinity with the hydrophobic plastic, so that there is an advantage that the adhesion is improved.
  • an aqueous polyester using terephthalic acid has a high adhesion to a molded article of a polyethylene terephthalate-based polyester, and is a preferred aqueous polyester
  • the dicarboxylic acid component constituting the aqueous polyester resin composition (E 1) it is preferable to use the above-mentioned aromatic dicarbonic acid or an ester thereof, but in addition to these, adipic acid, succinic acid, sebacic acid
  • An aliphatic dicarboxylic acid such as dodecane diacid, a hydroxycarboxylic acid such as hydroxybenzoic acid, or an ester thereof can also be used as the dicarboxylic acid component or as a part thereof.
  • a lower alkyl ester such as a methyl ester or an ethyl ester is used. These esters can be monoesters or esters.
  • diol components include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyldaricol, cyclohexanedimethanol, and bisphenols.
  • the aqueous polyester resin composition (E1) used in the present invention is polymerized so that the molecule contains a sulfonic acid group or a carboxylic acid group as a hydrophilic group in order to impart water solubility or water dispersibility.
  • a dicarboxylic acid component such as 5-sodium sulfoisofluoric acid
  • I can do it. Its use amount is preferably 2 to 15 mol% in the dicarboxylic acid component.
  • a carboxylic acid-containing aqueous polyester resin composition (E1) is prepared by, for example, a method of grafting a saturated carboxylic acid, and a salt with a substance that forms a water-soluble salt with an alkali metal, various amines, an ammonium compound, and the like. And the like.
  • the amount of the carboxylic acid salt in the aqueous polyester resin composition (E1) is preferably such that the acid value of the produced aqueous polyester resin composition (E1) is in the range of 15 to 250 K KHmg / g.
  • the polyester used in the water-based polyester resin composition (E 1) has a molecular weight of from 4,000 to 300,000. If the molecular weight is less than 4,000, water resistance and blocking resistance are obtained. However, resin properties such as adhesion tend to decrease, and if it exceeds 30,000, it is difficult to uniformly dissolve or disperse it in water, and it tends to gel over time. Particularly, those having a molecular weight of 5,000 to 2,500 are preferable.
  • the aqueous polyester resin composition (E1) is converted into an aqueous solution or an aqueous dispersion.
  • the aqueous polyester resin composition (E1) is preferably 50 to 90% under stirring. Dissolve or disperse in warm water at ° C. In this case, a water-soluble organic solvent may be used in combination to facilitate dissolution or dispersion of the resin.
  • water-soluble organic solvent examples include lower alcohols, polyhydric alcohols and alkyl ethers or alkyl esters thereof, and specifically, lower alcohols such as methanol, ethanol, normal propanol and isopropanol, and ethylene glycol.
  • Polypropylene alcohol such as propylene glycol, diethylene glycol, dipropylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol acetate , Diethylene glycol monomethyl ether, dipropylene Recall monomethyl ether and the like can be used.
  • a carboxylate-containing polyester resin In the case of a carboxylate-containing polyester resin, it is dissolved in warm water (preferably 50 to 90 ° C) to which an alkaline compound such as aqueous ammonia, sodium hydroxide, potassium hydroxide, or various amines is added, with stirring. Or disperse. In this case, the water-soluble organic solvent may be used in combination.
  • the water-based polyester resin composition (E1) thus obtained may be used alone, or may be used in combination of a plurality of water-based polyester resin compositions (E1). Resins and additives can be blended.
  • the water-based polyester resin composition (E1) exemplified in the description of the water-based polyester resin composition can be preferably used.
  • the saponified product (e 2 ) of the vinyl acetate-based copolymer for grafting the saponified product (B) of the vinyl acetate-based copolymer exemplified in the description of the saponified product of the vinyl acetate-based copolymer is preferable. Can be used.
  • the hydrophilic radical polymerizable vinyl monomer (e 3 ) may be a hydrophilic monomer comprising the polyalkylene oxide group-containing monomer exemplified in the description of the cationic (meth) acrylic copolymer.
  • the group-containing monomer (a 2 ) can be preferably used.
  • the other radically polymerizable vinyl monomer (e 4) may be any of the nonionic monomers exemplified in the description of the above-mentioned ionic (meth) acrylic copolymer.
  • the polyester-based graft polymer mixture (E) is obtained by mixing the above-mentioned aqueous polyester resin for grafting (e) with a saponified vinyl acetate copolymer (e 2 ) for grafting.
  • the hydrophilic radical polymerizable vinyl monomer (e 3) 100 ⁇ 60 wt% with other copolymerizable radically polymerizable vinyl monomer (e ⁇ 0 to 40 by weight%
  • the content of the hydrophilic radically polymerizable vinyl monomer (e 3 ) is 60% by weight or less, the absorbability of the aqueous ink becomes poor.
  • the ratio of the water-based polyester resin (e and saponified vinyl acetate copolymer (e 2 ) and the radical polymerizable vinyl monomer [(e 3 ) + (e 4 )] is based on the solid content ratio of the water-based polyester.
  • the radically polymerizable vinyl monomer (e 3 ) is 10 to 500 parts by weight, preferably 20 to 300 parts by weight. If the amount of the saponified vinyl acetate copolymer is less than 10 parts by weight, the sharpness of the image and the ink absorbency are apt to decrease.If the amount exceeds 500 parts by weight, the adhesiveness to the base material such as a polyester film plastic film Becomes defective. When the amount of the radical polymerizable vinyl monomer (e 3 ) is less than 10 parts by weight, the ink absorbency is poor. When the amount is more than 500 parts by weight, not only the water resistance is poor, but also the adhesion to a base material such as a plastic film. Also tends to decrease.
  • a conventionally known method can be used as a polymerization method for obtaining the polyester graft polymer mixture (E).
  • a polymerization initiator and, if necessary, a small amount of an emulsifying dispersant are added to an aqueous solution Z of an aqueous polyester resin for grafting (e and an aqueous solution of a vinyl acetate copolymer (e 2 ) for grafting (e 2 ).
  • the hydrophilic radically polymerizable vinyl monomer (e 3 ) is gradually added with stirring, and then the mixture is aged for 2 to 5 hours to complete the polymerization, and the polymer mixture (E ) Can be obtained.
  • the hydrophilic radical polymerizable vinyl monomer (e 3 ) is graft-polymerized to the water-based polyester resin (e) and the vinyl acetate-based copolymer (e 2 ), this polyester-based graft polymer mixture is used.
  • (E) has excellent water ink absorption and It also has properties such as adhesion, water resistance, and toughness that are characteristic of polyester resin.
  • polymerization initiator a general radical polymerization initiator, for example, the polymerization initiator exemplified in the above-mentioned polyurethane-based graft polymer mixture (D) can be used.
  • the additives exemplified in the description of the polyurethane-based graft polymer mixture (D) can be similarly used in the obtained polyester-based polymer mixture.
  • the blocked isocyanate compound (F) according to the HI of the present invention is obtained by reacting an isocyanate compound with a blocking agent by a conventional method until free isocyanate groups disappear.
  • the isocyanate compounds exemplified in the description of the aqueous polyurethane resin can be preferably used.
  • Known blocking agents can be used, for example, oximes such as methylethylketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime and benzophenone oxime; phenols such as m-cresol and xylenol Alcohols such as methanol, ethanol, butanol, 2-ethylhexanol, cyclohexanol, ethylene glycol monoethyl ether; lactams such as prolactam, getyl malonate, acetate acetate, etc. Diketones; mercaptans such as thiophenol, and the like.
  • ureas such as thiourea; imidazoles; carbamic acids.
  • Block isocyanate compounds are commercially available.
  • Desmodur Series Suditomo Bayer Urethane Co., Ltd.
  • Burnock D Series Densitomo Bayer Urethane Co., Ltd.
  • Takenate B Series Takeda Pharmaceutical Co., Ltd.
  • Aquanate 200 series Nippon Polyurethane Industry Co., Ltd.
  • Elastron BN series No. Ichi Kogyo Seiyaku Co., Ltd.
  • the resin composition for an ink jet recording sheet according to II is a crosslinked group-containing cationic acrylic copolymer ( ⁇ - ⁇ to ⁇ - ⁇ ), a vinyl acetate copolymer having a degree of polymerization of 200 to 1,000.
  • a modifier (R) is compounded under the following conditions under the following conditions:
  • the modifier (R) is 0 to 80% by weight, preferably 5 to 60% by weight, more preferably 5 to 65% by weight.
  • the modifying material (R) can take the preferred embodiment described above.
  • the modifier (R) further comprises a water-based polyurethane resin (C), a polyurethane-based graft polymer mixture (D), and a polyester-based graft polymer mixture (E) under the following predetermined conditions.
  • ( ⁇ - ⁇ to ⁇ - ⁇ ) is 2 to 80% by weight, preferably 5 to 50% by weight
  • (B) is 5 to 80% by weight, preferably 15% by weight.
  • (C) is ( ⁇ , ⁇ 0) wt%, preferably (! ⁇ -0) wt%
  • (D) is ( ⁇ 2 -60) wt%, preferably ( ⁇ 2 ⁇ ( ⁇ ) is blended at ( ⁇ 3 -60) wt%.
  • ⁇ ⁇ 2 and ⁇ 3 each have a minimum value of 0% by weight, but (r ⁇ + nz + ns) is ⁇ 5% by weight, preferably 10% by weight or more.
  • (A-I- ⁇ - ⁇ ) degrades the ink fixing property, water resistance and print quality outside the range of 2 to 80% by weight, and (B) absorbs ink outside the range of 5 to 80% by weight.
  • (C) shows a decrease in water resistance and adhesion to a substrate outside the range of (n) to 80% by weight
  • (D) and (E) show both In both cases, when the content is out of the range of (n 2 to 60) wt%, water resistance, ink absorbency, and print quality deteriorate.
  • the resin composition for an ink jet recording sheet according to the fourth aspect of the present invention comprises a monomer having a polyalkylene oxide group (a, a monomer having a hydrophilic group (a 2 ), a monomer having a crosslinkable group (a) a 3), and cationic monomer (cationic obtained by copolymerizing a monomer containing a (meth) acrylic copolymer (A- IV) 2 ⁇ 100 wt%, acetic acid vinyl-based copolymer It comprises a saponified polymer (B) in an amount of 0 to 90% by weight and a modifier (R) in an amount of 0 to 80% by weight.
  • a monomer having a polyalkylene oxide group a, a monomer having a hydrophilic group (a 2 ), a monomer having a crosslinkable group (a) a 3
  • cationic monomer cationic obtained by copolymerizing a monomer containing a (meth) acrylic copolymer
  • the resin composition for an ink jet recording sheet according to the fifth aspect of the present invention comprises a cationic (meth) acrylic copolymer (A-V) of 70 to 100% by weight, a saponified vinyl acetate copolymer (B 0-30% by weight (the total of these is 100% by weight), and
  • the modifier (R) is added in an amount of 0 to 15 parts by weight based on 100 parts by weight in total of (A-V) and (B).
  • all constituent ratios of each component are expressed in terms of solid content.
  • the ratio of each component constituting the recording sheet resin composition is within a range that does not impair ink absorption, water resistance, print image quality, gloss, roll adhesion, and the like. Can be selected with.
  • the saponified vinyl acetate copolymer (B) affects the ink absorbency and the trace adhesion of Gizarol
  • the degree of polymerization of the saponified vinyl acetate copolymer (B) affects the print quality such as beading.
  • the modifier (R) affects the print quality, such as water resistance, adhesion to the substrate, and beading.
  • the fifth aspect of the present invention relates to the relationship between the composition ratio among the above three types of components of the resin composition for an ink jet recording sheet according to the present invention and the properties of a recording sheet when the composition is used as an image receiving layer material. Will be described as a representative.
  • the mixing ratio of the cationic (meth) acrylic copolymer (A-V) and the saponified vinyl acetate copolymer (B) is (70-100% by weight) / (0-30% by weight) (B) exceeds 30% by weight, the ink absorbency increases, but (B) tends to soften due to ink absorption, so that gizarol marks are likely to adhere. It is not preferable.
  • (A-V) has a characteristic that no gizarol mark adheres because the degree of softening is small even when ink is absorbed.
  • (A-V) general cationic (meth) acrylic copolymers other than (AV) have low ink absorbency, but (A-V) according to the present invention includes monomers (a,) and (a) having a polyalkylene oxide group. Since the hydrophilic group-containing monomer (a 2 ) is used as a constituent monomer, it has a relatively high ink absorption, and a good printed image can be obtained.
  • the modifier (R) is blended in a ratio of 0 to 15 parts by weight based on 100 parts by weight of the total of (AV) and (B). Tends to decrease the ink absorbency of the ink, which tends to affect the image quality.
  • the composition ratio of the resin composition for an ink jet recording sheet according to the fifth aspect of the present invention can be adjusted by considering the various influences and trends which are problematic as described above, when the cationic (meth) acrylic copolymer (A-V ) 70 to 100% by weight, saponified vinyl acetate copolymer (B) 0 to 30% by weight (total of both is 100% by weight), and 100 parts by weight of (AV) and (B) in total And a modifier (R) having a composition of 0.2 to 10 parts by weight is more preferable; more preferably, (AV) 75 to 95% by weight, (B) 5 to 25% by weight,
  • the mixing ratio is 0.5 to 5 parts by weight of (R) based on 100 parts by weight of the total of (A-V) and (B).
