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

• the present invention Nos. I-VII relate to a resin composition to be employed for an image-receiving layer in an ink jet recording sheet and an ink jet recording sheet having an image-receiving layer in which the resin composition is employed and, in more detail, relate to a resin composition employed for an image-receiving layer in an ink jet recording sheet which is excellent in an ink-absorbing ability, water resistance, and clearness of a recorded image, and relate to an ink jet recording sheet having an image-receiving layer which is formed by the use of the resin composition.
• the present invention No. I relates to a resin composition to be employed for an ink jet recording sheet which comprises a cationic acrylic copolymer containing a crosslinkable group, a saponified product of a vinyl acetate-based copolymer having a polymerization degree of 200-1000, and a improving material, and a recording sheet in which it is employed is high in an image quality of printing, and a characteristics that beading is not caused even in an ink jet printer having a quick printing speed, water resistance is highly improved in addition to clearness and an ink absorbability such as image uniformity, and water resistance and an ink absorbing ability can be coexisted which are of a contrary property in each other.
• the present invention No. II particularly relates to a resin composition for an ink jet recording sheet which comprises a cationic acrylic copolymer containing a crosslinkable group, a saponified product of a vinyl acetate-based copolymer, a water-based polyurethane resin and a polyester-based graft polymer mixture, and a recording sheet in which it is employed has a high clearness, high printing quality, and an ink absorbing ability, in which water resistance is highly improved, and which has a characteristics being capable of coexisting water resistance and an ink absorbing ability which are of a contrary property in each other.
• the present invention No. III relates to a resin composition for an ink jet recording sheet which comprises a cationic acrylic copolymer containing a crosslinkable group, a saponified product of a vinyl acetate-based copolymer, a water-based polyurethane resin composition, and a block isocyanate compound and a recording sheet in which it is employed has a characteristics being capable of highly improving water resistance while maintaining an ink absorbing ability and a printing ability.
• the present invention No. IV relates to a resin composition for an ink jet recording sheet which comprises a cationic copolymer obtained by copolymerization of a monomer having a polyalkylene oxide group, a monomer containing a hydrophilic group, a monomer containing a crosslinkable group, and a cationic monomer, a saponified product of a vinyl acetate-based copolymer and a modifier, and in a recording sheet in which it is employed, there is obtained a printing quality which is excellent in uniformity and blur resistance, and even in a circumstance in which a shift of high resolution and high speed is required, there are highly-improved water resistance, an ink absorbing ability, and a printing image quality, it has a characteristics that water resistance and an ink absorbing ability can be coexisted which are a contrary property each other while improving a printing quality such as a photographic picture image.
• the present invention No. V relates to a resin composition for an ink jet recording sheet which comprises a cationic (meth)acrylic copolymer obtained by copolymerization of a (meth)acrylic monomer containing a polyalkylene oxide group, a monomer containing a hydrophilic group, a monomer containing a crosslinkable group, and a cationic monomer, a saponified product of a vinyl acetate-based copolymer and a modifier, and a recording sheet in which it is employed has an image-receiving layer having an excellent roll-adhering resistance, an excellent high glossiness, and no-occurrence of worse in an image such as beading.
• the present invention No. VI relates to an ink jet recording sheet in which there is employed a composition (P) composed of a (meth)acrylic-based copolymer containing a hydrolyzable silyl group obtained by copolymerization of monomers containing a polymerizable unsaturated monomer having a hydrolyzable silyl group and a (meth)acrylic-based polymerizable unsaturated monomer and inorganic compound-based fine particles, and it has an image-receiving layer which is excellent in glossiness, etc. regardless of using a composition containing the inorganic compound-based fine particles.
• a composition (P) composed of a (meth)acrylic-based copolymer containing a hydrolyzable silyl group obtained by copolymerization of monomers containing a polymerizable unsaturated monomer having a hydrolyzable silyl group and a (meth)acrylic-based polymerizable unsaturated monomer and inorganic compound-based fine
• the present invention No. VII relates to a resin composition for recording which contains a resin composition composed of a cellulose derivative and a good solvent for the cellulose derivative, an organic acid which can dissolve in the good solvent or a weak solvent of the cellulose derivative, and a recording sheet in which it is employed is excellent in a blocking resistance, and it can form an image-receiving layer in which there can be improved surface glossiness of the picture image-receiving layer, clearness of a recorded image, and reproducibility of colors.
• the present invention No. VIII relates to a resin composition containing a polymer having a monomer unit shown by formula (14) described below and a hot-melt adhesive resin, and a heat-transfer sheet in which it is employed is excellent in an ink absorbing ability, an ink-fixing ability, printing ability, a water resistance of a recorded image, micro crack resistance, durability, and washing resistance.
• An ink jet recording method in which is low in cost, and in which full-coloration can be readily attained, and since it is low in noise and excellent in a printing ability, it is recently being rapidly spread, and it has been widely employed as a printer in an office and usual home use and a printer for a sign display.
• a water-based ink is mainly employed from a viewpoint of safeness and applicability to recording
• recording is conducted by spraying small droplets of an ink from a fine nozzle toward a recording sheet.
• a quick absorbable ink is desired. That is, in a recording sheet having a low ink absorbing ability, an ink remains on the surface of the recording sheet for a long time of period after completion of recording, whereby, it is anxious that a recording portion becomes dirty by contact with a portion of an apparatus and handling person, and by overlapping of the sheets.
• JP-A-57036692 Official Gazette discloses a technology concerning an ink jet recording sheet in which there is coated a basic latex polymer together with a water-soluble polymer and pigments in order to improve water resistance and dissolution.
• JP-A-63115780 Official Gazette discloses an ink jet recording sheet in which a polymer containing a quaternary ammonia salt is coated on a base material for a recording sheet, and it also states that a synthesized silica is employed together and a polyvinyl alcohol, etc. is employed together as a binder.
• JP-A-07061113 Official Gazette discloses an ink jet recording medium in which an ink-receiving layer is constructed by a polyvinyl alcohol resin and a cationic compound.
• JP-A-06227114 Official Gazette discloses an ink jet recording medium in which an ink receiving-layer which is constructed by pigments such as finely-powdered silica and a amphoteric ion latex.
• the Official Gazettes teach that there can be fairly improved a fixing-ability and water resistance by a modification to non-flowing of an ink in the ink jet recording sheet.
• the ink-fixing ability since there is a contrary relationship between the ink-fixing ability, water resistance, and an ink absorbing ability, if the water resistance and the ink-fixing ability are elevated, the ink absorbing ability lowers. Accordingly, both of the water resistance and the ink absorbing ability cannot be maintained in a high level by conventional technologies.
• JP-A-01174484 Official Gazette discloses an ink jet recording sheet in which a covering layer containing a copolymer of a fatty acid vinyl ester such as vinyl acetate with a cationic monomer and pigments is formed on the surface of a base material for the recording sheet, and the cationic copolymer may be a copolymer with a cationic monomer and a graft copolymer with a polyvinyl alcohol, and it may further contain even a water-soluble polymer binder.
• a covering layer containing a copolymer of a fatty acid vinyl ester such as vinyl acetate with a cationic monomer and pigments is formed on the surface of a base material for the recording sheet
• the cationic copolymer may be a copolymer with a cationic monomer and a graft copolymer with a polyvinyl alcohol, and it may further contain even a water-soluble polymer binder.
• JP-A-62083178 Official Gazette proposes an ink jet recording sheet having a coating layer containing a finely-powdered silicate and a cationic polymer emulsion, and it also states that it is preferred to employ together a self-crosslinkable acrylic emulsion having a glass transition temperature of not more than 0°C as an adhesive.
• the improvement is a low level, and water resistance is low, accordingly, a recording portion is flown out by water droplets, and blots are caused at a printing portion and an image portion, in the case that the blots are remarkable, the portions dissolve out and disappear. Accordingly, it cannot help being said that a quality concerning a recording property is still insufficient.
• conventional technologies cannot attain to a high level of improvement of water resistance and an ink absorbing ability while maintaining a printing quality.
• a recording sheet has become severely and severely employed at a high dissolution printing such as not less than 1000 dpi, multiple-printing by a light-colored ink at a high speed printing such as several times compared to. conventional speed in order to actualize a printing by a photographic image quality, and it is difficult to improve a problem of a worse image quality such as beading caused by a highest photographic image quality mode in a printer, and a high glossiness such as a print for silver chloride photograph becomes also desired in an outer appearance, there is a new problem of a mark of an embossed roll (a pressurized mark by a paper-discharging roll having a gear shape) which is printed on the surface of a high gloss recording sheet.
• a mark of an embossed roll a pressurized mark by a paper-discharging roll having a gear shape
• JP-A-57014091 and JP-A-61019389 Official Gazettes disclose an ink jet recording sheet which is constructed by a colloidal silica and a water-soluble resin.
• a colloidal silica and a water-soluble resin.
• JP-A-02276670 and JP-A-03281385 Official Gazettes disclose an ink jet recording sheet formed from a pseudo boehmite fine particles. Although the recording sheet shows a high ink absorbing ability and water resistance, an ink-receiving layer does not show a sufficient gloss.
• JP-A-59174381 and JP-A-60224578 Official Gazettes propose the use of a hydrophilic polymer such as starches, a water-soluble cellulose derivative, and a polyvinyl alcohol as an ink-receiving layer on a base material.
• a hydrophilic polymer such as starches, a water-soluble cellulose derivative, and a polyvinyl alcohol
• it satisfies an ink absorbing ability, it is poor in water resistance and an ink-receiving layer is dissolved out, and blocking is caused by sticking of surface when recording sheets are overlaid, resulting in that it is practically problematic.
• JP-B-91072460 Official Gazette proposes a method in which an ink is absorbed at an under-layer and a blocking resistance is improved at a surface layer, which comprises a combination of an ink-permeable surface layer with an ink-absorbing under layer.
• a surface layer which comprises a combination of an ink-permeable surface layer with an ink-absorbing under layer.
• JP-A-58110287 and JP-A-05051470 propose recording sheets in which there is formed a porous layer having air cells formed by spaces between particles themselves by coagulating fine particles such as silica on a base material.
• a porous layer having air cells formed by spaces between particles themselves by coagulating fine particles such as silica on a base material.
• JP-A-61085251 proposes a recording sheet in which a porous plastic thin layer is laminated with an ink-absorbing layer, since the porous plastic thin layer is formed by a hydrophobic plastics such as a polyethylene and polypropylene, an ink permeability is not sufficient in ink jet recording in which a water-based ink is mainly employed, and since the porous plastic thin layer is laminated by a thermally-compressurizing method, pores are crushed and deformed.
• an ink-fixing ability and water resistance cannot be elevated to a high level. Particularly, it is difficult to thermally-transfer an image to be recorded to a body to be transferred. Still further, even though an image can be transferred to the body to be transferred, washing resistance and durability are poor.