  • the monomer ( ai ) having a polyalkylene oxide group (polyoxyalkylene group) constituting the cationic (meth) acrylic copolymer (A-IV to AV) has a polyalkylene oxide group, Copolymerizable with a hydrophilic group-containing monomer (a 2 ), a cross-linkable group-containing monomer ( a 3 ), a cationic monomer (a 4 ) or a nonionic monomer (a 5 )
  • Examples of such monomers include acrylate monomers containing a polyalkylene oxide group, such as mono, di, tri, or monoesters of polyalkylene glycol and (meth) acrylic acid.
  • vinyl monomers having an oxyalkylene group exemplified in the description of the component of the genated product (B) of the vinyl acetate copolymer are preferably used. it can.
  • preferred monomers include (meth) acrylates, which are vinyl monomers in which the oxyalkylene group is an oxyethylene group, particularly polyoxyalkylene (meth) aryl ethers (among others, polyoxyethylene aryl ether). .
  • vinyl monomers can be used alone or in combination of two or more.
  • the structural formula of alkylene O key side groups of these monomers the general formula: A [(CHR one n - ⁇ ] m - represented by R 2.
  • R 1 represents a hydrogen atom, a methyl group or a hydroxyl group
  • R 2 represents a hydrogen atom or a methyl group
  • n represents a number of 1 to 5
  • m represents a number of 1 to 20
  • n m R 1 's may be the same or different from each other.
  • n exceeds 5
  • m exceeds 20
  • the stickiness becomes severe, which is not preferable. More preferably, n is 2-3 and m is 2-9.
  • hydrophilic group-containing monomer (a 2 ) constituting the cationic (meth) acrylic copolymer (A-IV to AV) examples include the crosslinkable group-containing cationic (meth) acrylic copolymer (A-IV).
  • the hydrophilic group-containing monomers exemplified in the description of ⁇ - ⁇ to ⁇ - ⁇ ) can be used similarly.
  • monomers preferred are those containing a carboxyl group-containing monomer [(me Evening) acrylic acid and the like, and hydroxyl-containing monomers [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate].
  • the crosslinkable group-containing monomer (a 3 ) used in the cationic (medium) acrylic copolymer (A-IV to AV) includes the crosslinkable group-containing cationic (meth) acrylic
  • the crosslinkable group-containing monomers exemplified in the description of the copolymers ( ⁇ - ⁇ to ⁇ - ⁇ ) can be used in the same manner.
  • preferred crosslinkable group-containing monomer hydrolytic condensable group, especially alkoxysilyl groups (methoxy silyl groups, C such as ethoxy silyl group, - 4 such as alkoxy Kishishiriru group) to have Monomer.
  • alkoxysilyl groups methoxy silyl groups, C such as ethoxy silyl group, - 4 such as alkoxy Kishishiriru group
  • Examples of the cationic monomer (a 4 ) constituting the cationic (meth) acrylic copolymer (A-IV to AV) include the crosslinkable group-containing cationic (meth) acrylic copolymer.
  • the cationic monomers exemplified in the description of (A-): to A-m) can be similarly used.
  • These monomers are generally used as monomers constituting the cationic (meth) acrylic copolymer (A-1V to AV), and are generally different from the above-mentioned various monomers in terms of film formability and film properties. It is used in combination with the nonionic monomer ( a5 ) for preparation.
  • Nonionic monomer (a 5) intended to be used as a non-ionic monomers exemplified in the description of the crosslinking group-containing cationic acrylic copolymer ( ⁇ - ⁇ ⁇ - ⁇ ) is preferably Can be used.
  • nonionic monomer (a 5) usually (meth) acrylic acid C, - 1 8 Ji al Kill ester [in particular acrylic acid 2.
  • Alkyl esters ⁇ alkyl methacrylates], aromatic vinyls [especially styrene], and vinyl esters [especially vinyl acetate] are used.
  • These non-ionic monomer (a 5) may be used alone or in combination on two or more.
  • the amounts of the cationic monomer (a 4 ) and the crosslinkable group-containing monomer (a 3 ) can be selected within a range that does not impair water resistance and ink absorbency.
  • cation on monomer (a 4) are preferably cationic acrylic copolymer (a-IV) configuration 0.1 to 50% by weight (for example, 1 to 45% by weight), more preferably 0.5 to 40% by weight (for example, 2 to 35% by weight), and especially It is preferably about 1 to 30% by weight (for example, 3 to 25% by weight), and usually about 2 to 25% by weight.
  • the amount of the crosslinkable group-containing monomer (a 3) is preferably from 0.1 to 2 5% by weight of the total monomers, more preferably from 0.2 to 20% by weight, in particular rather preferable 0 It is about 5 to 15% by weight, and usually about 0.3 to 10% by weight.
  • the proportion of each monomer can be selected in consideration of the preferable ranges of the components (A-IV ⁇ A- V) constituting the (a ⁇ (a 5).
  • the monomer (a) having a polyalkylene oxide group is preferably 0.1 to 40% by weight, more preferably 3 to 35% by weight. %, Particularly preferably 5 to 30% by weight, hydrophilic group-containing monomer
  • (a 2 ) is preferably 0.1 to 50% by weight, more preferably 2 to 45% by weight, particularly preferably 5 to 40% by weight
  • the crosslinkable group-containing monomer (a 3 ) is preferably 0.5 to 20 wt%, more preferably 1 to 1 5% by weight, particularly preferably from 2 to 1 0 wt%
  • cationic monomer (a 4) is preferably 1 to 40 wt%, more preferably 3-3 5 wt%, particularly preferably 5 to 30 wt%
  • the hard monomer (a 6) is preferably 1 0 to 60 wt%, more preferably 20 to 5 5 wt%, particularly preferably 25 to 50 weight %
  • the soft monomer (a?) Is preferably from 10 to 60% by weight, more preferably from 15 to 50% by weight, particularly preferably from 20 to 45% by weight.
  • Preferred embodiments of the cationic acrylic copolymer (AV) include a polyalkylene oxide group-containing (meth) acrylate monomer (a!), Preferably 8 to 40% by weight, more preferably 12 to 30% by weight, particularly preferably 1 5 to 25% by weight, the hydrophilic group-containing monomer (a 2), preferably 1 to 30 wt%, more preferably 2 to 20% by weight, particularly preferably from 4 to 5 wt%, cross-linked Functional group-containing monomer (a 3 ), preferably 0.2 to 10% by weight, more preferably 0.4 to 6% by weight, particularly preferably 0.7 to 3% by weight, cationic monomer (a 4), preferably 1 0 to 50 wt%, more preferably 20-40% by weight, particularly preferably 25 to 35 wt%, content of 10 to 80% by weight of non-ionic monomer (a 5), more preferably 20 to 70 wt%, particularly preferably 30 to 60 % By weight.
  • a! polyalkylene oxide group-containing (
  • the weight average molecular weight of the cationic (meth) acrylic copolymer (A-IV ⁇ AV) include, but are not limited especially, preferably, 0. 2 X 1 0 4 ⁇ 1 0 0 X 1 0 4 More preferably, there can be mentioned cationic acrylic copolymers (A-IV to AV) which can be selected from the range of 1 ⁇ 10 4 to 50 ⁇ 10 4 . If it is less than 0.2 ⁇ 10 4 , the amount of low molecular weight components increases, which causes the fogging. On the other hand, if it exceeds 100 ⁇ 10 4 , the viscosity becomes high, which causes inconvenience in production.
  • the glass transition temperature of the cationic (meth) acrylic copolymer (A-IV to AV) can be selected within a range that does not impair the film-forming property and the like, and is preferably, for example, from 1 to 50, and more preferably from ⁇ 10 to 50. To 40 ° (: particularly preferably about 0 to 30.
  • the polymer having such a glass transition temperature includes the cationic monomer (a 4 ), the crosslinkable group-containing monomer (a 3 ) and other monomers can be prepared by combining appropriate.
  • the monomer is usually a non-ionic monomer (a 5) Hadomonoma one [e.g.,
  • a copolymer is formed in combination with a monomer such as an alkyl ester which forms a homopolymer having a glass transition temperature of about 85 to 10 ° C (particularly -85 to 120 ° C).
  • the polymerization mode of the cationic (meth) acrylic copolymer (A-IV to AV) composed of the monomers is not particularly limited. Accordingly, the obtained copolymer may be, for example, any of a random copolymer, a graft copolymer, a block copolymer and the like.
  • the form of the cationic (meth) acrylic copolymer (A-IV to A-V) is although it may be a solution such as an aqueous solution, it is usually in the form of a cationic emulsion (particularly an aqueous emulsion).
  • Cationic emulsions containing such cationic (meth) acrylic copolymers can be prepared by a conventional method, for example, by using a nonionic surfactant and a Z- or surfactant surfactant.
  • the surface potential ( ⁇ potential) of the polymer particles contained in the cationic emulsion is, for example, preferably +10 to +60 mV, more preferably +12 to 150 mV (for example, +15 To +55 mV), particularly preferably about +20 to +55 mV.
  • the surface potential ( ⁇ potential) of the polymer particles can be similarly measured under the above conditions.
  • the average particle size of the polymer particles in the cationic emulsion is, for example, about 1 to 200 nm, preferably about 3 to 100 nm, and more preferably about 5 to 50 nm.
  • the cationic emulsion containing such a cationic acryl copolymer (A-IV to AV) can be prepared by a conventional method, for example, an emulsion polymerization system containing a nonionic surfactant and Z or a cationic surfactant.
  • the saponified product of the vinyl acetate copolymer is preferably used as the saponified product of the present invention.
  • the saponified product (B) of the vinyl acetate copolymer described in II can be preferably used.
  • Those preferably used as the modifier (R) in the IV and V of the present invention include the aqueous polyurethane resin composition (C 1) and / or the aqueous polyester resin composition. (El).
  • the aqueous polyurethane resin composition (C1) and the aqueous polyester resin composition (E1) are the same as the aqueous polyurethane resin composition (C1) and the aqueous polyester resin composition (E1) in the second aspect of the present invention. is there.
  • the composition (P) constituting the ink image-receiving layer comprises a polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group and a (meth) acrylate polymerizable unsaturated monomer.
  • a polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group and a (meth) acrylate polymerizable unsaturated monomer is a hydrolyzable silyl group-containing (methyl) acrylate copolymer (A-VI) obtained by copolymerizing a monomer containing the monomer (a 9 ).
  • Examples of the polymerizable unsaturated monomer having a hydrolyzable silyl group (a 8 ) include a polymerizable unsaturated monomer having a silyl group represented by the following general formula (1).
  • RR 2 and R 3 may be the same or different from each other, and include a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyloxy group, and a hydroxyl group.
  • a halogen atom an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyloxy group, and a hydroxyl group.
  • R 1 , R 2 and R 3 constituting the silyl group represented by the general formula (1) can be selected from the above-mentioned various groups. Usually, at least one of them is a halogen atom, an alkoxy group or It is preferably a hydroxyl group.
  • the hydrogen atom mentioned here includes fluorine, chlorine, bromine and iodine, but usually a chlorine atom is preferable.
  • alkyl group examples include methyl, ethyl, propyl, butyl, pentyl, and hexyl. Alkyl groups can be exemplified as suitable groups.
  • aryl groups such as phenyl groups are C e-!
  • An aryl group can be exemplified as a suitable group
  • an aralkyl group is a C--such as a benzyl group.
  • An aralkyl group can be exemplified as a suitable group.
  • alkoxy groups examples include d alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, and dodecyloxy.
  • Alkoxy groups are more preferred, and methoxy and ethoxy groups are particularly preferred.
  • the alkoxy group also includes, for example, an alkoxy-alkoxy group such as a methoxyethoxy group.
  • aryloxy groups such as phenoxy group.
  • Preferred examples of the aryloxy group include, and preferred examples of the acyloxy group include C 2-6 acyloxy groups such as acetyloxy (acetoxy), propionyloxy, and butyryloxy.
  • the amino group also includes an amino group which may have a substituent such as a dimethylamino group, and the aminooxy group may have a substituent such as a dimethylamino group.
  • suitable groups include a dimethylamino group and a dimethylamino group.
  • alkylthio group a C-6 alkylthio group such as a methylthio or ethylthio group can be exemplified as a suitable group.
  • Examples of the polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group include the following monomers.
  • R 4 is a C.! Alkyl group, Cs- 1 £ 1 aryl group or aralkyl group, R 5 is a hydrogen atom or a methyl group, X is fluorine, chlorine, bromine or iodine. Represents an atom, and a represents an integer of 0 to 2.
  • Specific examples of the compound represented by the general formula (2) include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinylmethylphenylchlorosilane, isopropenyltrichlorosilane, isopropenylmethyldichlorosilane, and isopropenyldimethylchlorosilane. And isopropenylmethylphenylchlorosilane.
  • Specific examples of the compound represented by the general formula (3) include aryltrichlorosilane, arylmethyldichloromethane, aryldimethylamine and the like.
  • Specific examples of the compound represented by the general formula (4) include 2- (meth) acryloxyethyltrichlorosilane, 3- (meth) acryloxypropyltrichlorosilane, and 2- (meth) acryloxyl Examples thereof include tylmethyldichlorosilane, 3- (meth) acryloxypropylmethyldichlorosilane, 2- (meth) acryloxyshetyldimethylchlorosilane, and 3- (meth) acryloxypropyldimethylchlorosilane.
  • R 4 , R 5 and a are the same as described above.
  • R 6 represents d- ie alkoxy group.
  • R 7 represents either an alkylene group or a phenylene group.
  • Specific examples of the compound represented by the general formula (7) include 2- (meth) acryloxyethyltrimethoxysilane and 2- (meth) acryloxyshethyltriethoxysila. 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) -acryloxypropylmethyldimethoxysilane, 3- (meta) ) 1-acryloxypropyl tris (2-methoxyethoxy) silane and the like.
  • Specific examples of the compound represented by the general formula (8) include 3- [2- (aryloxycarbonyl) phenylcarbonyloxy] propyldimethoxymethylsilane and 3- [2- (aryloxycarbonyl) phenylcarbonyl Oxy] propylmethoxydimethylsilane, 3- [2- (aryloxycarbonyl) phenylcarbonyloxy] propyltrimethoxysilane, 3_ [2- (isoprobenylmethoxycarbonyl) phenylcarbonyloxy] propyldimethoxy Methylsilane, 3—
  • R 4 , R s , R 6 and a are the same as above.
  • R 8 represents a fuylene group or
  • Specific examples of the compound represented by the general formula (9) include 3- (vinylphenylamino) propyl trimethoxysilane, 3- (vinylphenylamino) propyltriethoxysilane, and 3- (vinyl benzyl) Examples thereof include (amino) propyltriethoxysilane and 3- (vinylpenzylamino) propyltriethoxysilane.
  • Specific examples of the compound represented by the general formula (10) include 3- [2- (N-vinylphenylmethylamino) ethylamino] propyltrimethoxysilane and 3_ [2- (N-isopropenyl) Phenylmethylamino) ethylamino] propyltrimethoxysilane and the like.
  • Specific examples of the compound represented by the general formula (11) include 2- (vinyloxy) ethyltrimethoxysilane, 3- (vinyloxy) propyltrimethoxysilane, 4- (vinyloxy) butyltriethoxysilane, and 2- (vinyloxy) butyltriethoxysilane. Isoprobenyloxy) ethyltrimethoxysilane and the like.
  • R 9 is one CH 20 —
  • R 4 , R 5 , R 6 , n and a are the same as described above.
  • M represents an integer of 1 to 12.
  • Specific examples of the compound represented by the general formula (13) include 3-[(meth) acryloxyethoxy] propyl trimethoxysilane, 3-[(meth) acryloxyethoxy] propyldimethoxymethylsilane, and the like.
  • polymerizable unsaturated monomer having a hydrolyzable silyl group (a 8) in addition to the above illustration, for example, divinyl dimethoxysilane, divinyl jet silane, divinyl di (/ 3-Metokishetokishi) silane May be a divinyl group-containing monomer.
  • a silyl group-containing monomer may include, for example, a vinyl monomer containing an alkoxysilyl group, from the viewpoints of handleability, economy, and suppression of side reactions. Is preferred.
  • the composition (P) comprises a polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group and a (meth) acrylate-based polymerizable unsaturated monomer described below. obtained by copolymerizing a monomer containing (a 9), hydrolyzable silyl group-containing (meth) ⁇ Kurire Bok based copolymer (a-VI) and one of the main components.
  • the (meth) acrylate-based polymerizable unsaturated monomer (a 9 ) can be used alone or in combination of two or more.
  • the above copolymerization component as the (meth) acrylic polymerizable unsaturated monomers in (a 9), for example (menu evening) Akurireto, (meth) acrylamides include (meth) Atari Ronitoriru like.
  • Examples of the (meth) acrylate include alkyl (meth) acrylate [eg, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate.
  • C,- ⁇ alkyl such as acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc.
  • (Meth) acrylate, etc.) cycloalkyl (meth) acrylate [eg, hexyl hexyl (meth) acrylate, etc.], aryl (meth) acrylate [eg, phenyl (meth) acrylate, etc.], aralkyl (meth) acrylate [eg, benzyl] (Meth) acrylate, etc., hydroxyalkyl (meth) acrylate
  • (meth) acrylamides As the (meth) acrylamides, (meth) acrylamide, hydroxy Shiarukiru (meth) acrylamides [such as N- methylol (meth) Akurirua bromide or the like N- hydroxy-C -! 4 alkyl (meth) acrylamide], Arco Kishiarukiru Examples thereof include (meth) acrylamide (eg, N- 4 alkoxy-C! 4 alkyl (meth) acrylamide such as N-methoxymethyl (meth) acrylamide) and diacetone (meth) acrylamide.
  • Preferred as the (meth) acrylate-based polymerizable unsaturated monomer (a 9 ) according to the present invention are (meth) acrylates (for example, 18 alkyl (meth) acrylate, hydroxy-C 2-4 alkyl (methacrylate), and glycidyl.
  • (meth) Akuri rate, di C physician 4 alkylamino over C 2 - 4 other alkyl (meth) Akurireto etc.] can be exemplified (meth) acrylamide, in a more preferred, C 2 - Alkyl ⁇ chestnut rate, alkyl methacrylate, hydro alkoxy C 2 - 3 alkyl (meth) Akurireto, glycidyl (meth) Akurireto, di (3, - can be exemplified 3 alkylamino over C 2 3 alkyl (meth) Akurireto like.
  • Hydrolyzable silyl group-containing according to the present invention is those obtained by copolymerizing a monomer containing (a 8) and (a 9) , the latter of 9), or (further added to other a 9), hard monomers in order to adjust the glass transition temperature (Tg) of the copolymer [for example (meth) acrylate, glass, such as styrene A monomer component that forms a homopolymer having a transition temperature of about 80 to 120 ° C (especially 90 to 105 ° C)], and a soft monomer [for example, acrylic acid. 2-.
  • a monomer component that forms a single polymer having a glass transition temperature of about 85 to 110 ° C (particularly about 85 to 120 ° C) such as an alkyl ester is often used in combination.
  • a carboxyl group As described above, as (a 9 ), or in addition to (a 9 ), a carboxyl group
  • a monomer component having an ionic functional group such as a diamino group [eg, dialkylaminoalkyl (meth) acrylate] has an advantage that an aqueous resin composition can be obtained without using an emulsifier.
  • the range of the amount of each monomer component used is not limited.
  • a preferred range of each of (a 8 ) and (a 9 ) is the following range (here, the sum of (a 8 ) and (a 9 ) is 100% by weight), and is appropriately selected in this range. Is preferred.
  • the ratio of the amount used is not particularly limited, but the preferred range is the following range (here, the total of these is 100% by weight), and it is preferable to appropriately select within this range. .
  • Hard monomer 0 to 90% by weight [preferably 10 to 80% by weight, more preferably 15 to 75% by weight, particularly preferably 20 to 70% by weight]
  • Soft monomer 0 to 90% by weight [preferably 10 to 80% by weight, more preferably 15 to 75% by weight, particularly preferably 20 to 70% by weight]
  • Ionic group-containing monomer 0 to 90% by weight [preferably 1 to 50% by weight, more preferably 2 to 20% by weight, particularly preferably 2 to 10% by weight] (Aspects of using A-VI)
  • the hydrolyzable silyl group-containing (meth) acrylate copolymer (A-VI), which is one of the main components of the composition (P) according to the present invention, comprises an aqueous solution, an aqueous emulsion (aqueous polymer). Emulsion), non-aqueous organic solvent solution, non-aqueous organic solvent emulsion, solid powder, etc., although there is no particular problem in use, but handling, manufacturing, or other main component inorganic compound fine particles From the viewpoint of handling when producing the composition (P) from (G), the aqueous resin is preferably used.
  • a polymerizable compound having a hydrolyzable silyl group can be used without using a special cross-linking resin such as a cross-linked product of an acrylic silicone oligomer having a hydrolyzable alkoxysilyl group. Because it is an aqueous resin component composed of a copolymer of an unsaturated monomer (a 8 ) and a copolymerizable component such as a (meth) acrylate polymerizable unsaturated monomer (a 9 ). Easy to handle.
  • the average particle size of the polymer particles is from 0.01 to 2 m, preferably from 0.01 to l ⁇ m, and more preferably from 0.01 to 1 m. To 0.5 m, more preferably about 0.01 to 0.3 xm. The selection from these ranges is made so as not to impair the dispersion stability, adhesion and the like.
  • the method for preparing the aqueous solution or the aqueous emulsion of the hydrolyzable silyl group-containing (meth) acrylate copolymer (A-VI) is not particularly limited.
  • the copolymer obtained by copolymerizing the monomer with an alkali eg, an alkanolamine such as triethylamine, a cyclic amine such as morpholine, an alkanolamine such as triethanolamine, pyridine, ammonia, etc.
  • an alkali eg, an alkanolamine such as triethylamine, a cyclic amine such as morpholine, an alkanolamine such as triethanolamine, pyridine, ammonia, etc.
  • an acid inorganic Acids (eg, hydrochloric acid, sulfuric acid, etc.), organic acids (eg, carboxylic acids such as acetic acid, propionic acid, etc.) Acid or the like)
  • the copolymer may be prepared by a solution polymerization method, or may be prepared by an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, or the like.
  • the polymerization system may be either a batch system or a continuous system.
  • an organic solvent for example, an alcohol (ethanol, isopropanol, n-butanol, etc.), an aromatic hydrocarbon,
  • the organic solvents may be used alone or in combination of two or more.
  • organic solvent alcohols such as isopropanol, aromatic hydrocarbons such as toluene, and ketones such as methylethyl ketone are usually used.
  • the amount of the organic solvent used is not particularly limited, but (organic solvent) Z (total amount of monomers) is preferably 0.1 to 1/1 to 5/1 (weight ratio), and more preferably 0.1 to 5/1. It is selected from the range of about 5/1 to 2Z1 (weight ratio).
  • polymerization may be initiated by irradiation with an electron beam or ultraviolet light or by heating. In many cases, polymerization is started using a polymerization initiator.
  • the polymerization initiator As the polymerization initiator, the polymerization initiator exemplified in the description of the polyurethane graft polymer mixture (D) can be used.
  • the amount of the polymerization initiator to be used is, for example, preferably from 0.001 to 20% by weight, and more preferably from 0.01 to 20% by weight based on the total weight of the monomers (silyl group-containing monomer and copolymer). 10 weight % Is more preferable, and 0.1 to 10% by weight is particularly preferable, and is usually selected from this range.
  • the reaction temperature in the solution polymerization is preferably about 50 to 150 ° C, more preferably about 70 to 130 ° C.
  • the reaction time is preferably about 1 to 10 hours, more preferably about 2 to 7 hours.
  • the end point of the polymerization was confirmed by the disappearance of the double bond absorption (1648 cm- 1 ) in the infrared absorption spectrum or the reduction of unreacted monomers by gas chromatography. can do.
  • an emulsifier for example, an anionic surfactant such as an alkyl sulfate, an alkyl aryl sulfonate, an alkyl phosphate or a fatty acid salt, an alkylamine Salts, cationic surfactants such as alkyl quaternary ammonium salts, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl ethers, and polyoxyethylene-polyoxypropylene condensates from Asahi Denka Co., Ltd.
  • an anionic surfactant such as an alkyl sulfate, an alkyl aryl sulfonate, an alkyl phosphate or a fatty acid salt, an alkylamine Salts
  • cationic surfactants such as alkyl quaternary ammonium salts, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl ethers, and polyoxyethylene-polyoxypropylene condensates from As
  • a nonionic surfactant such as a pull-mouth nick type, an amphoteric surfactant such as a carboxylate type (amino acid type, betaine type, etc.) or a sulfonate type can be used.
  • the pH of the emulsion may be adjusted with a pH adjuster.
  • the copolymer When the copolymer is made aqueous, when the copolymer contains a cationic group such as an amino group, an imide group and a cation-forming group, the use of an acid improves the hydrophilicity, The coalescence can be easily dissolved or emulsified.
  • a cationic group such as an amino group, an imide group and a cation-forming group
  • Such acids include inorganic acids (hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, etc.), organic acids [saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, etc .; saturated aliphatic acids such as oxalic acid, adipic acid, etc. Polycarboxylic acids; unsaturated aliphatic monocarboxylic acids such as (meth) acrylic acid; unsaturated aliphatic polycarboxylic acids such as maleic acid and itaconic acid; aliphatic oxycarboxylic acids such as lactic acid and citric acid]; it can.
  • the amount of the acid used can be selected, for example, from the range of about 0.3 Z 1 to 1.5 / 1 (molar ratio) based on the total of the cationic groups.
  • the use of a base can easily dissolve or emulsify the copolymer.
  • bases examples include organic bases (alkylamines such as triethylamine, cyclic amines such as morpholine, alkanolamines such as triethanolamine, pyridine, etc.), inorganic bases (ammonia, alkali metal hydroxides) Etc.).
  • organic bases alkylamines such as triethylamine, cyclic amines such as morpholine, alkanolamines such as triethanolamine, pyridine, etc.
  • inorganic bases ammonia, alkali metal hydroxides
  • the amount of the base used can be selected, for example, from the range of about 1 to 1.5 / 1 (molar ratio) based on the total number of acidic groups.
  • Emulsification of the copolymer obtained by solution polymerization can be performed in the presence or absence of an organic solvent.
  • a water-soluble organic solvent for example, an alcohol such as isopropanol or the like
  • the organic solvent may be removed after the emulsification by evaporation or the like, and the emulsion may contain the organic solvent.
  • a low-boiling organic solvent for example, a ketone such as methyl ethyl ketone
  • an additive for example, an emulsifier, a pH adjuster, an acid, etc.
  • water is added to an organic solution containing the copolymer, and then water is added. It can be added and emulsified. In this case, it is preferable that water is gradually added by dropping or the like.