• JP-A-63060784 Official Gazette discloses an ink jet recording sheet in which there is formed an ink-absorbing layer containing organic polymer fine particles which are dissolved or swelled in solvents in an ink (particularly, an oily ink) on surface of a substrate.
• JP-A-07025133 Official Gazette discloses an ink jet recording sheet in which an ink-receiving layer is formed on at least one surface of a substrate which is formed by a polyolefine resin-coated paper or a polyester film, and the ink-receiving layer contains spherical fine particle polymers having an average particle diameter of 5-15 ⁇ m in a proportion of 5-30 g/m 2 by dry weight and thickness thinner than the average particle diameter of the spherical fine particle polymers.
• JP-A-08324106 Official Gazette discloses an ink jet recording sheet in which an ink-receiving layer having a porous structure is formed on one surface of a base material, and the layer is constructed by a hot-melt resin (an ethylene-vinyl acetate-based resin, a polyester-based resin, and a rubber-based resin, etc.).
• a hot-melt resin an ethylene-vinyl acetate-based resin, a polyester-based resin, and a rubber-based resin, etc.
• JP-A-08207425 Official Gazette discloses an ink jet recording sheet in which an ink-receiving layer is formed on one surface of a base material, and the layer contains a hot-melt resin (a polyamide-based resin, a polyester-based resin, and a water-soluble hot-melt resin such as an unsaturated polyester resin) and a hydrophilic resin (a polyacrylic amide, a polyvinyl alcohol, and polyvinyl pyrrolidone, etc.).
• the recording sheet can be thermallylaminated with a film, etc.
• washing resistance and durability are not sufficient, even though an image to be recorded is thermally-transferred to clothes, etc., a clear image transferred cannot become maintained for a long time of period.
• the purpose of the present invention Nos. I-III is to provide a resin composition for an ink-jet recording sheet by which an ink-absorbing ability and water resistance can be improved in a high level.
• the purpose of the present invention No. IV is to provide an ink-jet recording sheet in which there is not caused worse of an image such as beading even in a printer having a high printing speed by which a letter-printing quality is improved, and water resistance and an ink-absorbing ability are simultaneously satisfied.
• the purpose of the present invention No. V is to provide an ink-jet recording sheet having a photographic tone which is preferred in an ink jet recording type method by which an excellent letter-printing quality, water resistance, and high glossiness can be attained, in which an outer appearance of a printed image is not deteriorated by transferring to a recording paper of an embossed roll mark in the printer when the printer discharges the recording paper.
• the purpose of the present invention No. VI is to provide an ink-jet recording sheet which is excellent in a glossy property and, in which there are obtained an excellent ink-absorbing ability and water resistance.
• the purpose of the present invention No. VII is to provide a resin composition for recording and a recording sheet in which there is formed an image-receiving layer composed thereof.
• the image-receiving layer can be formed by the resin composition for recording, and which is excellent in an ink-absorbing ability and a blocking resistance and, in which there can be improved surface gloss of the image-receiving layer, clearness of the recorded image, water resistance, weatherability, and reproducibility of colors, etc.
• the purpose of the present invention No. VIII is to provide a resin composition for a heat transfer sheet and a heat transfer sheet.
• the resin composition is excellent in an ink-absorbing ability, an ink-fixing ability, a printing ability, water resistance of a recorded image, micro crack resistance, durability, and washing resistance, and which is useful for a heat transfer sheet.
• a recording sheet can be prepared by the combination of a cationic acrylic copolymer having a crosslinkable group and a saponified product of a vinyl acetate-based copolymer having a specified polymerization degree with a modifier, or by further combination of a water-based polyurethane resin, a polyurethane-based graft polymer mixture and a polyester-based graft polymer mixture, or a water-based polyurethane resin composition with a block isocyanate, in which water resistance, an ink-absorbing ability, and a printing image quality are remarkably improved and an excellent image quality can be obtained even in a high speed printer, and the present invention Nos. I-III were completed.
• the present inventors have obtained a finding that water resistance, an ink-absorbing ability, and a printing image quality can be remarkably improved even in a high speed printer having a high dissolution by a resin composition composed of a cationic acrylic copolymer (A-IV and A-V) obtained by copolymerization of a monomer having an alkylene oxide group, a monomer having a hydrophilic group, a monomer having a crosslinkable group, and a cationic acrylic monomer and a saponified product (B) of a vinyl acetate-based copolymer, particularly, a saponified product of a vinyl acetate-based copolymer having a specified polymerization degree, and a modifier (R), and there can be solved a various problems in adherence of an embossed roll mark and a high glossiness, etc., and the present invention Nos. IV and V were completed.
• the present inventors have found that an excellent glossiness, excellent ink absorbing ability, and water resistance can be obtained through constructing an image-receiving layer by a specified copolymer and fine particles of an inorganic compound, and the present invention No. VI was completed.
• the present inventors have found that surface glossiness of an image-receiving layer in a body to be recorded and clearness in a recorded image can be largely improved by the use of a resin composition for recording containing a cellulose derivative, a good solvent for the cellulose derivative, an organic acid which can dissolve in the good solvent or a weak solvent for the cellulose derivative and, optionally, the weak solvent for the cellulose derivative in a specified proportion, and the present invention No. VII was completed.
• the present inventors have found that there can be largely improved durability in a transferred image, particularly, micro crack resistance by forming an ink-absorbing layer which can be stripped from a base material using a resin composition of a polymer containing a specified polymerizable monomer unit and a hot-melt adhesive resin, and there can be further improved an ink absorbing ability, an ink-fixing ability, a letter-printing ability, and durability and washing ability in a picture image by copolymerization of the specified polymerizable monomer with a monomer having a cationic functional group, and the present invention No. VIII was completed.
• the present invention 1 provides a resin composition for an ink jet recording sheet having an image-receiving layer which is formed on at least one surface of a base material for an ink jet recording sheet, and which is constructed by,
• the present invention 2 provides a resin composition for an ink jet recording sheet as described in the present invention 1, in which the modifier (R) satisfies conditions that (n 1 -80)% by weight of a water-based polyurethane resin (C), (n 2 -60)% by weight of a polyurethane-based graft polymer mixture (D) [the mixture (D) is a graft polymer mixture obtained through graft-polymerization by adding a hydrophilic radical polymerizable vinyl monomer (d 3 ) and other radical polymerizable vinyl monomer (d 4 ) to a mixed aqueous solution or a dispersed liquid of a water-based polyurethane (d 1 ) with a saponified product (d 2 ) of a vinyl acetate-based copolymer in a proportion of 100-60% by weight: 0-40% by weight] , and (n 3 -60)% by weight of a polyester-based graft polymer mixture (E) [the mixture (E
• the present invention 3 provides a resin composition for an ink jet recording sheet as described in the present invention 2, in which a saponification degree is 75-100% and a polymerization degree is 200-5000, respectively, in the saponified products (d 2 ) and (e 2 ) of a vinyl acetate-based copolymer.
• the present invention 4 provides a resin composition for an ink jet recording sheet as described in the present invention 2, in which the water-based polyurethane resin (C) is cationic.
• the present invention 5 provides a resin composition for an ink jet recording sheet as described in the present invention 2, in which the polyurethane-based graft polymer mixture (D) and the polyester-based graft polymer mixture (E) are cationic.
• the present invention 6 provides a resin composition for an ink jet recording sheet having an image-receiving layer formed over at least one surface of a base material for an ink jet recording sheet, which comprises,
• the present invention 7 provides a resin composition for an ink jet recording sheet as described in the present invention 1 or 6, in which the cationic (meth)acrylic copolymer (A) having a crosslinkable group is a copolymer containing monomer units based on a respective monomer (1) or (2) described below,
• the present invention 8 provides a resin composition for an ink jet recording sheet as described in the present invention 1 or 6, in which the saponification degree is 70-95% in the saponified product (B) of a vinyl acetate-based copolymer.
• the present invention 9 provides a resin composition for an ink jet recording sheet as described in the present invention 7, in which the monomer having a hydrophilic group is a (meth)acrylate containing an ester bond with a polyoxyalkylene.
• the present invention 10 provides a resin composition for an ink jet recording sheet as described in the present invention 1, 6, or 7, in which the cationic (meth)acrylic copolymer (A) having a crosslinkable group is a copolymer containing 0.1-50% by mol of a monomer having a tertiary amino group or a quaternary ammonium salt group and 0.1-25% by mol of a monomer having a crosslinkable group.
• the present invention 11 provides a resin composition for an ink jet recording sheet which is a resin composition which constructs an image-receiving layer which is formed at at least one surface of surface of a base material for an ink jet recording sheet, which comprises 2-100% by weight of a cationic (meth)acrylic copolymer (A-IV) obtained by copolymerizing a (meth)acrylate monomer (a 1 ) having a polyalkylene oxide group, a monomer (a 2 ) having a hydrophilic group, a monomer (a 3 ) having a crosslinkable group, and a cationic monomer (a 4 ), 0-90% by weight of the saponified product (B) of a vinyl acetate copolymer, and 0-80% by weight of the modifier (R) (total thereof is 100% by weight).
• A-IV cationic (meth)acrylic copolymer
• the present invention 12 provides a resin composition for an ink jet recording sheet as described in the present invention 11, which is composed of 5-80% by weight of the cationic (meth)acrylic copolymer (A-IV), 15-80% by weight of the saponified product (B) of a vinyl acetate copolymer, and 5-60% by weight of the modifier (R) (total thereof is 100% by weight).
• the present invention 13 provides a resin composition for an ink jet recording sheet as described in the present invention 11 or 12, in which the cationic (meth)acrylic copolymer (A-IV) is composed of 0.1-40% by weight of the (meth)acrylate monomer (a 1 ) having a polyalkylene oxide group, 0.1-50% by weight of the monomer (a 2 ) having a hydrophilic group, 0.5-20% by weight of the monomer (a 3 ) having a crosslinkable group, 1-40% by weight of the cationic monomer (a 4 ), 10-60% by weight of a hard monomer (a 6 ), and 10-60% by weight of a soft monomer (a 7 ) (total thereof is 100% by weight), and a weight average molecular weight is 0. 2x10 4 -100x10 4 in the cationic (meth)acrylic copolymer (A-IV) having a crosslinkable group.
• the cationic (meth)acrylic copolymer (A-IV) is
• the present invention 14 provides a resin composition for an ink jet recording sheet which constructs an image-receiving layer which is formed at at least one surface of surface of a base material for an ink jet recording sheet, in which there are formulated 70-100% by weight of a cationic (meth)acrylic copolymer (A-V) obtained by copolymerizing a (meth)acrylate monomer (a 1 ) having a polyalkylene oxide group, a monomer (a 2 ) having a hydrophilic group, a monomer (a 3 ) having a crosslinkable group, and a cationic monomer (a 4 ), 0-30% by weight of the saponified product (B) of a vinyl acetate copolymer (total thereof is 100% by weight), and 0-15 parts by weight of the modifier (R) based on 100 parts by weight of total of the (A-V) and the (B).