  • the temperature at the time of emulsification is preferably a low temperature, preferably 70 ° C or less (for example, 5 to 70 ° C), more preferably 50 ° C or less (for example, 10 to 50 ° C). It is selected from a range of degrees.
  • Removal of the organic solvent after emulsification by adding water is performed, for example, at 80 ° C or less (5 to 80 ° C ), At normal pressure or under reduced pressure (for example, about 0.001 to 1 atm).
  • the monomer according to the present invention ((& 8) and (& 9) or (& 8), (a 9) and (ao))
  • a batch charging method for each monomer for example, a method for charging each monomer in an aqueous medium at a time and copolymerizing them
  • a monomer addition method a method in which each monomer is individually added to an aqueous medium, mixed and polymerized
  • the monomer may be used as a pre-emulsified pre-emulsion.
  • the emulsion may be emulsified using a polymerizable emulsifier as a copolymer component, or may be emulsified using an emulsifier.
  • polymerizable emulsifier examples include common polymerizable emulsifiers (including a (meth) aryl group or a (meth) acryl group as a polymerizable group, and a quaternary ammonium salt or a tertiary as an emulsifying functional group.
  • a cationic group such as an amine salt, an amino group or an imide group, an anionic group such as a sulfonate or a carboxylate, or a nonionic group such as an ethylene oxide group].
  • the amount of the polymerizable emulsifier used is, for example, preferably from 0.1 to 20% by weight, more preferably from about 0.5 to 10% by weight, based on the total amount of the monomers. You can choose.
  • a water-soluble polymerization initiator such as an inorganic peroxide among the polymerization initiators exemplified for the polyurethane-based graft polymer mixture (D) can be used.
  • a redox-type polymerization initiator system may be constituted.
  • emulsifier examples include an emulsifier that can be used in the emulsification of the solution polymer.
  • protective colloids partially saponified polyvinyl alcohol, carboxymethyl cellulose, Methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.
  • the emulsion may be adjusted for pH.
  • the conditions such as the temperature in the emulsion polymerization may be the same as those in the solution polymerization.
  • chain transfer agents such as alcohols such as catechol, thiols, and mercaptans (n_ lauryl mercaptan, n-dodecyl mercaptan, t-) are used to adjust the molecular weight of the copolymer.
  • chain transfer agents such as alcohols such as catechol, thiols, and mercaptans (n_ lauryl mercaptan, n-dodecyl mercaptan, t-) are used to adjust the molecular weight of the copolymer.
  • Dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, etc. may be used.
  • the ionicity of the emulsion is preferably non-ionic, and more preferably anionic.
  • hydrolyzable silyl group-containing (meth) acrylate copolymer (A-VI) is an aqueous resin
  • a fluororesin for example, a fluororesin, a silicone resin, or an organic resin
  • an aqueous resin for example, a fluororesin, a silicone resin, or an organic resin
  • Lubricants such as sulfonate compounds, organic phosphate compounds, organic carboxylate compounds, stabilizers such as antioxidants, ultraviolet absorbers, heat stabilizers, etc., radical scavengers, quenchers, antistatic agents,
  • Various additives such as a plasticizer, a thickener, and an antifoaming agent may be added.
  • composition (P) constituting the ink image-receiving layer according to the present invention comprises, as main components, a hydrolyzable silyl group-containing (meth) acrylate copolymer (A-VI) and inorganic compound-based fine particles (G). Things.
  • Examples of the inorganic compound fine particles (G) include oxides (including composite oxides and hydrates) of silica, alumina, white carbon, calcined diatomaceous earth, titanium dioxide, etc .; aluminum hydroxide, calcium hydroxide, water Hydroxides such as magnesium oxide; heavy calcium carbonate, light calcium carbonate, carbonates such as magnesium carbonate; calcium sulfate Sulfates such as shim; calcium silicate, magnesium silicate, talc, kaolin, delamikaolin, clay, bentonite, smectite, zeolite, magnesium aluminosilicate, sericite, etc .; Fine particles composed of an inorganic compound such as a clay mineral or a mixture thereof are exemplified.
  • the inorganic compound used in the present invention is not particularly limited, but preferred inorganic compound-based fine particles are inorganic compound-based fine particles such as silica and alumina. Beaded colloidal silica is preferred.
  • the bead-shaped colloidal silica dispersed in water is a colloidal suspension of silicon dioxide or a hydrate thereof, which is usually obtained by reacting an aqueous solution of silicate with dilute hydrochloric acid. Colloidal silica prepared by any method can be used.
  • the primary average particle diameter of the inorganic compound-based fine particles is usually preferably from 1 to 200 nm, more preferably from 5 to 100 nm, and most preferably from 15 to 50 nm.
  • the secondary particle size is preferably from 10 to 1000 nm, more preferably from 20 to 500 nm, and most preferably from 100 to 300 nm.
  • composition of composition (P) Composition of composition (P)
  • the weight ratio (%) between (A-VI) and (G), which are the main components of the composition (P) constituting the ink image-receiving layer, is determined when the (A-VI) component is aqueous, and ) Since each component may be colloidal silica dispersed in water, each component is preferably represented by a solid content equivalent (weight), and (A-VI) / (G) is 1 to 50Z50 to 99 (each numerical value). Is preferably in the range of 100% by weight).
  • composition (P) is preferably an aqueous liquid, and preferably an aqueous liquid adjusted to 10 to 50% by weight, depending on the method of forming the ink image receiving layer.
  • the method for producing the composition (P) containing the components (A-VI) and (G) as main components is not particularly limited, but both the components (A-VI) and (G) are solid. If there is
  • a method of dispersing in water by first order is preferred.
  • Either (A-VI) or (G) is aqueous, for example, (A-VI) is an aqueous emulsion and (G) component is dispersed in water.
  • silica the method of mixing by stirring as it is is preferable, and when either (A-VI) or (G) is a solid and the other is aqueous, the solid formed component is pulverized.
  • a method of dispersing with a homogenizer or the like is preferable.
  • the resin or resin composition used for forming the ink fixing layer is not particularly limited, but includes a hydrolyzable silyl group-containing (meth) acrylate copolymer (A-VI) or the hydrolyzable silyl group-containing (meth) acrylate copolymer (A-VI).
  • A-VI hydrolyzable silyl group-containing (meth) acrylate copolymer
  • A-VI saponified vinyl acetate copolymer
  • B water-based urethane graft polymer
  • a resin composition containing a blend with at least one resin selected from the group consisting of (D) and an aqueous polyester graft polymer mixture (E) is preferably used.
  • the cationic group-containing resin is preferably used alone or in the form of a resin composition comprising the other specific resin.
  • cationic group-containing resin examples include dicyan resins (dicyandiamide-formalin polycondensate), polyamine resins [aliphatic polyamines such as diethylenetriamine, triethylenetetramine, dipropylenetriamine, and polyallylamine; Aromatic polyamines such as bile diamine, condensates of dicyandiamide and (poly) C alkylene polyamines (such as polycondensates of dicyandiamide diethylenetriamine), and polycationic resins can be preferably exemplified.
  • dicyan resins dicyandiamide-formalin polycondensate
  • polyamine resins aliphatic polyamines such as diethylenetriamine, triethylenetetramine, dipropylenetriamine, and polyallylamine
  • Aromatic polyamines such as bile diamine, condensates of dicyandiamide and (poly) C alkylene polyamines (such as polycondensates of dicyandiamide diethylene
  • polycationic resin examples include an epichlorohydrin-di C alkylamine addition polymer (epichlorohydrin-dimethylamine addition polymer), a polymer of arylamine or a salt thereof (polyallylamine or a hydrochloride thereof).
  • Alkyl ammonium salt polymer di ( ⁇ -4 alkylamino Cyl (meth) acrylate quaternary salt polymer, diaryldi-4 alkylammonium salt-acrylamide copolymer (diaryldimethylammonium chloride-acrylamide copolymer, etc.), amine-monorubic acid copolymer Etc. can be exemplified.
  • cationic group-containing resins can be used alone or in combination of two or more. Further, in order to improve the water resistance of the ink fixing layer itself, it is preferable to use a resin having a ionic group having a crosslinkable reactive group.
  • a resin having a ionic group having a crosslinkable reactive group examples include, among the hydrolyzable silyl group-containing (meth) acrylate copolymers (A-VI), monomers having a cationic group or having a cationic property by acid neutralization.
  • a copolymer in which is used can be mentioned as a preferable example.
  • Examples of the saponified vinyl acetate copolymer used in the VI of the present invention include the saponified products of the present invention.
  • the vinyl chloride (B) of the vinyl acetate copolymer according to the invention (1) can be preferably used.
  • the proportion of the copolymerizable monomer can be selected within a range that does not impair the sharpness of the image, water resistance, etc., and the entire monomer used in the composition of the copolymer 0.1 to 5 Omo 1% is preferable, l to 30 mol% is more preferable, 2.5 to 25 mo 1% is more preferable, and 3 to 2 Omo 1% is particularly preferable. preferable.
  • a saponified product of one kind of vinyl acetate copolymer may be used, or a gently produced product of a plurality of vinyl acetate copolymers may be used.
  • a child (as described above) may be blended.
  • the aqueous polyurethane resin used in the VI of the present invention can be preferably used.
  • a poor solvent (K) for the cellulose derivative is contained in a proportion of 0 to 150 parts by weight.
  • the recording resin composition according to the Wth aspect of the present invention may further comprise: a recording resin composition in which the cellulose derivative (H) is cellulose acetate; and a poor solvent (K) ratio of the cellulose derivative of 50 to 15; 0 parts by weight of the recording resin composition and a good solvent for the cellulose derivative (I) Power Ketones, esters, ethers, cellosolves, cellosolve acetates, halogenated hydrocarbons and nitro compounds It may be a recording resin composition having at least one kind and a boiling point of 35 ° C. to 160 ° C.
  • the recording resin composition wherein the melting point of the organic acid (J) is 60 ° C. or more
  • Poor solvent for cellulose derivatives (K) At least one selected from esters, alcohols, ketones, and ethers, and having a boiling point of 100 to 300 ° C and a good recording resin composition.
  • the recording resin composition may be at least one selected from dialkyl ketones and C ethers.
  • the present invention relates to a recording medium wherein the difference in boiling point between the good solvent (I) and the poor solvent (K) of the cellulose derivative (TK-T I) is 10 ° C ⁇ (TK-T I) ⁇ 20 o ° c.
  • the resin composition may be a recording resin composition in which the solubility of the organic acid (J) in water at 20 ° C. is 2 gZl or less than 100 ml.
  • Cellulose derivatives (H) used in the present invention include cellulose esters such as organic acid esters such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butylate, cellulose nitrate, and sulfuric acid.
  • Inorganic acid esters such as cellulose and cellulose phosphate, mixed acid esters such as cellulose nitrate acetate, and cellulose ethers such as methyl cellulose, ethyl cellulose, isopropyl cellulose, butyl cellulose, benzyl cellulose, hydroxyethyl cellulose, and carboxymethyl cell Oral, carboxyethyl cellulose, cyanoethyl cellulose and the like.
  • cellulose esters are preferably used, and cellulose acetate is more preferably used. These may be used alone or as a mixture. Further, another polymer may be added as needed.
  • Examples of good solvents (I) for cellulose derivatives include acetone and methylethyl.
  • C 1-5 dialkyl ketones such as ketone, methyl propyl ketone, methyl butyl ketone and methyl isobutyl ketone; ketones such as cyclohexanone;
  • C- 4 alkyl esters of formic acid such as ethyl formate; methyl acetate; ethyl acetate; butyl acetate C-4 alkyl esters such as acetic acid, esters such as ethyl propionate and ethyl lactate, and cyclic or linear C 46 such as 1,4-dioxane, tetrahydrofuran, tetrahydropyran, getyl ether, diisopropyl ether, dimethoxyethane, etc.
  • Ethers such as ethers, cellosolves including C4 alkyl cellosolves such as methylcellosolve, ethylselvsolve, butylcellesolve, etc., cellosolve acetates (C-4 alkylcellosolves such as methylcellesolvesolve, ethylcellesolvesolve, etc.) Seteto), benzene, toluene, xylene and the like aromatic hydrocarbons, methylcarbamoyl Ren chloride, halogenated hydrocarbons such as ethylene chloride, formamide, Asetoamido,
  • Amides such as N-methylformamide, N-methylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, acetonitrile, propionitrile, ptyronitrile, benzonitrile And organic acids such as organic acid anhydrides (maleic anhydride, acetic anhydride), and mixtures thereof.
  • Good solvents for example, lower alcohols (e.g., 4- alkyl alcohols such as methanol, ethanol, isopropanol and butanol, diacetone alcohol, etc.), cycloalkanols (cyclopentanol, cyclohexanol, methylcyclohexanol, dimethyl cyclohex is C alkyl group such as hexanol may be substituted C 4 - 8 cycloalkanol) or the like, depending on the kind of the resin may become poor solvent.
  • Good solvents may include nitro compounds (nitromethane, nitroethane, nitropropane, etc.).
  • a solvent that is at least one selected from the group of these solvents and has a boiling point of 35 ° C. to 160 ° C. is preferably used.
  • preferred good solvents include acetone, methyl ethyl ketone, ethyl acetate, dioxane, and dimethoxine.
  • acetone is preferably used.
  • Poor solvent means a solvent that has no solubility in the cellulose derivative used or is less soluble than the good solvent used, and has a higher boiling point than the above-mentioned good solvent used in combination.
  • the type is not particularly limited.