• A-V cationic (meth)acrylic copolymer
• the present invention 15 provides a resin composition for an ink jet recording sheet as described in the present invention 14, in which the cationic (meth)acrylic copolymer (A-V) is a copolymer obtained by copolymerizing a (meth)acrylate monomer (a 1 ) having a polyalkylene oxide group, a monomer (a 2 ) having a hydrophilic group, a monomer (a 3 ) having a crosslinkable group, and a cationic monomer (a 4 ), and a nonionic monomer (a 5 ).
• the cationic (meth)acrylic copolymer (A-V) is a copolymer obtained by copolymerizing a (meth)acrylate monomer (a 1 ) having a polyalkylene oxide group, a monomer (a 2 ) having a hydrophilic group, a monomer (a 3 ) having a crosslinkable group, and a cationic monomer (a 4 ), and a non
• the present invention 16 provides a resin composition for an ink jet recording sheet as described in the present invention 14, in which there are formulated 75-95% by weight of the cationic (meth)acrylic copolymer (A-V), 5-25% by weight of the saponified product (B) of a vinyl acetate copolymer (total thereof is 100% by weight), and 0.5-5 parts by weight of the modifier (R) based on 100 parts by weight of total of the (A-V) and the (B).
• A-V cationic (meth)acrylic copolymer
• B saponified product
• R modifier
• the present invention 17 provides a resin composition for an ink jet recording sheet as described in the present invention 14, in which there are formulated 75-95% by weight of the cationic (meth)acrylic copolymer (A-V), 5-25% by weight of the saponified product (B) of a vinyl acetate copolymer (total thereof is 100% by weight), and 0.5-3 parts by weight of the modifier (R) based on 100 parts by weight of total of the (A-V) and the (B).
• A-V cationic (meth)acrylic copolymer
• B saponified product
• R modifier
• the present invention 18 provides a resin composition for an ink jet recording sheet as described in any one of the present inventions 14-17, in which the cationic (meth)acrylic copolymer (A-V) contains 8-40% by weight of the (meth)acrylate monomer (a 6 ) having a polyalkylene oxide group, 1-30% by weight of the monomer (a 2 ) having a hydrophilic group, 0.2-10% by weight of the monomer (a 3 ) having a crosslinkable group, 10-50% by weight of the cationic monomer (a 4 ), and 10-80% by weight of the nonionic monomer (a 5 ) (total thereof is 100% by weight).
• the cationic (meth)acrylic copolymer (A-V) contains 8-40% by weight of the (meth)acrylate monomer (a 6 ) having a polyalkylene oxide group, 1-30% by weight of the monomer (a 2 ) having a hydrophilic group, 0.2-10% by weight of the monomer (a 3
• the present invention 19 provides a resin composition for an ink jet recording sheet as described in any one of the present inventions 11, 13, 14, 15, and 18, in which a polyalkylene oxide group in the (meth)acrylate monomer (a 1 ) having a polyalkylene oxide group has a structure shown by a general formula: -[(CHR 1 ) n -O] m -R 2 .
• R 1 represents a hydrogen atom, methyl group, or hydroxyl group
• R 2 represents a hydrogen atom or methyl group
• n is an integer of 1-5
• m is an integer of 1-20, respectively
• n and m pieces of R 1 may be even identical to or different from each other.
• the present invention 20 provides a resin composition for an ink jet recording sheet as described in any one of the present inventions 7, 11, 13, 14, 15, and 18, in which the hydrophilic group in the monomer (a 2 ) having a hydrophilic group is at least one selected from the group consisting of carboxylic group or a salt thereof, an anhydride group, hydroxyl group, sulphonic acid group or a salt thereof, an amide group, and an ether group.
• the present invention 21 provides a resin composition for an ink jet recording sheet as described in any one of the present inventions 7, 11, 13, 14, 15, and 18, in which the monomer (a 3 ) having a crosslinkable group is a monomer having a hydrolyzable condensible group.
• the present invention 22 provides a resin composition for an ink jet recording sheet as described in any one of the present inventions 7, 11, 13, 14, 15, and 18, in which the monomer (a 3 ) having a crosslinkable group is a monomer having an alkoxysilyl group.
• the present invention 23 provides a resin composition for an ink jet recording sheet as described in any one of the present inventions 7, 11, 13-15, and 18, in which the cationic monomer (a 4 ) is a monomer having a tertiary amino group or a monomer having a quaternary ammonium salt group.
• the present invention 24 provides a resin composition for an ink jet recording sheet as described in any one of the present invention 15 or 18, in which the nonionic monomer (a 5 ) is any one of (meth)acrylates, aromatic vinyls, and vinyl esters.
• the present invention 25 provides a resin composition for an ink jet recording sheet as described in any one of the present invention 1, 6, 8, 11, 12, 14, 16 or 17, in which a polymerization degree is 200-1000 in the saponified product (B) of a vinyl acetate copolymer.
• the present invention 26 provides a resin composition for an ink jet recording sheet as described in any one of the present invention 1, 11, or 16, in which the modifier (R) contains a water-based polyurethane (C) and/or a water-based polyester resin (e 1 ).
• the present invention 27 provides an ink jet recording sheet characterized in that an ink-receiving layer formed on at least one surface of a base material for an ink jet recording sheet is constructed by a composition (P) containing a (meth)acrylic-based copolymer (A-IV) having a hydrolyzable silyl group prepared by copolymerization of monomers containing a polymerizable unsaturated monomer (a 8 ) and a (meth)acrylic-based polymerizable unsaturated monomer (a 9 ), and inorganic compound fine particles (G).
• the present invention 28 provides an ink jet recording sheet as in the present invention 27, in which an ink-fixing layer is formed between a base material for the ink jet recording sheet and the ink-receiving layer.
• the present invention 29 provides an ink jet recording sheet as in the present invention 27, in which the (meth)acrylic-based copolymer (A-IV) having a hydrolyzable silyl group is a water-based copolymer.
• the present invention 31 provides an ink jet recording sheet as in the present invention 27, in which the inorganic compound fine particles (G) is a rosary-like colloidal silica which is dispersed in water.
• the present invention 33 provides an ink jet recording sheet as in the present invention 27, in which the ink-fixing layer is composed of a resin composition containing a formulated product of at least one resin selected from the group consisting of a cationic group-contained resin or a saponified product of a copolymer of the cationic group-contained resin with a vinyl acetate-based copolymer, a water-based polyester-based resin and a water-based polyurethane-based resin.
• the ink-fixing layer is composed of a resin composition containing a formulated product of at least one resin selected from the group consisting of a cationic group-contained resin or a saponified product of a copolymer of the cationic group-contained resin with a vinyl acetate-based copolymer, a water-based polyester-based resin and a water-based polyurethane-based resin.
• the present invention 34 provides an ink jet recording sheet as in the present invention 33, in which the cationic group-contained resin is a cationic group-contained copolymer prepared by copolymerization of monomers containing 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 a (meth)acrylate-based polymerizable unsaturated monomer.
• the cationic group-contained resin is a cationic group-contained copolymer prepared by copolymerization of monomers containing 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 a (meth)acrylate-based polymerizable unsaturated monomer.
• the present invention 35 provides a resin composition for recording, which is a resin composition for recording for forming an ink recording layer, characterized by containing in a ratio of 100 parts by weight of a resin composition composed of (1) 1-30% by weight of a cellulose derivative (H) and (2) 70-99% by weight of a good solvent (I) for the cellulose derivative (total is 100% by weight), 0.1-20 parts by weight of (3) an organic acid (J) which can dissolve in the good solvent (I) or a weak solvent (K) for the cellulose derivative, and optionally, 0-150 parts by weight of (4) the weak solvent (K) for the cellulose derivative.
• a resin composition for recording which is a resin composition for recording for forming an ink recording layer, characterized by containing in a ratio of 100 parts by weight of a resin composition composed of (1) 1-30% by weight of a cellulose derivative (H) and (2) 70-99% by weight of a good solvent (I) for the cellulose derivative (total is 100% by weight), 0.1-20 parts by weight of (3) an
• the present invention 36 provides a resin composition for recording as in the present invention 35, in which the cellulose derivative (H) is a cellulose acetate.
• the present invention 37 provides a resin composition for recording as in the present invention 35, in which proportion of the weak solvent (K) for the cellulose acetate is 50-150 parts by weight.
• the present invention 38 provides a resin composition for recording as in the present invention 35, characterized in that the good solvent (I) for the cellulose derivative is at least one kind selected from the group consisting of ketones, esters, ethers, cellosolves, cellosolve acetates, halogenated hydrocarbons, and nitro compounds, and a boiling point of the solvent is 35-160°C.
• the good solvent (I) for the cellulose derivative is at least one kind selected from the group consisting of ketones, esters, ethers, cellosolves, cellosolve acetates, halogenated hydrocarbons, and nitro compounds, and a boiling point of the solvent is 35-160°C.
• the present invention 39 provides a resin composition for recording as in the present invention 35, characterized in that a melting point of the organic acid (J) is not less than 60°C.
• the present invention 40 provides a resin composition for recording as in the present invention 35 or 37, characterized in that the weak solvent (K) for the cellulose derivative is at lest one kind selected from esters, alcohols, ketones and ethers, and a boiling point of the solvent is 100-300°C.
• the weak solvent (K) for the cellulose derivative is at lest one kind selected from esters, alcohols, ketones and ethers, and a boiling point of the solvent is 100-300°C.
• the present invention 41 provides a resin composition for recording as in the present invention 35, characterized in that the good solvent (I) for the cellulose derivative is at least one kind selected from a C 1-5 dialkyl ketone, a C 1-4 alkyl acetate, a C 4-6 cyclic or linear ether, and a C 1-4 alkyl cellulose and a C 1-4 alkyl cellulose acetate, and the weak solvent (K) for the cellulose derivative is at least one kind selected from a C 5-8 alkyl formate, a C 1-4 alkyi benzoate, a C 4-8 cycloalkanol, a C 6-10 dialkyl ketone, and a C 7-10 ether.
• the good solvent (I) for the cellulose derivative is at least one kind selected from a C 1-5 dialkyl ketone, a C 1-4 alkyl acetate, a C 4-6 cyclic or linear ether, and a C 1-4 alkyl cellulose and a C 1-4 al
• the present invention 42 provides a resin composition for recording as in the present invention 35 or 41, characterized in that boiling point difference (TK-TI) between the good solvent (I) and the weak solvent for the cellulose derivative is 10°C ⁇ (TK-TI) ⁇ 200°C.