  • esters formic acid C 5, such as formic acid isoamyl - 8 alkyl ester, amyl acetate, carboxymethyl Le to acetic acid, acetic Okuchiru, 3-methoxybutyl acetate C 2-4 aliphatic carboxylic acid C 6 i which may have an alkoxyl group, such as 3-ethoxybutyl acetate, butyl propionate, 3-methoxybutyl propionate, alkyl ester, methyl benzoate, benzoic acid Benzoic acid d-4 alkyl esters such as ethyl, propyl benzoate, etc.), alcohols (Ce-!
  • aliphatic polyhydric alcohols ethylene glycol
  • Diethylene glycol ethylene glycol
  • propylene glycol polyethylene glycol
  • glycerin polyethylene glycol
  • Preferred poor solvents are amyl formate, cyclohexanol, methylcyclohexanol, ethyl benzoate, or mixtures thereof, especially cyclohexanol. Further, a solvent having a boiling point of 100 to 300 ° C is more preferable.
  • Examples of the organic acid (J) include formic acid, acetic acid, propionic acid, lactic acid, citric acid, oxalic acid, benzoic acid, sulfamic acid, fumaric acid, maleic acid, and fluoric acids (phthalic acid, isophthalic acid ) And p-toluenesulfonic acid. Of these, particularly preferred are fluoric acids and their derivatives. Among these, an organic acid having a melting point of 60 ° C. or more is more preferable.
  • a good solvent and a poor solvent examples include a good solvent (I) dialkyl ketone, C 1-4 alkyl acetate, cyclic or linear C 4-6 ether, and alcohol. Kiruserosorubu, and C -! 4 alkyl cellosolve is least one selected from acetate, a poor solvent for the cellulose derivative (K) Power formic acid C 5 - 8 alkyl Es ether, benzoic acid d - 4 alkyl ester, C4-8 cycloalkanol,. Dialkyl ketone and C 7-,. A combination of at least one solvent selected from ethers is also preferable.
  • a cellulose derivative (H) and an organic acid (J) are dissolved in a good solvent (I), and then a poor solvent (K) is added and stirred by a conventional method. And so on.
  • the recording resin composition contains conventional additives within a range that does not impair the properties of the present invention, for example, an antifoaming agent, a coating improver, a thickener, a heat stabilizer, a lubricant, an ultraviolet absorber, and lightfastness. Stabilizers, antistatic agents, cross-linking agents, anti-blocking agents and the like may be added.
  • the method for applying the recording resin composition to the base sheet is not particularly limited, and a known method such as roll coating, air knife coating, blade coating, bar coating, comma coating, or gravure coating can be used.
  • the applied resin layer is dried to obtain a recording sheet having an image receiving layer formed on a recording medium.
  • the drying method is not particularly limited, and when the dry phase inversion method is used, first, the good solvent evaporates to convert the cellulose derivative into micelles, and then the micelles contact each other due to the evaporation of the poor solvent to form a network structure. It is necessary to control the temperature, vapor pressure, etc. so that they form.
  • the corian resin composition of the present invention has the following general formula (14)
  • R 2 — H, — CH 3 or 1 OH
  • a plurality of R 2 may be the same or different from each other, and m (CHR 2) n ⁇ 1 may be bonded to a random or block.
  • the polymer (L) includes a monomer represented by the formula (14) (hereinafter sometimes referred to as a “(poly) alkylene oxide-modified monomer”), a cationic functional group-containing monomer, It may be composed of a copolymer with at least one monomer selected from a group-containing monomer and a hydrophilic group-containing monomer.
  • one component of a vinyl monomer having an oxyalkylene group used for the saponified product (B) of the vinyl acetate copolymer can be used in the same manner.
  • Examples of the cationic functional group-containing monomer used in the present invention include the cationic monomer used for the crosslinkable group-containing ionic (meth) acrylic copolymer ( ⁇ - ⁇ to ⁇ - ⁇ ). Can be used as well. (Crosslinkable group-containing monomer)
  • crosslinkable group-containing monomer used in the present invention is the same as the crosslinkable group-containing monomer used in the crosslinkable group-containing cationic (meth) acrylic copolymer (A-I to Am). Can be used.
  • hydrophilic group-containing monomer used for the (meth) acrylic copolymer (A-I to Am) can be used in the same manner.
  • the cationic functional group-containing monomer, the crosslinkable group-containing monomer, and the hydrophilic group-containing monomer can be used alone or in combination of two or more. Preferred combinations of the above monomers are as follows.
  • Cationic functional group-containing monomer di. 4- alkylamino-C2-8-alkyl (meth) acrylate or quaternary ammonium salt thereof
  • Crosslinkable group-containing monomer (meth) Akurirokishi - C 2 - 8 alkyl tri d-2 Arco Chishishiran
  • Hydrophilic group-containing monomer unsaturated carboxylic acid
  • These monomers are usually used in combination with a nonionic monomer to adjust film forming properties and film properties.
  • the nonionic monomer used for the crosslinkable group-containing cationic (meth) acrylic copolymer (A-II-III-III) can be used in the same manner.
  • the copolymer composed of the above monomers is not particularly limited with respect to the polymerization mode, and may be, for example, a random copolymer, a graft copolymer, a block copolymer, or the like.
  • composition of polymer (L) The content of the monomer of the formula (14) with respect to all the monomers of the polymer (L) is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, and most preferably 15 to 25% by weight. It is about.
  • the content of the monomer having a cationic functional group with respect to all monomers of the polymer (L) is preferably 1 to 50% by weight, more preferably 5 to 45% by weight, and a monomer having a crosslinkable group. Is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and most preferably about 1 to 5% by weight.
  • the content of the hydrophilic group-containing monomer is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, most preferably about 0.5 to 15% by weight, and the balance is a nonionic monomer, preferably 10 to 80% by weight. %, More preferably about 20 to 70% by weight.
  • the proportion of the monomers is preferably 5 to 300 parts by weight of the cationic functional group-containing monomer with respect to 100 parts by weight of the (poly) alkylene oxide-modified monomer of the formula (14). And more preferably about 10 to 250 parts by weight, a cross-linkable group-containing monomer is preferably 1 to 30 parts by weight, and more preferably about 5 to 20 parts by weight, and a hydrophilic group-containing monomer. Is preferably 5 to 80 parts by weight, more preferably about 10 to 60 parts by weight.
  • the glass transition temperature (Tg) of the copolymer constituting the polymer (L) can be selected within a range that does not impair the film-forming properties and the like, and is preferably -85 to 30 ° C, and more preferably -60 to 0 ° C. Most preferably, the temperature is about 50 to about 10 ° C.
  • the polymer having such a glass transition temperature is obtained by appropriately combining the cationic functional group-containing monomer, the crosslinkable group-containing monomer, and the hydrophilic group-containing monomer / non-ionic monomer. Can be prepared.
  • the monomer is usually a hard monomer, for example, a monomer which forms a homopolymer having a glass transition temperature of 80 to 120 ° (especially, about 90 to 105 ° C.) such as methyl (meth) acrylate and styrene. , glass transition temperature -85 one 10 °, such as acrylic acid C 2 alkyl ester (:., monomers, especially forming an 85-1 20 ° C approximately homopolymer
  • hot melt adhesive resin (M) used in the present invention various resins, for example, polyethylene, ethylene-propylene copolymer, olefinic resin such as acrylic polypropylene, ethylene-vinyl acetate copolymer, ethylene (Meth) acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene copolymer resin such as ionomer, nylon resin, polyester resin, polyurethane resin, acrylic resin, rubber, etc. Can be exemplified. These hot melt adhesive resins can be used alone or in combination of two or more. Hot melt adhesive resins are usually water-insoluble.
  • the hot melt adhesive resin may be a reactive hot melt adhesive resin having a reactive group such as a carboxyl group, a hydroxyl group, an amino group, an isocyanate group, or a silyl group at a terminal.
  • Preferred resins for imparting heat transferability and durability are nylon resins, polyester resins, and polyurethane resins.
  • a hot-melt adhesive resin composed of a nylon-based resin can impart excellent washing resistance and water resistance to a transferred image and a high texture when the object to be transferred is clothing or the like.
  • nylon-based hot melt adhesive resin a polyamide resin having at least one unit selected from nylon 11 and nylon 12 (e.g., homopolyamide such as nylon 11, nylon 12, nylon 61, nylon 6; Nylon 6 Z12, Nylon 6 Z12, Copolyamide such as copolymer of dimeric acid and diamine and lauric lactone or aminoundecanoic acid, formed by reaction of dimeric acid with diamine Polyamide resin and the like are included.
  • nylon 11 and nylon 12 e.g., homopolyamide such as nylon 11, nylon 12, nylon 61, nylon 6; Nylon 6 Z12, Nylon 6 Z12, Copolyamide such as copolymer of dimeric acid and diamine and lauric lactone or aminoundecanoic acid, formed by reaction of dimeric acid with diamine Polyamide resin and the like are included.
  • the polyester hot melt adhesive resin includes at least a homopolyester resin or a copolyester resin using an aliphatic diol.
  • Homopolyester resins include ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.
  • Polyoxy C 2 such as alkylene diol and jetty render glycol.
  • Aliphatic diene such as alkylene glycol
  • aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid, and, if necessary, a saturated aliphatic polyester resin formed by the reaction with lactone.
  • copolyester resin polyethylene Nterefu evening rate or ethylene glycol a part of the constituting components of the polybutylene terephthalate evening rate, propylene glycol, 1, other diol or the aliphatic, such as C 6 alkylene glycol such as 1,4-butanediol Saturated polyester resins substituted with dicarboxylic acids or lactones such as asymmetric aromatic dicarboxylic acids such as dicarboxylic acid, phthalic acid and isophthalic acid are included.
  • the polyurethane-based hot-melt adhesive resin includes, as at least a part of a diol component, a polyester resin using a polyester diol corresponding to the polyester-based hot-melt adhesive resin, and the diisocyanate component includes aromatic and aromatic fatty acids.
  • An aliphatic, cycloaliphatic or aliphatic diisocyanate can be used.
  • the hot melt adhesive resin may contain, for example, the following conventional additives, waxes, and the like.
  • the melting point of the hot melt adhesive resin is preferably in the range of 70 to 250 ° C, more preferably 70 to 200 ° C (:, most preferably 100 to: L50 ° C). You can choose from.
  • the hot melt adhesive resin is used as a powder.
  • the hot-melt adhesive resin is usually composed of a powdery resin having an average particle size larger than the thickness of the ink-receiving layer, so that the hot-melt adhesive resin is projected from the surface of the ink-receiving layer to effectively exhibit hot-melt adhesiveness. I have.
  • the average particle size of the hot melt adhesive resin is, for example, preferably about 1 to 100 urn, more preferably about 3 to 80 m, and most preferably about 5 to 50 ⁇ m.
  • the powder of the hot-melt adhesive resin may be a porous material in order to improve the ink absorbency and the washing resistance.
  • Polymer (L) Force When composed of a copolymer of the above-mentioned monomers, the polymer (L) (the copolymer) is preferably 100 to 150 parts by weight based on 100 parts by weight.
  • the resin composition of the present invention can be obtained by using about 0 parts by weight, more preferably about 100 to 900 parts by weight, particularly preferably about 80 to 900 parts by weight of a hot melt adhesive resin. .
  • a hot melt adhesive resin preferably about 80 to 900 parts by weight
  • a curing agent (a curing catalyst or a curing accelerator) may be added to the resin composition for an ink jet recording sheet according to any one of the Ith to Wth aspects of the present invention in order to promote a curing reaction.
  • the curing agent include organic tin compounds (dibutyltin dilaurate, dibutyltin dityltin diacetate, dibutyltin dimethoxide, tributyltin sulfate, dibutyltin thioglycolate, tin octoate, etc.), and organic aluminum compounds (aluminum isopropylate, aluminum tris ( Ethyl acetate acetate, aluminum tris (acetyl acetate), ethyl acetate aluminum diisopropylate, etc., organic titanium compounds (isopropyl tristearoyl titanate), tetraisopropyl bis (dioctyl phosphate) titanate, bis (d
  • curing agents can be used alone or in combination of two or more.
  • the amount of the curing agent used is within a range capable of accelerating the curing, for example, in terms of solid content, a crosslinked group-containing cationic acrylyl copolymer (A-I to A-VI) and a saponified product of a vinyl acetate copolymer (B) 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin composition composed of the hydrophilic polymer compound such as (B).
  • Dye fixatives usually have a cationic group (particularly a guanidyl group or a strong quaternary ammonium salt type cation group) in the molecule.
  • the dye fixative may be water-soluble.
  • the dye fixing agent examples include a dicyan fixing agent (dicyandiamide-formalin polycondensate), a polyamine fixing agent [aliphatic polyamines such as diethylenetriamine, triethylenetetramine, dipropylenetriamine, and polyallylamine; aromatic polyamines such as Renjiamin, dicyandiamide and a (poly) C 2 - 4 condensates of alkylene polyamines (dicyandiamide over diethylene Bok Riami down polycondensate)], polycationic fixing agent and the like.
  • a dicyan fixing agent (dicyandiamide-formalin polycondensate)
  • a polyamine fixing agent aliphatic polyamines such as diethylenetriamine, triethylenetetramine, dipropylenetriamine, and polyallylamine
  • aromatic polyamines such as Renjiamin, dicyandiamide and a (poly) C 2 - 4 condensates of alkylene polyamines (dicyandiamide over diethylene
  • polycationic fixing agent examples include epichlorohydrin-di-ci-4 alkylamine addition polymer (epichlorohydrin-dimethylamine addition polymer), and polymer of arylamine or a salt thereof (polyethylene).