• TK-TI boiling point difference
• the present invention 43 provides a resin composition for recording as in the present invention 35 or 39, characterized in that solubility of the organic acid (J) to water is not more than 2 g/100 ml at 20°C.
• the present invention 44 provides an ink jet recording sheet characterized in that there is employed a resin composition for an ink jet recording sheet as in any one of the present inventions 1-43, and an image-receiving layer is formed over at least one surface of a base material.
• the present invention 45 provides an ink jet recording sheet as in the present inventions 44, in which glossiness (60°-gloss measured according to JIS Z8741) in the surface of an ink-receiving layer is not less than 30%.
• the present invention 46 provides a resin composition for a heat transfer sheet containing a polymer (L) containing monomer units shown by formula (14) described below and a hot-melt adhesive resin (M).
• a plurality of R 2 may be identical to or different from each other, and m pieces of -(CHR 2 ) n O- may be combined in random or block.
• the present invention 47 provides a resin composition for a heat transfer sheet as in the present invention 46, in which the polymer (L) is constructed by a copolymer of a monomer of the formula (14) with at least one kind monomer selected from a monomer having a cationic functional group, a monomer having a crosslinkable group, and a monomer having a hydrophilic group.
• the present invention 48 provides a resin composition for a heat transfer sheet as in the present invention 46 or 47, in which content of the monomer of the formula (14) is 1-40% by weight based on total monomers in the polymer (L).
• the present invention 49 provides a resin composition for a heat transfer sheet as in the present invention 47, in which the monomer having a cationic functional group is at least one kind selected from a monomer having a group composed of a tertiary amino group or a salt thereof, a monomer having a quaternary ammonium salt group, and a monomer which forms a quaternary ammonium salt group, the monomer having a hydrophilic group is at least one kind selected from a monomer having a group composed of carboxylic group or a salt thereof, a monomer having an acid anhydride group, a monomer having hydroxyl group, a monomer having a group composed of sulphonic group or a salt thereof, a monomer having amide group, and a monomer having ether group, and the monomer having a crosslinkable group is at least one kind selected from a monomer having an epoxy group, a monomer having a methylol group, and a monomer having silyl group or an
• the present invention 50 provides a resin composition for a heat transfer sheet as in any one of the present inventions 46-48, in which Tg is -85 to 30°C in the copolymer which constructs the polymer (L).
• the present invention 51 provides a resin composition for a heat transfer sheet as in the present invention 46, in which the hot-melt adhesive resin (M) is at least one kind selected from a nylon-based resin, a polyester-based resin, and a polyurethane-based resin.
• the hot-melt adhesive resin (M) is at least one kind selected from a nylon-based resin, a polyester-based resin, and a polyurethane-based resin.
• the present invention 52 provides a resin composition for a heat transfer sheet as in the present invention 46, in which proportion of the hot-melt adhesive resin (M) is 10-1500 parts by weight based on 100 parts by weight of the polymer (L).
• the present invention 53 provides a heat transfer sheet, which is a sheet in which an ink-receiving layer being strippable from a base material is formed at one surface of the base material, in which the ink-receiving layer is constructed by a resin composition for a heat transfer sheet as in any one of the present invention 46-52.
• the present invention 54 provides a heat transfer sheet as in the present invention 53, in which the ink-receiving layer is formed at a base material through a protecting layer which is strippable from the base material.
• the present invention 55 provides a heat transfer sheet as in the present invention 54, in which the protecting layer is constructed by at least one kind selected from a thermoplastic resin, a thermosetting resin, and an elastomer.
• the present invention 56 provides a heat transfer sheet as in any one of the present invention 53 or 54, in which the ink-receiving layer contains at least one component of a dye-fixing agents and a plasticizer.
• the present invention 57 provides a method for the preparation of a heat transfer sheet, which is a method for the preparation of a sheet by forming an ink-receiving layer through coating a solution of a material which forms the ink-receiving layer which is capable of being stripped from a base material, in which the ink-receiving layer is constructed by a resin composition as in any one of the present inventions 46-56.
• the present inventions relate to a novel resin composition for an ink jet recording sheet and an ink jet recording sheet in which an image-receiving layer is formed on the surface of a base material for the sheet using thereof.
• the ink jet recording sheet in relation to the present inventions possess a base material and an image-receiving layer and, in at least one surface of the base material, the image-receiving layer is formed in at least one surface of the base material by the resin composition of the present inventions.
• a kind of materials for the base material (hereinafter, occasionally referred to as “a base material for recording” or merely “a base material”) in the ink jet recording sheet is not particularly limited, and there are enumerated, in addition to usual papers in which natural fibers are employed, a coated paper in which the papers is employed, a nonwoven web in which natural fibers and synthetic fibers are employed solely or in combination, a plastic film, and a synthetic paper (there is included a fiber-made one in addition to a plastic film-made one), etc. and, of the material examples, the plastic film and the synthetic paper are particularly preferred.
• a polyolefine such as a polyethylene and polypropylene, an ethylene-vinyl acetate copolymer, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a poly(meth)acrylate, a polystyrene, a polyvinyl alcohol, an ethylene-vinylalcohol copolymer, a cellulose derivative such as a cellulose acetate, a polyester (a polyalkylene terephthalate such as a polyethylene terephthalate, a polybutylene terephthalate, a polyalkylene naphthalate such as a polyethylene naphthalate and a polybutylene naphthalate, etc.), a polycarbonate, a polyamide (nylon 6, nylon 6/6, nylon 6/10, and nylon 6/12, etc.), a polyester amide,
• a polyolefine particularly, polypropylene
• a polyester particularly, a polyethylene terephthalate
• a polyamide there is most preferred the polyester (particularly, a polyethylene terephthalate) from a viewpoint of mechanical strength and workability, etc.
• Transparency is not particularly limited in the base material for the ink jet recording sheet in relation to the present invention, indistinct, transparent, or semitransparent ones are appropriately employed depending upon uses thereof.
• transparent ones are usually preferred.
• a paper and a coated paper for example, there can be employed a high quality paper, an art paper, and an RC paper, etc.
• Thickness of the base material is not also particularly limited and, it is appropriately selected depending upon uses thereof, and it is usually 5-500 ⁇ m, preferably 10-300 ⁇ m or so.
• plastic film or synthetic paper optionally, there may be even added additives such as a sizing agent, an antioxidant, an ultraviolet ray absorbent, a thermal stabilizer, a lubricant, and pigments, etc. which are commonly-used.
• additives such as a sizing agent, an antioxidant, an ultraviolet ray absorbent, a thermal stabilizer, a lubricant, and pigments, etc. which are commonly-used.
• surface of the base material is in advance treated by a corona discharging or an under-coating.
• the image receiving layer in relation to the present invention No. I is formed by the cationic (meth)acrylic copolymer (A-I) having a crosslinkable group, the saponified product (B) of a vinyl acetate copolymer having a specified polymerization degree, and the modifier (R).
• the image receiving layer in relation to the present invention No. II is formed by a composition composed of a cationic (meth)acrylic copolymer (A-II) having a crosslinkable group and a saponified product (B) of a vinyl acetate-based copolymer, a water-based polyurethane resin (C), a polyurethane-based graft polymer mixture (D) and/or a polyester-based graft polymer mixture (E).
• A-II cationic (meth)acrylic copolymer having a crosslinkable group and a saponified product (B) of a vinyl acetate-based copolymer, a water-based polyurethane resin (C), a polyurethane-based graft polymer mixture (D) and/or a polyester-based graft polymer mixture (E).
• the image receiving layer in relation to the present invention No. III is formed by a composition composed of a cationic (meth)acrylic copolymer (A-III) having a crosslinkable group and a saponified product (B) of a vinyl acetate-based copolymer, a water-based polyurethane resin (C), a polyurethane-based graft polymer mixture (D) and/or a polyester-based graft polymer mixture (E).
• A-III cationic (meth)acrylic copolymer having a crosslinkable group and a saponified product (B) of a vinyl acetate-based copolymer, a water-based polyurethane resin (C), a polyurethane-based graft polymer mixture (D) and/or a polyester-based graft polymer mixture (E).
• the image-receiving layer in relation to the present invention No. III is formed by a composition composed of a cationic (meth)acrylic copolymer (A-III) having a crosslinkable group and a saponified product (B) of a vinyl acetate-based copolymer, a water-based polyurethane resin composition (C), and a block isocyanate compound (F).
• A-III cationic (meth)acrylic copolymer having a crosslinkable group and a saponified product of a vinyl acetate-based copolymer, a water-based polyurethane resin composition (C), and a block isocyanate compound (F).
• the image-receiving layers in relation to the present invention No. IV and No. V are formed by a resin composition for a recording sheet composed of a cationic (meth)acrylate monomer (A-IV or A-V) obtained by copolymerization of a (meth)acrylate monomer (a 1 ) having a specified polyalkylene oxide group, a monomer (a 2 ) having a hydrophilic group, a monomer (a 3 ) having a crosslinkable group, and a cationic monomer (a 4 ), a saponified product (B) of a vinyl acetate-based copolymer, and a modifier (R).
• A-IV or A-V cationic (meth)acrylate monomer obtained by copolymerization of a (meth)acrylate monomer (a 1 ) having a specified polyalkylene oxide group, a monomer (a 2 ) having a hydrophilic group, a monomer (a 3 ) having a crosslinkable
• the image-receiving layer in relation to the present invention No. VI is formed from a resin composition for a recording sheet constructed by a composition (P) containing a (meth)acrylic-based copolymer (A-VI) having a hydrolyzable silyl group prepared by copolymerization of monomers containing a polymerizable unsaturated monomer (a 8 ) and a (meth)acrylic-based polymerizable unsaturated monomer (a 9 ), and inorganic compound-based fine particles (G).
• P containing a (meth)acrylic-based copolymer (A-VI) having a hydrolyzable silyl group prepared by copolymerization of monomers containing a polymerizable unsaturated monomer (a 8 ) and a (meth)acrylic-based polymerizable unsaturated monomer (a 9 ), and inorganic compound-based fine particles (G).
• the image-receiving layer in relation to the present invention No. VII is formed from a resin composition for a recording sheet constructed composed of a cellulose derivative (H) and a good solvent (I) for the cellulose derivative, an organic acid (J) which can dissolve in the good solvent (I) or a weak solvent (K) for the cellulose derivative, and optionally, a weak solvent (K) for the cellulose derivative.
• a method for forming the image-receiving layer is not particularly limited, and publicly-known and a variety of means can be applied. It is to be noted that details are described hereinafter.
• the resin composition (hereinafter, occasionally referred to as merely “resin composition for recording") for forming an image-receiving layer which is formed over at least one surface of a base material for an ink jet recording sheet in relation to the present invention is constructed by a resin composition for recording which is orderly illustrated hereinafter.
• the resin compositions for an ink jet recording sheet in relation to the present invention Nos. I and II are constructed by 2-80% by weight, and preferably 5-50% by weight of the cationic (meth)acrylic copolymer (A-I or A-II) having a crosslinkable group, 5-80% by weight, and preferably 15-70% by weight of the saponified product (B) of a vinyl acetate-based copolymer having a polymerization degree of 200-1000, and 0-80% by weight, and preferably 5-60% by weight of a modifier (R).
• constructing ratio of respective components is represented based on a solid content.
• Constructing components for the modifier (R) in relation to the present invention Nos. I and II satisfy conditions that (n 1 -80)% by weight of the water-based polyurethane resin (C), (n 2 -60)% by weight of the polyurethane-based graft polymer mixture (D) [the mixture (D) is a graft polymer mixture obtained through graft-polymerization by adding a hydrophilic radical polymerizable vinyl monomer (d 3 ) and other radical polymerizable vinyl monomer (d 4 ) to a mixed aqueous solution or dispersed liquid of a water-based polyurethane (d 1 ) with a saponified product (d 2 ) of a vinyl acetate-based copolymer in a proportion of (100-60% by weight):(0-40% by weight)], and (n 3 -60)% by weight of the polyester-based graft polymer mixture (E) [the mixture (E) is a graft polymer mixture obtained from a graf
• the water-based polyurethane resin (C) is (n 1 -50)% by weight
• the polyurethane-based graft polymer mixture (D) is (n 2 -50)% by weight
• the polyester-based graft polymer mixture (E) is (n 3 -60)% by weight, and (n 1 +n 2 +n 3 ) ⁇ 10% by weight.
• the modifier (R) is a resin composition of the water-based polyurethane resin (C) or the polyester graft mixture (E).
• the resin composition for an ink jet recording sheet in relation to the present invention No. III is constructed by 2-80% by weight of the cationic (meth)acrylic copolymer (A-III) having a crosslinkable group, 5-60% by weight of the saponified product (B) of a vinyl acetate-based copolymer, 0-80% by weight of the water-based polyurethane resin (C1) [total of (A-III), (B), (C1) is 100% by weight], 0.05-10 parts by weight of the block isocyanate compound (F) based on 100 parts by weight of the saponified product (B) of a vinyl acetate-based copolymer.
• the cationic acrylic copolymer (A-III) having a crosslinkable group is 10-60% by weight
• the saponified product (B) of a vinyl acetate-based copolymer is 15-50% by weight
• the water-based polyurethane resin (C1) is 5-60% by weight
• the block isocyanate compound (F) is 0.3-5 parts by weight based on 100 parts by weight of the (B).
• Constructing ratio of respective components based on the solid content ranges in a scope in which there are obtained properties such as an excellent ink-absorbing ability, water resistance, and printing image quality in an ink jet recording, and it is appropriately selected from the scope.
• the modifier (R) is employed in order to improve properties such as water resistance and an adhesion to a base material.
• the water-based polyurethane resin (C) affects to water resistance and an adhesion to a base material
• the polyurethane-based graft polymer mixture (D) and the polyester-based graft polymer mixture (E) mainly affect to an ink-absorbing ability.
• the cationic acrylic copolymers (A-I to A-III) having a crosslinkable group to be employed in the present inventions Nos. I-III, if those are a cationic acrylic copolymer having a crosslinkable group, are not particularly limited, and as an embodiment, there can be enumerated a copolymer containing respective monomer units of (1) or (2) described below, that is,
• the cationic monomer there can be employed, in addition to a variety of monomers having a tertiary amino group or a salt thereof, a variety of monomers having a quaternary ammonium salt or a variety of monomers which can form a quaternary ammonium salt and, for example, it is a diC 1-4 alkylamino-C 2-3 alkyl(meth)acrylic amide or a salt thereof, specifically, dimethylaminoethyl (meth)acrylic amide, diethylaminoethyl(meth)acrylic amide, dimethylaminopropyl(meth)acrylic amide, diethylaminopropyl (meth)acrylic amide, and a salt thereof, etc.
• diC 1-4 alkylamino-C 2-3 alkyl(meth)acrylate or a salt thereof dimethyl aminoethyl(meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl(meth)acrylate, diethylaminopropyl(meth)acrylate, and a salt thereof, etc.
• a diC 1-4 alkylamino-C 2-3 alkyl-substituted aromatic vinyl or a salt thereof specifically, 4-(2-dimethylaminoethyl)styrene, 4-(2-dimethylaminopropyl)styrene or a salt thereof.
• it is a nitrogen-contained heterocyclic monomer or a salt thereof, specifically, there can be enumerated vinyl pyridine, vinylimidazole, vinyl pyrrolidone or a salt thereof, etc.
• the salts there can be exemplified a halogenated hydrogen acid salt (hydrochloric acid and hydrobromic acid), a sulphate, an alkyl sulphate (methyl sulphate, ethyl sulphate, etc.), an alkyl sulphonic acid salt, an aryl sulphonic acid salt, and a carboxylic acid salt, etc. and, in the quaternary ammonium salt, there may be conducted a method in which it is produced by allowing to react an alkylation agent (epichlorohydrin, methyl chloride, and benzyl chloride, etc.) with a tertiary amino group.
• an alkylation agent epichlorohydrin, methyl chloride, and benzyl chloride, etc.
• the monomer components containing a crosslinkable group there are enumerated monomers having a variety of functions which have a self-crosslinkable or reactive functional group and, specifically, there can be exemplified an epoxy group-contained monomer such as glycidyl(meth)acrylate, (meth)allyl glycidylether, 1-allyloxy-3,4-epoxy butane, 1-(3-butenyloxy)-2,3-epoxy propane, and 4-vinyl-1-cyclohexene-1,2-epoxide, a methylol group-contained monomer such as N-methylol(meth)acrylic amide and N-butylol(meth)acrylic amide, or a derivative thereof, a monomer having a hydrolyzable condensible group (such as silyl group) such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributhoxysilane, vinylmethoxy dimethyls
• a preferred monomer having a crosslinkable group is a hydrolyzable condensible group-contained monomer having such as a hydrolyzable condensible group, particularly, an alkoxysilyl group (more specifically, a C 1- 4 alkoxysilyl group, etc. such as methoxysilyl group and ethoxysilyl group).
• the monomers containing a crosslinkable group can be employed solely or in combination of two or more kinds.
• the monomer components having a hydrophilic group there can be exemplified, for example, a monomer having a free carboxylic group or an acid anhydride group such as (meth)acrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and crotonic acid, or a monomer containing a salt thereof (an alkaline metal salt, an alkaline earth metal salt, an ammonium salt, and an amine salt, etc.), a half ester-contained monomer of an unsaturated polycarboxylic acid or an anhydride thereof with a linear or branched alcohol having a carbon number of 1-20 or so such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, and mono-2-ethylhexyl maleate, a monomer having a hydroxyl group such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-
• monomers having a hydrophilic group there are enumerated monomers having a polyoxalkylene ester such as diethyleneglycol mono(meth)acrylate, triethyleneglycol mono(meth)acrylate, and the polyethyleneglycol mono(meth)acrylate.
• the monomers having hydrophilic group can be employed solely or simultaneously in combination of two or more kinds.
• the cationic monomers, the monomers containing a crosslinkable group, and the monomers having hydrophilic group are usually employed in combination with nonionic monomers described below in order to adjust a film-formability and film-forming property.
• a C 1-18 alkyl (meth)acrylate such as methyl(meth)acrylate, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, t-butyl(meth)acrylate, n-butyl(meth)acrylate,hexyl(meth)acrylate,octyl(meth)acrylate,2-ethylhexyl(meth)acrylate, raulyl(meth)acrylate, and stearyl(meth)acrylate, a cycloalkyl ester such as cyclohexyl(meth)acrylate, an aryl ester such as phenyl(meth)acrylate, an aralkyl ester such as benzyl(meth)acrylate, aromatic vinyls such as styrene, vinyl to
• the nonionic monomers there are usually employed the C 1-18 alkyl(meth)acrylate, particularly, a C 2-10 alkyl ester of acrylic acid or a C 1-6 alkyl ester of methacrylic acid, aromatic vinyls, particularly, styrene, or vinyl esters, particularly, vinyl acetate.
• the nonionic monomers can be employed solely or in combination of two or more kinds.
• Use amount the above-described cationic monomer and monomers containing a crosslinkable group or use amount in the case of combining the monomers having a hydrophilic group can be selected within a range in which water resistance and ink-absorbing ability are not deteriorated, although it is not particularly limited, the use amount of the cationic monomer is 0.1-50% by mol (for example, 1-45% by mol), preferably 0.5-40% by mol (for example, 2-35% by mol), and more preferably 1-30% by mol (for example, 3-25% by mol) based on total amount of monomers, and usually 2-25% by mol or so.
• the use amount of the monomer containing a crosslinkable group is, for example, 0.1-25% by mol, preferably 0.2-20% by mol, and more preferably 0.5-15% by mol based on total amount of monomers, and usually 0.3-10% by mol or so.
• the use amount the monomer having hydrophilic group is 0-50% by mol, preferably 0-45% by mol (0.5-45% bymol), and more preferably 0-40% by mol (1-35% by mol) based on total amount of monomers, and usually 1-20% by mol or so.
• a copolymer is employed as the cationic acrylic copolymer containing a crosslinkable group in the present invention No. I-III (A-I to A-III), and the copolymer contains 0.1-50% by mol of monomers containing tertiary amino group or quaternary ammonium base and 0.1-25% by mol of monomers containing a crosslinkable group.
• the glass transition temperature can be selected within a range in which a film-formability, etc., is not deteriorated in the cationic acrylic copolymers (A-I to A-III) containing a crosslinkable group, and it is preferably -20 to 50°C, more preferably -10 to 40°C, and further preferably 0 to 30°C or so.
• the copolymer having such the glass transition temperature can be prepared by combining the above-described cationic monomer with the monomers containing a crosslinkable group, and optionally, the monomers having a hydrophilic group. Usually, it can be copolymerized in combination with a hard monomer, for example, a homo-polymerizable monomer having a glass transition temperature of 80 to 120°C. preferably, 90 to 105°C such as methyl(meth)acrylate and styrene and a soft monomer, for example, a homo-polymerizable monomer having a glass transition temperature of -85 to -10°C, preferably, -85 to -20°C such as a C 2-10 alkyl ester of acrylic acid.
• a hard monomer for example, a homo-polymerizable monomer having a glass transition temperature of 80 to 120°C. preferably, 90 to 105°C such as methyl(meth)acrylate and styrene and
• use proportion of the various monomers is not particularly limited, and an example can be enumerated below as the use proportion.
• a weight average molecular weight is not particularly limited in the cationic acrylic monomers (A-I to A-III) containing a crosslinkable group, and it ranges in preferably 0.2x10 4 to 100x10 4 , and more preferably 1x10 4 to 50x10 4 or so.