  • Polymers of allylamine or its hydrochloride for example, Nitto Boseki Co., Ltd., PA-10C, PAA-HCL-3L, PAA-HCL-10L, etc.
  • polymer of diaryl Ci-4 alkylamine or its salt Polymer of diarylmethylamine or its hydrochloride, for example, Nitto Boseki Co., Ltd., PAS-M-1 Etc.
  • the amount of the dye fixing agent used is within a range in which the ink fixing property can be improved, for example, in terms of solid content, the crosslinkable group-containing cationic acrylic copolymer (AI A-VI) and the vinyl acetate copolymer Compound (B), the aqueous polyurethane resin composition (C), and in the m-th invention, 0.140 parts by weight based on 100 parts by weight of the resin composition obtained by further adding the block isocyanate compound (D). And more preferably 130 parts by weight, and further preferably 220 parts by weight.
  • the cationic (meth) acrylic copolymer (A-IV A-V), the saponified vinyl acetate copolymer (B), and the modifier (R) are used. It is preferably selected from a range of about 0.140 parts by weight, more preferably about 130 parts by weight, particularly preferably about 220 parts by weight based on 100 parts by weight of the resin composition. it can. If the amount is more than 40 parts by weight, the coloring of the dye becomes poor and the ink absorbency is reduced.
  • the ink image receiving layer obtained by coating the substrate with the resin composition according to the sixth aspect of the present invention has a 60 ° gloss of preferably 30% or more, more preferably 50% or more, and still more preferably. Is 70% or more.
  • a porous layer, an anti-blocking layer, a lubricating layer, an antistatic layer, and the like may be formed on the image receiving layer, if necessary.
  • the recording sheets according to the first to VK of the present invention are useful as recording sheets by an ink jet method in which ink droplets are ejected and recorded, but printing sheets such as offset printing and flexographic printing (particularly, It can also be used as a sheet for aqueous ink).
  • the ink jet recording sheet according to the present invention has a force obtained by applying the above-described resin composition to the recording sheet base material.
  • the image receiving layer formed by the application may optionally include other components, for example, An aqueous emulsion containing a polymer or polymer particles having no crosslinkable group (for example, an acrylic resin emulsion, an ethylene monoacetate copolymer emulsion, a vinyl acetate emulsion, etc.) may be contained. (Granules)
  • the image receiving layer may further contain a powder (eg, a pigment).
  • a powder eg, a pigment
  • the powders include inorganic powders (white carbon, finely divided calcium silicate, zeolite, magnesium aminosilicate, calcined silica, finely divided magnesium carbonate, finely divided alumina, silica, talc, kaolin, delamikaolin, Minerals such as clay, heavy calcium carbonate, light calcium carbonate, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, magnesium silicate, calcium sulfate, sericite, bentonite, smectite, etc.
  • Organic powder etc.
  • organic powder Ross-linked or non-cross-linked organic fine particles such as polystyrene resin, acrylic resin, urea resin, melamine resin, and benzoguanamine resin, and organic powders such as fine hollow particles.
  • These powders can be used alone or in combination of two or more.
  • various hydrophilic polymer compounds described above can be used as the binder resin.
  • the ratio between the powder and the granule is not particularly limited, but the powder is preferably 0.1 to 80 parts by weight, more preferably 0.2 to 50 parts by weight, based on 100 parts by weight of the binder resin. .
  • additives such as antifoaming agents, coating improvers, thickeners, surfactants, lubricants, and stabilizers (antioxidants, ultraviolet absorbers, heat Stabilizers, etc.), antistatic agents, anti-blocking agents and the like may be added.
  • the ink receiving layer in the ring-shaped thermal transfer sheet of the present invention is composed of the resin composition.
  • the ink receiving layer may contain a plasticizer to impart high flexibility to the transferred image.
  • the plasticizer include phthalate plasticizers such as ethyl phthalate, butyl phthalate, hexyl phthalate, octyl phthalate, 2-ethylhexyl phthalate, and lauryl phthalate.
  • Aliphatic dicarboxylic acid plasticizers such as 2-ethylhexyl adipate, dibutyl sebacate, and 2-ethylhexyl sebacate; glycol-based plasticizers such as ethyl phthalyl-ethyl dicholate; polyethylene glycol ester; phosphoric acid Examples thereof include phosphate plasticizers such as trifrenyl, tricresyl phosphate, and triethylhexyl phosphate, and epoxy plasticizers such as polyester plasticizers and epoxy fatty acid esters. These plasticizers can be used alone or in combination of two or more.
  • the amount of the plasticizer used is, for example, 100% by weight of the total amount of the resin components such as the polymer and the hydrophilic polymer constituting the ink receiving layer, the hot melt adhesive resin, the cationic polymer, and the urethane polymer resin. Parts by weight, preferably 0.1 to 30 parts by weight, Preferably, it can be selected from a range of about 1 to 25 parts by weight, particularly preferably about 1 to 20 parts by weight.
  • the ink receiving layer may contain, independently or together with the plasticizer, a dye fixing agent in order to improve the fixability of the colorant (dye).
  • the recording sheet of the present invention is provided with the image receiving layer, the ink absorbing property and the ink fixing property are high, and the problems of water resistance, printing quality, and adhesion of roll marks are remarkably improved. That is, the printing portion or the image portion is formed with water-based ink by the ink jet recording method without occurrence of image quality defects such as beading and roll mark adhesion, and the dried printing portion or the image portion is exposed to water at a temperature of 30 ° C for 1 minute. When immersed, the color density retention is 80% or more (for example, 85 to about L00%), and preferably 85% or more (for example, about 90 to 99%).
  • the recording sheet of the present invention can be manufactured by forming an image receiving layer made of a resin composition for a recording sheet on at least one surface of the base material.
  • the ink absorbing layer can be formed by applying a coating solution prepared using an appropriate solvent (water, a hydrophilic solvent which may be water-soluble, a hydrophobic solvent or a mixed solvent thereof) to a support.
  • an appropriate solvent water, a hydrophilic solvent which may be water-soluble, a hydrophobic solvent or a mixed solvent thereof
  • the resin composition containing the crosslinkable group-containing cationic (meth) acrylic copolymer (A-I to A-VI) is in the form of an aqueous emulsion, it is used in the form of an aqueous coating solution.
  • the coating solution can be applied by a conventional coating method including a casting coating method, for example, a mouth-coat, a knife-coat, a blade-coat, a rod-coat, a bar-coater, a comma-coat, a gravure-coat. It is applied to at least one side of the substrate by the overnight or silk screen method.
  • a casting coating method for example, a mouth-coat, a knife-coat, a blade-coat, a rod-coat, a bar-coater, a comma-coat, a gravure-coat.
  • the image receiving layer can be formed by applying a coating solution containing the above components to at least one surface of the substrate and drying. Further, if necessary, after the application liquid is applied, the crosslinked ink absorbing layer may be formed by heating at an appropriate temperature selected from a range of about 50 to 150 ° C.
  • Image receiving layer formed by resin composition for ink jet recording sheet according to the present invention is preferably 3 to 50 m, more preferably 6 to 30 im, but usually about 5 to 30 ⁇ .
  • the ink jet recording sheet obtained by using the resin composition according to the present invention includes the above-mentioned image receiving layer, the ink absorbing property and the ink fixing property are high, the water resistance, the print quality are remarkably improved, and the printing is performed. Even when used on a high-speed printing press, a clear, uniform image without beading can be obtained. That is, it is preferable when the printed portion or the image portion is formed with water-based ink by an inkjet recording method without occurrence of image quality defects such as beading, and the dried printed portion or the image portion is immersed in water at a temperature of 30 ° C for 1 minute.
  • the color density retention is 80% or more (for example, about 85 to 100%), and more preferably 85% or more (for example, about 90 to 99%).
  • a porous layer, an anti-blocking layer, a lubricating layer, an antistatic layer, and the like may be formed on the ink absorbing layer, if necessary.
  • the ink jet recording sheet of the present invention is useful as an ink jet recording sheet for recording by flying small ink droplets, but it is useful for printing sheets such as offset printing and flexographic printing (especially water-based ink sheets). It can also be used as such. Further, in order to improve the fixability of the colorant (dye), it is advantageous to use a dye fixing agent, particularly a high molecular dye fixing agent.
  • Dye fixatives polymer dye fixatives usually have a cationic group (particularly a guanidyl group or a strong quaternary ammonium salt type cation group) in the molecule.
  • the dye fixative may be water-soluble.
  • a protective layer is provided on the ink receiving layer.
  • various thermoplastic resins and thermosetting resins can be used as long as they can be peeled off from the substrate and protect the ink receiving layer, and do not significantly impair the quality of the transferred image.
  • Polymers can be used.
  • the thermoplastic resin include polyamide resins such as nylon 11, nylon 12, and nylon 612, polyester resins such as PET-based copolyester and PBT-based copolyester, and styrene- (meth) acrylate copolymers.
  • Styrene resin polyethylene, polypropylene, Polyolefin resins such as ethylene-propylene copolymers, polycarbonate resins, polyvinyl acetate, polyvinyl acetate resins such as ethylene-vinyl acetate copolymer, acrylic resins such as poly (meth) acrylate, polyacetal
  • resins such as resins, vinyl chloride resins such as vinyl chloride-vinyl acetate copolymer, and fluorine resins.
  • the thermoplastic resins may be used alone or in combination of two or more.
  • the thermosetting resin include various resins such as urethane resin, epoxy resin, phenol resin, kirylene resin, melamine resin, urea resin, and silicone resin.
  • the protective layer In order to effectively protect the ink receiving layer after transfer and improve the durability, it is advantageous to form the protective layer with a soft polymer, especially a non-tacky polymer.
  • the soft polymer may be a non-elastomer, but an elastomer is preferred.
  • elastomer means a polymer having rubber-like elasticity, not limited to rubbers such as natural rubber and synthetic rubber.
  • Elastomers include at least one polymer selected from synthetic rubber, natural rubber, and elastoplastic elastomers.
  • Synthetic rubbers include, for example, diene rubbers such as styrene-butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, and ethylene-propylene rubber such as butyl rubber, EPM, EPDM, fluorine rubber, and the like.
  • diene rubbers such as styrene-butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, and ethylene-propylene rubber such as butyl rubber, EPM, EPDM, fluorine rubber, and the like.
  • Various rubbers such as acrylic rubber, ethylene-acrylic rubber, olefin rubber such as chlorosulfonated polyethylene rubber, and other rubbers (for example, silicone rubber, urethane rubber, ethylene-vinyl acetate copolymer, polynorbornene rubber, etc.)
  • thermoplastic elastomer an elastomer composed of a hard segment (or block) and a soft segment (or block), for example, a block such as a polybutene / polystyrene elastomer, a polyisoprene / polystyrene elastomer, etc.
  • Polystyrene-based elastomers such as copolymers and block copolymers such as polyester or polyether-based polyurethane elastomers
  • Polyolefins such as urethane elastomers, block copolymers such as polyester or polyether-based polyamide elastomers, polyamide elastomers, EPRZ polypropylene elastomers, EPDM / polypropylene elastomers, and polyolefin block copolymers
  • Various elastomers such as block copolymers such as polyester-based elastomers, polyethylene terephthalate-based elastomers, polybutylene terephthalate-based elastomers, and polyester-based elastomers, and polyvinyl chloride elastomers.
  • the protective layer and the ink receiving layer flexibly follow the transferable object even when the transfer object is expanded and contracted.
  • the protective layer is made of synthetic rubber, natural rubber, or thermoplastic elastomer.
  • the elastomer may be vulcanized with sulfur, peroxide, or the like.
  • a preferred protective layer can be composed of an elastomer having a Young's modulus of preferably about 0.1 to 100 MPa (for example, 1 to 10 OMPa), more preferably about 0.1 to 50 MPa (for example, 1 to 50 MPa).
  • the polymer of the protective layer has an elongation of at least 300% (for example, about 300 to 1000%), particularly preferably at least 400% (for example, about 400 to 1000%). Usually, the elongation of the polymer is about 400 to 900%.
  • the glass transition temperature of the polymer constituting the protective layer is preferably from -100 to 100 ° C, more preferably from 50 to 50 ° (:, particularly preferably from -30 to 30 ° C.
  • the glass transition temperature of the elastomer is preferably at most 10 ° C (for example, about ⁇ 100 to 110 ° C), more preferably at most 15 ° C (for example, —100 to 100 ° C).
  • the polymer constituting the protective layer may contain various additives used in the image receiving layer, if necessary.
  • the thickness of the protective layer is, for example, preferably about 1 to 90 m, more preferably about 3 to 70 ⁇ , and usually about 5 to 50 (particularly about 5 to 30 // m).
  • the first thermal transfer sheet of the present invention can be manufactured by forming an ink receiving layer that can be peeled off from the substrate on at least one surface of the release substrate.
  • the ink receiving layer is composed of a polymer (L) containing at least the monomer unit of the formula (14), a hot melt adhesive resin (M), and other components as necessary on the release surface of the base material. It can be formed by applying the applied coating agent.
  • At least the polymer (L) can be usually used in the form of an aqueous solution or emulsion, and the hot melt adhesive resin (M) can be used in the form of a powder.
  • a coating agent for the ink receiving layer can be prepared by mixing the aqueous solution or emulsion of the polymer (L), the powder of the hot melt adhesive resin (M), and other components as necessary.
  • the aqueous solution or the solvent of the aqueous emulsion may be water alone, or may contain a hydrophilic organic solvent such as an alcohol if necessary.