• Form in the cationic acrylic monomers (A-I to A-III) containing a crosslinkable group may be an organic solvent solution, an aqueous solution and, usually, preferably a cationic emulsion (particularly, a water-based emulsion).
• surface potential is +20 to +60 mV, preferably +12 to +55 mV, and more preferably +20 to +55 mV in polymer particles contained in the emulsion and, particularly preferably +15 to +55 mV or so.
• ⁇ potential is +20 to +60 mV, preferably +12 to +55 mV, and more preferably +20 to +55 mV in polymer particles contained in the emulsion and, particularly preferably +15 to +55 mV or so.
• the surface potential in polymer particles can be measured, for example, by the following apparatus and conditions.
• Apparatus for measurement An electrophoresis light scattering photometer (ELS-800) manufactured by Otsuka Denshi, Ltd.
• Average particle diameter of polymer particles in the cationic emulsion is 1-200 nm, preferably 3-100 nm, and more preferably 5-50 nm or so.
• the cationic emulsion containing the cationic acrylic copolymers (A-I to A-III) containing a crosslinkable group can be obtained by a commonly-used method, for example, a method in which the above-described two or three monomers are emulsion-polymerized in an emulsion polymerization-system containing a nonionic surface active agent and/or a cationic surface active agent, or a method in which a water-based emulsion is prepared by allowing to form a tertiary amine salt or a quaternary ammonium salt after copolymerization of the monomers.
• a printing quality and water resistance can be elevated in combination of a hydrophilic polymer compound (a water-soluble polymer compound or a water-insoluble and water-absorbable polymer compound) with other constructing components without losing an ink-absorbing ability so much.
• a hydrophilic polymer compound a water-soluble polymer compound or a water-insoluble and water-absorbable polymer compound
• the saponification product (B) of a vinyl acetate-based polymer there is employed the saponification product (B) of a vinyl acetate-based polymer, and the saponification product may be even employed together with a plurality of saponification products of a vinyl acetate-based polymer and, other hydrophilic polymer compounds may be even further employed.
• hydrophilic polymer compound components for example, there are enumerated hydrophilic natural polymers or derivatives thereof (starches, corn starches, a sodium alginate, gum arabic, gelatine, casein, and dextrin, etc.), cellulose derivatives (a methyl cellulose, an ethyl cellulose, a hydroxyethyl cellulose, a carboxymethyl cellulose, a cellulose sulphate, and a cyanoethyl cellulose, etc.), a vinylalcohol-based derivative (a polyvinyl alcohol and an ethylene-vinyl acetate copolymer, etc.), an ethylene-based polymer (an ethylene-maleic anhydride copolymer, etc.), a vinyl acetate-based copolymer (a vinyl acetate-methylmethacrylate copolymer, etc.), a polyalkylene oxide (a polyethylene oxide, an ethylene oxide-propylene oxide block copolymer, etc.), a polyalky
• hydrophilic polymer compound there are preferred the cellulose derivatives (particularly, a hydroxyethyl cellulose, etc.), the vinylalcohol-based derivative, the vinyl ester-based polymer, and polyvinyl pyrrolidone, etc.
• hydrophilic polymer having at least one functional group selected from a polyoxyalkylene group, acetoacetyl group, carboxylic group, acid anhydride group, and amino group.
• the other hydrophilic polymer compounds are employed solely or in combination of two or more kinds.
• the saponified product (B) of a vinyl acetate-based copolymer in relation to the present invention Nos. I-VI includes a vinyl acetate homopolymer or a partially- or completely-saponified product of a copolymer of a vinyl acetate with other copolymerizable monomers, and a saponification degree is 70-95%, preferably 75-92%, and more preferably 79-89%. However, in the present invention No. II, it is 70-100%, preferably 75-95%, and more preferably 79-92%.
• the saponified product (B) of a vinyl acetate-based copolymer there is preferably employed a saponified product of a vinyl acetate-based copolymer having a polymerization degree of 200-1000, and preferably 300-800.
• the polymerization is less than 200 in the polymer, an effect for improving water resistance is not occasionally shown and, in the case of exceeding 1000, beading is caused, resulting in that it is afraid that uniformity in a picture image is deteriorated.
• a monomer having a hydrophilic group for example, carboxylic group and a salt thereof, sulphonic acid group and a salt thereof, an acid anhydride group, amide group, hydroxyl group, and ether group, etc.
• the vinyl monomer having an oxyalkylene group there are included, for example, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, tripropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)allylether, triethylene glycol mono(meth)allylether, polyethylene glycol mono(meth)allylether, dipropylene glycol mono(meth)allylether, tripropylene glycol mono(meth)allylether, polypropylene glycol mono(meth)allylether, polyethylene glycol polypropylene glycol mono(meth)acrylate, hydroxypropyl(meth)acrylate, polyethylene glycol polytetramethylene glycol(meth)acrylate, polypropylene glycol polytetramethylene glycol(meth)acrylate, and
• a (meth)acrylate which is a vinyl monomer in which the oxyalkylene group is oxyethylene group, particularly, a polyoxyalkylene (meth)allylether (of those, a polyoxyethylene allylether).
• the vinyl monomer can be employed solely or in combination of two or more kinds.
• the ratio of the copolymerizable monomers which are copolymerized with vinyl acetate can be freely selected within a range in which clearness and water resistance are not deteriorated in order to obtain the saponified product (B) of a vinyl acetate-based copolymer in relation to the present inventions I-VI, and it is preferably 0.1-50% by mol, more preferably 1-30% by mol, and further preferably 2.5-25% by mol (for example, 3-20% by mol).
• a copolymer (a modified vinyl acetate-based resin) of vinyl acetate with the monomer components having an oxyalkylene group can be obtained, for example, as "OKS-7158G” which is a trade name of Nihon Gosei Kagaku, Ltd.
• hydrophilic polymer components to be employed together for the saponified product (B) of a vinyl acetate-based copolymer there is also included a hydrophilic polymer compound having a functional group which reacts with a reactive functional group (for example, an epoxy group such as glycidyl group and alkoxy silyl group, etc.) in the above-described cationic acrylic copolymer containing a crosslinkable group.
• a reactive functional group for example, an epoxy group such as glycidyl group and alkoxy silyl group, etc.
• a water-based polyurethane resin C
• a urethane-based graft polymer mixture D
• a polyester-based graft polymer mixture E
• a block isocyanate compound F
• a resin composition composed of the water-based polyurethane resin (C) and/or the polyester-based graft polymer mixture (E).
• the water-based polyurethane resin (C) in relation to the present invention Nos. I-VI is obtained by dissolving or dispersing a polyurethane resin synthesized from a polyol component, a polyisocyanate component, and a low molecular weight chain extender having at least two active hydrogens in the molecule which reacts with the polyisocyanate component into water, and it is synthesized by publicly-known methods.
• a polyurethane having a relatively high molecular weight is synthesized in a solvent which does not react with isocyanate group, followed by emulsifying through phase conversion while gradually adding water and optionally removing the solvent under reduced pressure
• a method in which the polyurethane is dispersed into water by vigorously agitating after adding an emulsifier and a method in which a reaction is conducted by adding a chain extender after dissolving or dispersing into water a urethane prepolymer into which a hydrophilic group, for example, a polyethylene glycol and carboxylic group are introduced.
• an aromatic polyisocyanate for example, a diisocyanate such as m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tollylene diisocyanate, 2,6-tollylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and 1,5-naphthalene diisocyanate, a polyisocyanate such as triphenylmethane triisocyanate, etc.), an aromatic-aliphatic polyisocyanate (for example, a diisocyanate such as 1,3-xylilene diisocyanate, 1,4-xylilene diisocyanate, tetramethyl xylilene diisocyanate, and a polyisocyanate such as 1,3,5-trisocyanatemethyl benzene, etc.), an aromatic-aliphatic polyisocyanate (for example, a diisocyanate such as 1,3-xylilene
• polyisocyanate components may be even an adduct in which a polyisocyanate compound is added to a polyvalent alcohol and has isocyanate group at terminals, an isocyanurate compound produced by a buret reaction, a dimer, and a trimer.
• polyisocyanate components can be solely or also in combination of two or more kinds.
• the polyol component to be employed for constructing the water-based polyurethane resin (C) there are included a polyester polyol, a polyether polyol (for example, a polyether diol having an oxy-C 2-4 alkylene such as a polyoxytetramethylene glycol), and a polycarbonate polyol (for example, a polycarbonate diol, etc.), etc.
• the polyester polyol is a polyester having hydroxyl group which is obtained by a reaction of a polyvalent alcohol with a polycarboxylic acid or a low alkyl ester thereof or an acid anhydride, and it may be even a derivative from a lactone.
• the diol components for, example, a polyester diol, etc.
• the diol components are preferably employed.
• polyol component can be employed solely or in combination of two or more kinds.
• an aliphatic polyvalent alcohol for example, a C 2-10 alkylene diol such as ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butane diol, tetramethylene glycol, hexamethylene glycol, and neopentyl glycol, a polyoxy-C 2-4 alkylene glycol such as diethylene glycol and triethylene glycol, and a polyol such as trimethylol propane and pentaerythritol, etc.), a cycloaliphatic polyvalent alcohol (for example, a cycloaliphatic diol such as 1,4-cyclohexane dimethanol and hydrogenated bisphenol A), and an aromatic polyvalent alcohol [for example, an aromatic diol, etc. such as 2,2-bis(2-hydroxyethylphenyl)propane], etc., and as the polyvalent alcohol, the aliphatic di
• polyvalent alcohol can be employed solely or in combination of two or more kinds.
• the polyvalent carboxylic acid for the preparation of the polyester polyol there can be exemplified an aliphatic polyvalent carboxylic acid (for example, a saturated aliphatic carboxylic acid such as adipic acid, sberic acid, azelaic acid, sebasic acid, and dodecane dicarboxylic acid, and an unsaturated aliphatic carboxylic acid such as maleic acid), a cycloaliphatic polyvalent carboxylic acid (for example, a cycloaliphatic dicarboxylic acid, etc.
• an aliphatic polyvalent carboxylic acid for example, a saturated aliphatic carboxylic acid such as adipic acid, sberic acid, azelaic acid, sebasic acid, and dodecane dicarboxylic acid, and an unsaturated aliphatic carboxylic acid such as maleic acid
• a cycloaliphatic polyvalent carboxylic acid for example, a cycloaliphatic dicar
• 1,4-cyclohexane dicarboxylic acid such as 1,4-cyclohexane dicarboxylic acid
• aromatic polyvalent carboxylic acid for example, an aromatic dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, and 1,5-naphthalene dicarboxylic acid, an aromatic polycarboxylic acid such as trimellitic acid
• the polyvalent carboxylic acid can be employed solely or in combination of two or more kinds.