  • a protective layer coating agent composed of an elastomer or the like is applied, and if necessary, dried to form a protective layer.
  • the ink receiving layer may be formed as described above.
  • the coating agent for the protective layer can be prepared using an organic solvent or an aqueous solvent depending on the type of the polymer, and may be in the form of a solution or an emulsion.
  • the coating agent can be coated by a conventional method (described above). By drying the coating at a temperature of about 50 to 150 ° C (preferably 80 to 120 ° C), the ink receiving layer and A protective layer can be formed.
  • the ink receiving layer thus formed is suitable for forming an image by an ink jet system in which, for example, a small droplet of ink (particularly aqueous ink) is ejected and recorded.
  • the recorded image is formed at an appropriate temperature (for example, preferably about 140 to 250 ° C., and more preferably about 140 to 200 ° C.) while the ink receiving layer is in contact with the transfer object. ) and pressure 0.
  • the ink-receiving layer from the substrate to The transfer can be smoothly transferred or transferred to the transfer target by peeling off the transfer transfer containing the transfer image, if necessary, may be crosslinked by heating.
  • the transfer object a two-dimensional or three-dimensional structure formed of various materials such as fiber, paper, wood, plastic, ceramics, and metal can be used.
  • a plastic film, a plastic sheet, paper, cloth, or the like is used as the transfer object.
  • the ink receiving layer When at least an ink receiving layer that can be peeled off from the base material is formed on one surface of the base material using the resin composition, for example, the ink receiving layer is recorded by an inkjet recording method, and the recorded image is thermally transferred to a transfer target body. It can be used for a thermal transfer sheet for an ink jet to form a transfer image. Even when transferred to an elastic transfer object, the recorded image follows the expansion and contraction of the transfer object well and does not crack.
  • the thermal transfer sheet of the present invention is useful as an ink image receiving sheet by an ink jet system for recording by flying small ink droplets, but may also be used as a thermal transfer sheet (particularly, a sheet for aqueous ink) for offset printing, flexographic printing, and the like. Available.
  • the methods for evaluating various characteristics of the recording sheets obtained in the examples and comparative examples are as follows, but items that cannot be shared are described in individual inventions.
  • an inkjet printer (Seiko Epson Corporation, PM-7770C)
  • color sheets using cyan, yellow, magenta, and black were applied to the recording sheets obtained in Examples and Comparative Examples.
  • One pattern was printed in photo glossy paper mode to form a recorded image.
  • each color of cyan, yellow, magenta, and black was used for the recording sheets obtained in Examples and Comparative Examples.
  • the printed color pattern was printed in HQ mode to form a recorded image.
  • the ink-jet printing unit is referred to as BJC-420J manufactured by Canon Inc. in the second part of the present invention, and DeskJerce manufactured by Hyured Packard Co., Ltd. in the first IE of the present invention. et895Cxi was used.
  • the recorded image was visually observed, and the sharpness was determined based on the following criteria.
  • the recorded image was visually observed, and the sharpness was determined based on the following criteria. : Image uniformity under high-speed printing conditions was evaluated.
  • ⁇ The same color density portion is uniform and there is no image quality defect such as unevenness or beading.
  • Ink is uneven over a wide area, and image quality defects such as unevenness and beading have occurred.
  • the recorded image was visually observed, and the sharpness was determined based on the following criteria.
  • ⁇ The portions having the same color density are uniform, and there is no image quality defect such as uneven bleeding.
  • ⁇ The ink was partially non-uniform, causing unevenness and beading.
  • the printed part was immersed in water at 30 ° C for 1 hour, pulled up vertically, drained well, and dried. After drying, the water resistance was visually evaluated according to the following criteria.
  • ⁇ The printed image is partially blurred or the color is faint.
  • the printed part was immersed in water at 30 ° C for 1 hour, pulled up vertically, drained well, and dried. After drying, the water resistance was visually evaluated according to the following criteria.
  • ⁇ The glossiness of the image receiving layer is not conspicuous.
  • the image receiving layer is very glossy and conspicuous.
  • aqueous polyurethane resin As an aqueous polyurethane resin, HUX-670 manufactured by Asahi Denka Kogyo Co., Ltd. was used. [Polyurethane-based graft polymer mixture (D-I)]
  • an aqueous solution or dispersion obtained by mixing an aqueous polyurethane resin and a vinyl acetate-based copolymer a hydrophilic vinyl monomer of 100 to 60% by weight and a copolymerizable vinyl monomer 0 to A composition obtained by graft polymerization of 40% by weight was used.
  • an aqueous polyurethane resin composition NS-120X manufactured by Takamatsu Yushi Kogyo Co., Ltd. was used.
  • a hydrophilic vinyl monomer is mixed with 100 to 60% by weight of a copolymerizable vinyl monomer 0 to A composition obtained by graft polymerization of 40% by weight was used.
  • an aqueous polyester resin composition NS-141 LX manufactured by Takamatsu Yushi Kogyo Co., Ltd. was used.
  • An aqueous coating solution was obtained by mixing (solid content) and (CI) 30 parts (solid content) of HUX-670 manufactured by Asahi Denka Kogyo Co., Ltd.
  • Adhesive-treated Polyethylene Lentelefu rate film with a thickness of 100 manufactured by ICI Japan Corporation, Melinex 705, (Hereinafter referred to simply as PET film)
  • an aqueous coating solution is applied, and dried at 100 ° C for 3 minutes to form an ink-absorbing layer having a thickness of 15 m to obtain a recording sheet I-1.
  • Example 1-4 (B-I) Recording sheet 1-4 was obtained in the same manner as in Example I-1 except that PVA-205 was used instead of PVA-405 manufactured by Kuraray Co., Ltd. Was. (Comparative Example I-1)
  • a (D-I) NS-120X made by Takamatsu Yushi Kogyo Co., Ltd. is applied to a 100-m thick PET film and dried at 100 ° C for 3 minutes to absorb a 15-m-thick ink.
  • a collecting layer was formed to obtain a recording sheet 1-10.
  • Table 1-1 shows the evaluation results of the recording sheets obtained in Examples I-1 to I-3 and Comparative Examples I-1 to I-6.
  • all of the recording sheets used in the examples have higher clarity, higher water resistance and higher print image quality than the comparative examples.
  • the resin composition for an ink jet recording sheet of the present invention and a recording sheet using the same and having an image receiving layer on at least one surface of a substrate have no beading even in an ink jet printing machine having a high printing speed. It was found that water absorbency as well as ink absorbency such as clarity and image uniformity can be improved to a high degree. In addition, the inventors succeeded in achieving both of the contradictory characteristics of water resistance and ink absorption while improving the printing quality. Next, an embodiment according to the present invention will be described.
  • crosslinkable group-containing cationic acrylic copolymer (A-II-1) the same as the crosslinkable group-containing thione acrylic copolymer (A-I-1) was used.
  • PVA-210 manufactured by Kuraray Co., Ltd. was used as a saponified product (B-II) of a vinyl acetate copolymer.
  • HUX-670 manufactured by Asahi Denka Kogyo KK was used as the aqueous polyurethane resin (C-II).
  • aqueous solution or dispersion in which an aqueous polyurethane resin and a saponified vinyl acetate copolymer are mixed, a hydrophilic vinyl monomer 100 to 60 wt% and a copolymerizable vinyl monomer 0 to 4 A composition obtained by graft polymerization of Owt% was used.
  • a composition an aqueous polyurethane resin composition, NS-120X manufactured by Takamatsu Yushi Kogyo Co., Ltd. was used.
  • aqueous solution or dispersion obtained by mixing an aqueous polyester resin and a saponified vinyl acetate copolymer a hydrophilic vinyl monomer 100 to 60 wt% and a copolymerizable vinyl monomer 0 to 4
  • a composition obtained by graft-polymerizing Owt% was used.
  • NS-141 LX manufactured by Takamatsu Oil & Fats Co., Ltd. which is an aqueous polyester resin composition, was used.
  • Example II-1 Except that (D-II) NS-120X manufactured by Takamatsu Yushi Kogyo Co., Ltd. was used instead of HUX-670 manufactured by Asahi Denka Kogyo Co., Ltd. In the same manner as in the above, recording sheet I-2 was obtained.
  • Example II- Except for using (E-II) NS-141 LX manufactured by Takamatsu Yushi Kogyo K.K. instead of HUX-670 manufactured by Asahi Denka Kogyo Co., Ltd. for the component (C-II). In the same manner as in 1, recording sheet I-3 was obtained.
  • the crosslinkable group-containing cationic acrylic copolymer ( ⁇ - ⁇ ) obtained in the above step is applied to a PET film with a thickness of 100 ⁇ , and dried at 100 ° C for 3 minutes. A 15 ⁇ 1 ink absorbing layer was formed to obtain a recording sheet ⁇ -4.
  • a 100-m-thick PET film is coated with NS-141 LX manufactured by Takamatsu Yushi Kogyo Co., Ltd. of the (E-II) component, and dried at 100 for 3 minutes to give a thickness of 150 m.
  • An xm ink absorbing layer was formed to obtain a recording sheet ⁇ -8.
  • Table II-1 shows the evaluation results of the recording sheets obtained in 1-5.
  • the recording sheet used in the example is not any of the recording sheets compared to the comparative example. It also has high clarity, high water resistance and high print quality.
  • the resin composition for an ink jet recording sheet of the present invention and a recording sheet using the same, which has an image receiving layer on at least one surface of the substrate, have ink absorption properties such as clarity and image uniformity as well as water resistance. It was found that it could be improved to a high degree. In addition, we have succeeded in improving the printing quality and at the same time, achieving both of the contradictory characteristics of water resistance and ink absorption. Next, an example according to the m-th embodiment of the present invention will be described.
  • crosslinkable group-containing cationic acrylic copolymer (A-m-1) the same as the crosslinkable group-containing thione acrylic copolymer (A-I-1) was used.
  • KS-7158 G was used.
  • aqueous coating solution was applied to a 100 / in-thick adhesive-treated polyethylene terephthalate rate film (manufactured by DuPont, Melinex 705; sometimes simply referred to as PET film), and then applied at 120 ° C. By drying at C for 3 minutes, a 15 m-thick ink absorbing layer was formed, and a recording sheet m-1 was obtained. (Example m-2)
  • a recording sheet m-3 was obtained in the same manner as in Example mi, except that the block isocyanate compound (F-in) was changed to 0 parts.
  • Recording sheet m-4 was obtained in the same manner as in Example m-1 except that the amount of the block isocyanate compound (F- ⁇ ) was changed to 5 parts.
  • a recording sheet m-5 was obtained in the same manner as in Example mi, except that (F-II) was changed to 0 parts.
  • a recording sheet m_6 was obtained in the same manner as in Example mi, except that the block isocyanate compound (D-m) was replaced with the same amount of isophorone diisocyanate.
  • Table mi shows the evaluation results of the recording sheets obtained in the examples and the comparative examples.
  • Table HI-1 shows the evaluation results of the recording sheets obtained in the examples and the comparative examples.
  • all of the recording sheets obtained in the examples have better print image quality such as image uniformity and sharpness as compared with the comparative example, and do not cause problems such as glossiness and water resistance. Is also excellent.
  • the recording sheet having at least one surface of the recording resin composition of the present invention and the image receiving layer formed therefrom can be highly improved in water resistance while maintaining ink absorbency and print image quality.
  • the copolymerization components were 93.7 parts of methyl methacrylate, 98.7 parts of n-butyl acrylate, 49.3 parts of getylaminoethyl methacrylate, and Trimethoxysilamp mouth pill methacrylate 4. Synthesize in the same manner as in (A-IV_1) except that it is 93 parts, and obtain a cross-linkable group-containing cationic acrylic copolymer containing no alkylenoxide group. (A-IV-2) was obtained.
  • P VA-405 (Saponification degree: 88.0-83.0%, Degree of polymerization: 500)
  • P VA-420 (Saponification degree: 78.0-81.0%, Degree of polymerization: 2000)
  • P VA- 205 (Genification degree: 86.5 to 89.5%, polymerization degree: 500)
  • P VA-217 (Genification degree: 87.0 to 89.0%, Polymerization degree: 1700)
  • aqueous polyurethane resin An aqueous polyurethane resin was used.
  • Asahi Denka as water-based polyurethane (C-IV) HUX_670 manufactured by Kogyo Co., Ltd. was used.
  • An aqueous coating liquid was obtained by mixing the cationic acrylic copolymer, the saponified vinyl acetate copolymer, and the modifier obtained in the above step.
  • a water-based coating solution is applied to a 100 m thick adhesive-treated polyethylene terephthalate film (made by DuPont, Melinex 705, sometimes simply referred to as PET film) at 100 ° C. After drying for 15 minutes, an ink absorbing layer having a thickness of 15 m was formed, and an evaluation sample was obtained.
  • the printed part was immersed in water at 30 ° C. for 1 hour, pulled up vertically, drained well, and dried. The retention of the color density of the image remaining after drying was measured.
  • the aqueous coating solution of the resin composition described in Table IV-1 shows the type and the mixing ratio of the cross-linkable group-containing cationic acrylic copolymer, the genated product of the vinyl acetate-based copolymer, and the aqueous urethane. Coating and drying were performed in the same manner as in Example 1 to form an ink-absorbing layer as an image receiving layer having a thickness of 15 m, and each recording sheet IV-1 was obtained.
  • Component A-IV Crosslinkable group-containing cationic acrylyl copolymer
  • Component C-IV Water-based polyurethane resin The numbers in the formulation column indicate the solid content in the composition in%. Industrial applicability
  • all of the recording sheets used in the examples can obtain a print image excellent in uniformity, bleeding, and water resistance as compared with the comparative example.
  • the recording sheet having at least one surface of the recording resin composition of the present invention and the image receiving layer formed therefrom has excellent water resistance, ink absorption and printing even in an environment where high resolution and high speed are required. Image quality can be improved to a high degree. Further, the present invention can achieve both the water resistance and the ink absorption, which are contradictory properties, while improving the print quality to the same level as the photographic image quality. Next, a fifth embodiment of the present invention will be described.
  • a resin composition for an ink jet recording sheet according to the present invention and a resin composition in which the components of the resin composition were changed were prepared, a recording sheet having an image receiving layer was prepared, and provided for Examples and Comparative Examples.
  • Recording sheets V- :! to V-3 as examples and recording sheets V-4 to V-6 as comparative examples were produced, and various characteristics were evaluated. The specific evaluation method of the various characteristics and the method of displaying the evaluation result will be described later.
  • AV-1 cationic methyl acryl copolymer
  • B-V saponified vinyl acetate copolymer
  • C-V water-based polyurethane resin
  • Recording sheet V-2 was obtained in the same manner as in Example V-1, except that PVA-405 (B-V) manufactured by Kuraray Co., Ltd. was not added.
  • Example V-3 A water-based polyurethane resin (C-V) (manufactured by Asahi Denka Kogyo Co., Ltd., HUX-670-M2) used in Example V-1 and having a feature of a large amount of cationic group was used instead of HUX-670. 670—Recording sheet V-3 was obtained in the same manner as in Example V-1, except that less water-based polyurethane resin (CV) (HUX-670) was used than M2. (Example V-4)
  • Recording sheet V-4 was obtained in the same manner as in Example V-1, except that HUX-670-M2 (C-V) manufactured by Asahi Denka Kogyo KK was not added.
  • Recording sheet V-5 was prepared in the same manner as in Example V-1, except that the components (A-V-1) and (BV) used in Example V-1 were changed to 20 parts by weight and 80 parts by weight, respectively. Obtained. (Comparative Example V-2)
  • a recording sheet V-6 was obtained in the same manner as in Comparative Example V-1, except that HUX-670-M2 (C-V) manufactured by Asahi Denka Kogyo KK was not added.
  • the recorded image was visually observed, and the state of adhesion of the gizarol trace was determined based on the following criteria. ⁇ : Gizarol traces are not attached at all.
  • the gloss of the recording screen was measured using a gloss meter according to JIS Z 8741. ⁇ : 70% or more at 60 ° gloss
  • the recorded image was visually observed, and the ink absorption and image quality were determined based on the following criteria.
  • ⁇ The same color density area is uniform, and there is no image quality defect such as bleeding, unevenness and beading.
  • ⁇ Poor image quality such as partial bleeding, unevenness and beading.
  • Example V-2 Record sheet V-2 ⁇ ⁇ ⁇
  • Example V-3 Recording sheet V- 3 ⁇ ⁇ ⁇
  • the compounding ratio of each component (AV), (BV) and (CV) of the resin composition forming the image receiving layer of the recording sheet is within the range specified in the present invention, All of the recording sheets obtained are good in that the traces of the jagged roll do not easily adhere and do not impair the appearance of the recorded image.
  • Evaluation images were recorded on the recording sheets obtained in Example VI and Comparative Example VI using a dye ink jet pudding (PM-770C, manufactured by Seiko Epson Corporation) and a pigment ink jet printer (ENCAD NOVA JET Pro). Formed.
  • the 60 ° gloss was measured using a gloss meter.
  • Acrylate resin (A-VI-2) was obtained by polymerizing in the same manner as in A-VI-1 except that 3-methacryloxypropyl trimethoxysilane was not used.
  • White PET sheet having a basis weight of 140 g / m 2 (thickness 1 00 / xm), crosslinkable group-containing tree A mixture of 55.2 parts by weight (solids 20 parts by weight) of Fatty A-VI-1 and beaded colloidal sily (Snowtex PS_M manufactured by Nissan Chemical Co., Ltd.) 400 parts by weight (solids 80 parts by weight) was applied to a dry thickness of 15 / xm to obtain a recording sheet VI-1.
  • the evaluation results of the recording sheet are shown in Table VI-1.
  • the cationic group-containing resin B-VI was applied to the white PET sheet used in Example VI-1 to a dry coating thickness of 30 m to form an ink fixing layer. Further, the composition used in Example VI-1 was similarly applied thereon to obtain a recording sheet VI-2. The evaluation results of the recording sheet are shown in Table VI-1.
  • Example VI-1 In the white PET sheet used in Example VI-1, 57.6 parts by weight of the cationic group-containing resin B-VI (solid content: 20 parts by weight), polyvinyl alcohol (Kuraray Co., Ltd. PVA4055) 25% by weight aqueous solution 200 100 parts by weight (solid content: 30 parts by weight) and 100 parts by weight (solid content: 30 parts by weight) of a water-based polyurethane resin (Asahi Denka Co., Ltd. HUX-670) It was applied to form an ink fixing layer. Furthermore, the composition used in Example VI-1 was applied in the same manner to obtain a recording sheet VI-3. The evaluation results of the recording sheet are shown in Table VI-1.
  • Example VI-1 The same procedure as in Example VI-1 was carried out except that the acrylic resin A-VI-2 was used instead of the crosslinkable group-containing resin A-VI-1 used in Example VI-1. Got 4 The evaluation results of the recording sheet are shown in Table VI-1.
  • a recording sheet was prepared in the same manner as in Example VI-1 except that a spherical colloidal silica (Snowtex ST-20 manufactured by Nissan Chemical Industries, Ltd.) was used instead of the beaded colloidal silica used in Example VI-1. VI-5 was obtained. The evaluation results of the recording sheet are shown in Table VI-1.
  • Example VI-2 An ink fixing layer was formed in the same manner as in Example VI-2, and no ink receiving layer was formed.
  • a recording sheet VI-6 was obtained in the same manner as in Example VI-2. The evaluation results of the recording sheet are shown in Table VI-1.
  • a copolymer containing a monomer having a hydrolyzable silyl group and a (meth) acrylate monomer is added to an ink image receiving layer of an ink jet recording sheet. It was found that the use of the composition in which the fine particles were added and mixed significantly improved the ink absorbency, water resistance and glossiness of the recording sheet. Next, an embodiment according to the seventh embodiment of the present invention will be described.
  • Example w and Comparative Example ⁇ were evaluated for ink absorption, water resistance, image resolution, and blocking resistance as follows.
  • Ink jet pudding Yuichi (Graft Tech, Master Jet— JC2 008), a pigment-type aqueous ink (each color of cyan, yellow and magenta) was printed on the recording sheets obtained in Examples and Comparative Examples in solid color to form a recorded image.
  • place the copy paper for PPC on the print section at regular intervals apply a load of 24.5 kPa (250 gf Zcm 2 ) from the top of the copy paper for 10 seconds, and peel off the copy paper. The degree of ink set-off was visually determined, and the time until no set-off was detected was measured.
  • Example VE Using ink jet pudding (Graphtec Co., Ltd., Master Jet—JC2008), the recording sheet obtained in Example VE and Comparative Example W was printed with a yellow-based mazen evening line (100 m wide). ) was printed, and the dots were observed with a microscope at a magnification of 50 times, and evaluated according to the following criteria.
  • Example W Two or more recording sheets obtained in Example W and Comparative Example W were stacked, and a load of 3.92 kPa (40 gf / cm 2 ) was applied thereon, and the temperature was reduced to 40 ° C, 90% It was stored under RH humidity for one day and evaluated according to the following criteria.
  • Example VH-3 One side of a synthetic paper having a thickness of 110 xm (manufactured by Oji Yuka Paper Co., Ltd., Upo FPG110) was coated with the recording resin composition ⁇ —a shown in Example YE-I at 80 ° After drying at C for 5 minutes, a recording sheet having a porous image-receiving layer with a thickness of 7 ⁇ in which pores having an average pore diameter of 1 xm were present at high density was obtained.
  • Table VH-1 shows the evaluation results of the recording sheet.
  • a recording medium or a recording sheet excellent in ink absorption, blocking resistance, color reproducibility, recorded image or character water resistance, weather resistance, and surface gloss can be manufactured.
  • the copolymer component is methyl methacrylate 93.7 parts, n_butyl acrylate 98.8 parts, dimethylethyl ethyl methacrylate 49.3 parts, and pill methacrylate at the trimethoxysilane lamp 4.
  • a polymer (A-ring-2) was obtained in the same manner as in the above (A) except that the amount was 93 parts.
  • Printing method Inkjet pudding Yuichi (Seiko Epson Corporation, PM-770 Use 0 to print a color pattern using each color of cyan, magenta, yellow, and black on the recording sheets obtained in Examples and Comparative Examples, and set the paper setting to iron print paper. was done.
  • Ink absorbency evaluation After printing, place PPC copy paper on the print section at regular intervals, apply a load of 24.5 kPa (250 gf / cm 2 ) for 10 seconds from the top of the copy paper, and then copy. The paper was peeled off, and the presence or absence of ink transfer was visually judged, and the evaluation was made based on the time when it was not recognized.
  • Image quality evaluation The recorded image was visually observed, and the sharpness was determined based on the following criteria.
  • ⁇ The part with the same color density is uniform, and no unevenness is observed in the image.
  • ⁇ The ink is non-uniform in a very small area, and slight unevenness is observed in the image.
  • X The ink is uneven in a wide range, and the image unevenness is remarkable.
  • washing resistance evaluation 1 g of commercially available detergent was added to 1 liter of water at a temperature of 40 ° C, and a T-shirt sample (5 x 10 cm) on which the recorded image was transferred was added. The mixture was stirred at 600 rpm for 20 minutes. After stirring, the sample was taken out, water was thoroughly removed and dried, and the transferred image area was observed, and the washing resistance was evaluated according to the following criteria.
  • This coating solution was applied onto a base material (release paper) having a thickness of 100 / xm by Barco overnight to obtain a thermal transfer sheet.
  • the resin coating amount was 40 gZm 2 .
  • the resin composition of the present invention is composed of the polymer (L) and the hot-melt adhesive resin (M), it is formed on a peelable base material to form a thermal transfer sheet. It can be transferred to a stretchable transfer target to greatly improve the crack resistance, durability, water resistance, and washing resistance of the transferred image, as well as the ink absorption during image formation. .

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  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne une composition de résine destinée à des feuilles d'enregistrement par jet d'encre, cette composition comprenant: (1) un copolymère acrylique cationique possédant des groupes réticulables, (2) un copolymère d'acétate de vinyle saponifié, et (3) un modificateur. L'utilisation de cette composition permet d'améliorer les propriétés d'absorption de l'encre et la résistance à l'eau des feuilles. A titre d'exemples de modificateur, on peut citer une résine polyuréthanne compatible avec l'eau, un mélange de polymères greffés à base de polyuréthanne, un mélange de polymères greffés à base de polyester, ainsi qu'un composé isocyanate séquencé. A l'aide de ce modificateur, on régule les propriétés de la composition de résine. On peut utiliser, à la place du copolymère (1), un copolymère acrylique cationique obtenu par copolymérisation d'un monomère possédant un groupe oxyde alkylène, ou bien un copolymère acrylique obtenu par copolymérisation d'un monomère possédant un groupe silyle hydrolysable. L'invention concerne encore une solution d'un dérivé de cellulose, placée dans un solvant mixe et que l'on applique et sèche pour former une couche réceptrice d'image possédant une structure en réseau. On transfère sur une étoffe, après enregistrement, cette couche réceptrice d'image comprenant un mélange d'un copolymère d'un monomère possédant un groupe oxyde alkylène, avec un adhésif thermofusible.
PCT/JP2000/003611 1999-06-04 2000-06-02 Composition de resine destinee a une feuille d'enregistrement par jet d'encre et feuille realisee a l'aide de cette composition WO2000074945A1 (fr)

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Applications Claiming Priority (16)

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JP11/158814 1999-06-04
JP11158814A JP2000343811A (ja) 1999-06-04 1999-06-04 記録シート用樹脂組成物及びそれを使用した記録シート
JP11/305943 1999-10-27
JP30578199A JP2001121814A (ja) 1999-10-27 1999-10-27 インクジェット記録シート用樹脂組成物及びそれを使用した記録シート
JP11/305781 1999-10-27
JP30594399A JP2001123075A (ja) 1999-10-27 1999-10-27 樹脂組成物、それを用いた熱転写シート及びその製造方法
JP11/330510 1999-11-19
JP33051099A JP2001146072A (ja) 1999-11-19 1999-11-19 記録用樹脂組成物及びそれからなる受像層が形成された記録シート
JP11/336876 1999-11-26
JP33687699A JP2001150804A (ja) 1999-11-26 1999-11-26 インクジェット記録シート用樹脂組成物及び記録シート
JP36001699A JP2001171227A (ja) 1999-12-17 1999-12-17 記録シート用樹脂組成物及びそれを使用した記録シート
JP11/360016 1999-12-17
JP2000/28639 2000-02-07
JP2000028639A JP2001213046A (ja) 2000-02-07 2000-02-07 インクジェット記録シート用樹脂組成物及びそれを使用した記録シート
JP2000/33986 2000-02-10
JP2000033986A JP2001219640A (ja) 2000-02-10 2000-02-10 インクジェット記録シート

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US20220084721A1 (en) * 2019-01-16 2022-03-17 Autonetworks Technologies, Ltd. Insulated wire with bonding layer
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