• polyester alcohol can be derived from a lactone, and as the lactone, there may be included butyrolactone, varelolactone, and caprolactone, etc. and, of those, one or more kinds may be even employed in combination.
• a short chain polyol for example, the above-described aliphatic polyvalent alcohol, etc.
• aliphatic polyvalent alcohol etc.
• the chain extender be employed for the preparation of the water-based polyurethane resin (C), there are a polyamine component and, as the polyamine, there are enumerated diamines such as ethylene diamine, triethylene diamine, tetramethylene diamine, pentamethylene diamine, 1,7-diamino heptane, 1,8-diamino octane, xylilene diamine, 1,4-diamino cyclohexane, isophorone diamine, and phenylene diamine, and polyamines such as triaminopropane.
• diamines such as ethylene diamine, triethylene diamine, tetramethylene diamine, pentamethylene diamine, 1,7-diamino heptane, 1,8-diamino octane, xylilene diamine, 1,4-diamino cyclohexane, isophorone diamine, and phen
• the polyurethane obtained by such the raw materials and the method for the preparation may be solely, and a plurality of polyurethane resins may be even employed together. Further, optionally, other resins and additives can be also formulated.
• the polyurethane resin composition (C1) to be employed in the present invention No. III in addition to the water-based polyurethane resin (C), may be even a composition containing the polyurethane-based graft polymer mixture (D) and/or the polyester-based graft polymer mixture (E) which are described hereinafter.
• the polyurethane-based graft polymer mixture (D) may be even employed as the modifier (R).
• water-based polyurethane (d 1 ) for grafting there can be preferably employed the water-based polyurethane resin (C) exemplified in the illustration of the above-described water-based polyurethane resin.
• the saponified product (d 2 ) of a vinyl acetate-based copolymer for grafting there can be preferably employed the saponified product (B) of a vinyl acetate-based copolymer exemplified in the illustration of the above-described saponified product of a vinyl acetate-based copolymer.
• hydrophilic radical polymerizable vinyl monomer (d 3 ) there can be preferably employed the monomer having a hydrophilic group which contains a polyalkylene side chain and a crosslinkable group exemplified in the illustration of the above-described cationic acrylic copolymer.
• the other radical polymerizable vinyl monomer (d 4 ) there can be preferably employed the nonionic monomer exemplified in the illustration of the above-described cationic acrylic copolymer.
• a proportion of the water-based polyurethane (d 1 ), the saponified product (d 2 ) of a vinyl acetate-based copolymer, the radical polymerizable vinyl monomer (d 3 ) and the (d 4 ), and the saponified product (d 2 ) of a vinyl acetate-based copolymer is preferably 10-500 parts by weight, and more preferably 20-300 parts by weight and, as the radical polymerizable vinyl monomer (d 3 ), total of the (d 3 ) and (d 4 ) is preferably 10-500 parts by weight, and more preferably 20-300 parts by weight, which are all based on 100 parts by weight of the water-based polyurethane (d 1 ) in a solid ratio.
• the saponified product (d 2 ) of a vinyl acetate-based copolymer is less than 10 parts by weight, clearness of a picture image and ink-absorbing ability become insufficient and, in the case of exceeding 500 parts by weight, there lower adhesion to a polyester film and a synthetic paper, water resistance, and blocking resistance.
• the radical polymerizable vinyl monomers (d 3 ) and (d 4 ) are less than 10 parts by weight, an ink-absorbing ability tends to become worse and, in the case of exceeding 500 parts by weight, there tends to lower water resistance, and there is apt to lower adhesion to a base material such as a plastics film and a synthetic paper.
• the polyurethane-based graft polymer mixture (D) is obtained by graft-polymerization of the water-based polyurethane (d 1 ) and the saponified product (d 2 ) of a vinyl acetate-based copolymer with 100-60% by weight of the hydrophilic radical polymerizable vinyl monomer (d 3 ) and 0-40% by weight (preferably, 95-60:5-40% by weight) of the other radical polymerizable vinyl monomer (d 4 ).
• the hydrophilic vinyl monomer (d 3 ) is not more than 60% by weight, absorbing ability of a water-based ink becomes worse.
• the polymerization method for obtaining the polyurethane-based graft polymer mixture (D) conventionally publicly-known methods can be applied. For example, there is enumerated a method in which a polymerization initiator and optionally a small amount of an emulsifier are added into a water dispersion composed of the water-based polyurethane (d 1 ) and the saponified product (d 2 ) of a vinyl acetate-based copolymer, and the radical polymerizable vinyl monomers (d 3 ) and (d 4 ) are gradually added while maintaining at 70-80°C and agitating, followed by aging for 2-5 hours to complete the polymerization and to obtain the polyurethane-based graft polymer mixture (D).
• a polymerization initiator and optionally a small amount of an emulsifier are added into a water dispersion composed of the water-based polyurethane (d 1 ) and the saponified product (d 2 ) of a vinyl acetate
• the hydrophilic radical polymerizable vinyl monomers (d 3 ) is graft-polymerized in the water-based polyurethane (d 1 ) and the saponified product (d 2 ) of a vinyl acetate-based copolymer
• the polyurethane-based graft polymer mixture (D) is excellent in the absorbing ability of a water-soluble ink and, in addition, it has adhesion, water resistance, transparency, and ductility, etc. which are a characteristic in a polyurethane resin.
• a usual radical polymerization initiator for example, an azo compound Lazobisisobutyronitrile, 2,2-azobis (2,4-dimethylvarelo) nitrile, azobiscyano valeric acid, 2,2-azobis(2-amidinopropane) hydrochloride, and 2,2-azobis(2-amidinopropane)acetate, etc.], an inorganic peroxide (persulphates such as potassium persulphate, sodium persulphate, and ammonium persulphate, and hydrogen peroxide), an organic peroxide [benzoyl peroxide, di-t-butyl peroxide, cumenhydroperoxide, di(2-ethoxyethyl)peroxycarbonate], and a redox catalyst [a sulphite or a bisulphite (an alkaline metal salt and ammonium salt, etc.), etc.], a reducing agent such as L-ascor
• resinous components such as an epoxy resin, an amino resin, an acrylic resin, a polyurethane-based resin, a polyester-based resin, starches, and a polyamine-based resin, crosslinking agents such as an isocyanate-based compound, an epoxy-based compound, carbodiimide, and a silane-coupling agent, inorganic fillers such as silica, talc, kaoline clay, calcium carbonate, and mica, inorganic pigments and organic pigments, a film-forming auxiliary agent, a thickener, a leveling agent, an antiblocking agent, an antistatic agent, an ultraviolet ray absorbent, and an oxidant, etc. which are conventionally publicly-known additives.
• resinous components such as an epoxy resin, an amino resin, an acrylic resin, a polyurethane-based resin, a polyester-based resin, starches, and a polyamine-based resin
• crosslinking agents such as an isocyanate-based compound, an epoxy-based compound, carbodiimide,
• the water-based polyester resin composition (E1) to be employed in the present invention is prepared by esterification (or a transesterification) through a condensation polymerization of a dicarboxylic acid with a diol, and a method for the preparation thereof is not limited at all.
• an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid, or an ester thereof.
• a reason depends upon an advantage of an improvement in adhesion because an aromatic ring in the aromatic dicarboxylic acid has a large affinity to a hydrophobic plastics.
• a water-based polyester in which terephthalic acid is employed has a large adhesion to a molded article made from a polyethylene terephthalate-based polyester, it is an excellent water-based polyester.
• dicarboxylic acid components which construct the water-based polyester resin composition (E1) there are also employed the above-described aromatic dicarboxylic acid or the ester thereof and, in addition, there can be employed an aliphatic dicarboxylic acid such as adipic acid, succinic acid, sebasic acid, and dodecanoic diacid and a hydroxycarboxylic acid such as hydroxybenzoic acid or the ester thereof as the dicarboxylic acid components or a portion thereof.
• a lower alkyl ester such as a methyl ester and an ethyl ester. The ester may be even a monoester and diester.
• diol components there are employed ethylene glycol, propylene glycol, 1,4-butane diol, 1,6-hexane diol, neopentyl glycol, cyclohexane dimethanol, and bisphenols, etc.
• the water-based polyester resin composition (E1) to be employed in the present invention is polymerized so as containing sulphonic acid salt group or carboxylic acid salt group in the molecule in order to give a water-soluble or water-dispersible property.
• a dicarboxylic acid component such as 5-sodium sulphoisophthalic acid is employed as a portion of the dicarboxylic acid component, and the use amount is preferably 2-15% by mol in the dicarboxylic acid component.
• a polyvalent carboxylic acid having three or more functionalities is employed as a condensed acid component in the preparation of the water-based polyester resin composition (E1), or a method in which a water-based polyester resin composition (E1) is prepared by a method in which a polymerizable unsaturated carboxylic acid is grafted on a polyester resin, and then, there are prepared salts of a substance which forms a water-soluble salt together with an alkaline metal, a variety of amines, and an ammonium compound etc.
• Amount of the carboxylic salt in the water-based polyester resin composition (El) is preferably 15-250 KOH mg/g as an acid value in the water-based polyester resin composition (E1) produced.
• a molecular weight is 4000-30,000 and, in the case, in the case that the molecular weight is less than 4000, there are apt to lower physical properties in resins such as water resistance, blocking resistance, and adhesion, and in the case of exceeding 30,000, uniform dissolution or dispersion into water is difficult, resulting in that gelation tends to be caused with a lapse of time.
• the molecular weight is preferably 5,000-25,000.
• the water-based polyester resin composition (E1) is changed to an aqueous solution or a water dispersion and, as a means thereof, in the case of a water-based polyester resin composition (E1) containing a sulphonic acid salt, it is preferably dispersed into warm water of 50-90°C under agitation.
• an water-soluble organic solvent may be even employed together in order to readily dissolve or disperse the resin composition.
• the water-soluble organic solvent there are enumerated lower alcohols, polyvalent alcohols, and alkyl ethers or alkyl esters thereof and, specifically, there can be employed the lower alcohols such as methanol, ethanol, normal propanol, and isopropanol, the polyvalent alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and glycerine, ethylene glycol monomethylether, ethylene glycol monoethylether, propylene glycol monomethylether, propylene glycol monoethylether, propylene glycolacetate, diethylene glycol monomethylether, and dipropylene glycol monomethylether, etc.
• the lower alcohols such as methanol, ethanol, normal propanol, and isopropanol
• the polyvalent alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and glycerine, ethylene glycol monomethylether, ethylene glyco
• the polyester resin containing a carboxylic acid salt it is preferably dissolved or dispersed into water of 50-90°C under agitation, in which there are added alkaline compounds such as an aqueous ammonia, sodium hydroxide, potassium hydroxide, and a variety of amines. Also in the case, the water-soluble organic solvent may be even employed together.
• Thus-obtained water-based polyester resin composition (E1) may be even employed solely or in combination of two or more kinds of the water-based polyester resin composition (E1).
• Other resins and additives can be optionally formulated.
• polyester-based graft polymer mixture (E) may be even employed as the modifier (R). It is, for example, a composition in which a hydrophilic radical polymerizable vinyl monomer (e 3 ) is polymerized with other radical polymerizable vinyl monomer (e 4 ) in an aqueous solution or dispersion composed of a water-based polyurethane (e 1 ) for grafting and a saponified product (e 2 ) of a vinyl acetate-based copolymer.
• a hydrophilic radical polymerizable vinyl monomer (e 3 ) is polymerized with other radical polymerizable vinyl monomer (e 4 ) in an aqueous solution or dispersion composed of a water-based polyurethane (e 1 ) for grafting and a saponified product (e 2 ) of a vinyl acetate-based copolymer.
• water-based polyester resin (e 1 ) for grafting there can be preferably employed the water-based polyester resin composition (E1) exemplified in the illustration of the above-described water-based polyester resin composition.
• the saponified product (e 2 ) of a vinyl acetate-based copolymer there can be preferably employed the saponified product (B) of a vinyl acetate-based copolymer exemplified in the illustration of the above-described saponified product of a vinyl acetate-based copolymer.
• hydrophilic radical polymerizable vinyl monomer (e 3 ) there can be preferably employed the monomer (a 2 ) having a hydrophilic group composed of the monomer having a polyalkyleneoxide group exemplified in the illustration of the above-described cationic (meth)acrylic copolymer.
• the other radical polymerizable vinyl monomer (e 4 ) there can be preferably employed the nonionic monomer (a 5 ) exemplified in the illustration of the above-described cationic (meth)acrylic copolymer.
• the polyester-based graft polymer mixture (E) is obtained by graft polymerization of 100-60% by weight of the hydrophilic radical polymerizable vinyl monomer (e 3 ) with 0-40% by weight of other radical polymerizable vinyl monomer (e 4 ) in an aqueous solution or dispersion of a mixture of the above-described water-based polyester resin (e 1 ) for grafting with the above-described saponified product (e 2 ) of a vinyl acetate-based copolymer.
• the hydrophilic radical polymerizable vinyl monomer (e 3 ) is not more than 60% by weight, an absorbing ability of a water-based ink becomes worse.
• the saponified product (e 2 ) of a vinyl acetate-based copolymer is 10-500 parts by weight, and preferably 20-300 parts by weight
• the radical polymerizable vinyl monomer (e 3 ) is 10-500 parts by weight, and preferably 20-300 parts by weight, which are based on and 100 parts by weight of the water-based polyester resin (e 1 ) and which based on solid ratio.
• the saponified product of a vinyl acetate-based copolymer is less than 10 parts by weight
• a clearness and ink-absorbing ability are apt to lower and, in the case of exceeding 500 parts by weight, there becomes worse an adhesion to a plastic film-synthesized paper such as a polyester film which is a base material.
• the radical polymerizable vinyl monomer (e 3 ) is less than 10 parts by weight
• an ink-absorbing ability becomes worse and, in the case of exceeding 500 parts by weight, water resistance becomes worse and there is shown a tendency that there lowers an adhesion of a plastic film to a base material.
• the polymerization method for obtaining the polyester-based graft polymer mixture (E) conventionally publicly-known methods can be applied. For example, there is enumerated a method in which a polymerization initiator and optionally a small amount of an emulsifier are added into an aqueous solution/dispersion of a mixture of the above-described water-based polyester resin (e 1 ) for grafting with the above-described saponified product (e 2 ) of a vinyl acetate-based copolymer, and the hydrophilic radical polymerizable vinyl monomer (e 3 ) is gradually added while maintaining at 70-80C° , followed by aging for 2-5 hours to complete the polymerization and to obtain the polymer mixture (E).
• a polymerization initiator and optionally a small amount of an emulsifier are added into an aqueous solution/dispersion of a mixture of the above-described water-based polyester resin (e 1 ) for grafting with the above-described
• the polyester-based graft polymer mixture (E) is excellent in the absorbing ability of a water-soluble ink and, in addition, it has adhesion, water resistance, and toughness, etc. which are a characteristic in a polyurethane resin.
• polymerization initiator there can be employed a usual radical polymerization initiator, for example, there can be employed the polymerization initiator exemplified in the above-described polyurethane-based graft polymer mixture (D).
• polyester-based graft polymer mixture obtained optionally, there can be likewise employed the additives exemplified in the illustration of the above-described polyurethane-based graft polymer mixture (D).
• the block isocyanate compound (F) in relation to the present invention No. III is obtained by allowing to react an isocyanate compound with a blocking agent until free isocyanate groups disappears by a usual method.
• polyisocyanate there can be preferably employed the isocyanate compound exemplified in the illustration of the above-described water-based polyurethane resin (C).
• the blocking agent there can be employed a large number of publicly-known ones, for example, there are enumerated oximes such as methylethyl ketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; phenols such as m-cresol and xylenol; alcohols such as methanol, ethanol, butanol, 2-ethylhexanol, cyclohexanol, andethyleneglycolmonomethylether; lactams such as ⁇ -caprolactam; diketones such as diethyl maloate, acetoacetic acid ester; and mercaptans such as thiophenol, etc.
• ureas such as thiourea
• imidazoles imidazoles
• carbamic acids etc.
• the block isocyanate compounds are commercially supplied, for example, there can be obtained Desmodule series (Sumitomo Beyaer Urethane, Ltd.), Bernok D series (Dainippon Ink Kagaku Kogyo, Ltd.), Takenate B series (Takeda Yakuhin Kogyo, Ltd.), Aquanate 200 series (Nihon Polyurethane Kogyo, Ltd.), and Elastolon BN series (Daiichi Kogyo Seiyaku, Ltd.), etc. there is preferred a block isocyanate compound blocked by an oxime or a lactam.
• the cationic acrylic-based copolymers (A-I to A-III) having a crosslinkable group the saponified product (B) of a vinyl acetate copolymer having a polymerization degree of 200-1000 and, further, the modifier (R) under fixed conditions described hereinafter.
• the modifier (R) is 0-80% by weight, preferably 5-60% by weight, and more preferably 5-65% by weight. Further, as the modifier (R), there can be applied the preferred embodiment as described hereinabove.
• the modifier (R) is constructed by the water-based polyurethane resin (C), the polyurethane-based graft polymer mixture (D), and the polyester-based graft polymer mixture (E) and, formulating is conducted in 2-80% by weight of the (A-I to A-III), and preferably 5-50% by weight, 5-80% by weight of the (B), and preferably 15-75% by weight, (n 1 -80)% by weight of the (C), and preferably (n 1 -50)% by weight, (n 2 -60)% by weight of the (D), and preferably (n 2 -50)% by weight, (n 3 -60)% by weight of the (E) in 100% by weight of the resin composition for an ink jet recording sheet.
• minimum number is 0% by weight, respectively, and (n 1 +n 2 +n 3 ) is ⁇ 5, preferably not less than 10% by weight.
• the (A-I to A-III) is outside of a range of 2-80% by weight, there lower ink-fixing ability, water resistance, and printing quality, and in the case that the (B) is outside of a range of 5-80% by weight, ink-absorbing ability lowers and, further, under the fixed conditions described hereinabove, in the case that the (C) is outside of a range of (n 1 -80)% by weight, there lower water resistance and adhesion to a base material and, in the case that both of the (D) and (E) are outside of a range of (n 2 -60)% by weight, there lower water resistance, ink-absorbing ability, and printing quality.
• a cationic (meth)acrylic copolymer (A-IV) obtained by copolymerizing a monomer (a 1 ) having a polyalkylene oxide group, a monomer (a 2 ) having a hydrophilic group, a monomer (a 3 ) having a crosslinkable group, and a cationic monomer (a 4 ), 0-90% by weight of a saponified product (B) of a vinyl acetate copolymer, and 0-80% by weight of a modifier (R).
• A-IV cationic (meth)acrylic copolymer obtained by copolymerizing a monomer (a 1 ) having a polyalkylene oxide group, a monomer (a 2 ) having a hydrophilic group, a monomer (a 3 ) having a crosslinkable group, and a cationic monomer (a 4 ), 0-90% by weight of a saponified product (B) of a vinyl acetate copolymer, and
• the resin composition for ink jet recording in relation to the present invention No. IV, there can be enumerated a resin composition composed of 5-80% by weight of the cationic (meth)acrylic copolymer (A-IV), 15-80% by weight of the saponified product (B) of a vinyl acetate copolymer, and 5-60% by weight of the modifier (R).
• No. V there are formulated 70-100% by weight of the cationic (meth)acrylic copolymer (A-V), 0-30% by weight of the saponified product (B) of a vinyl acetate copolymer (total of those is 100% by weight), and 0-15 parts by weight of the modifier (R) based on 100 parts by weight of the total of the (A-V) and the (B).
• constructing ratio of respective components is represented based on solid components.
• the ratio of respective components which construct the resin composition for a recording sheet can be selected within a range in which there are not deteriorated an ink-absorbing ability, water resistance, printing quality, glossiness, and roll-mark resistance, etc.
• the cationic (meth)acrylic copolymer (A-IV or A-V) affects to an ink-fixing ability, water resistance, an ink-absorbing ability, and printing quality, which is obtained by copolymerizing a monomer (a 1 ) having a polyalkylene oxide group, a monomer (a 2 ) having a hydrophilic group, a monomer (a 3 ) having a crosslinkable group, and a cationic monomer (a 4 ),
• the saponified product (B) of a vinyl acetate copolymer affects to an ink-absorbing ability and an embossed roll mark adherence property
• the polymerization degree in the saponified product (B) of a vinyl acetate copolymer affects to a printing quality such as beading
• the modifier (R) affects to water resistance, adhesion to a base material, and a printing quality such as beading.
• Composition ratio of the respective components in the composition in relation to the present invention enables to well-balance in a high level of respective performances in consideration thereof.
• Formulation ratio of the cationic (meth)acrylic copolymer (A-V) with respect to the saponified product (B) of a vinyl acetate copolymer is (70-100% by weight)/(0-30% by weight) (total of both is 100% by weight).
• the (B) exceeds 30% by weight, although an ink-absorbing ability elevates, since the (B) tends to be softened by absorbing an ink, an embossed roll-mark is unpreferably apt to become adhered.
• the (A-V) absorbs an ink, since a softening degree is small, it has a characteristic that an embossed roll-mark is not marked.
• the modifier (R) is formulated in 0-15 parts by weight based on 100 parts by weight of the total of the (A-V) and the (B), and in the case of exceeding 15 parts by weight, an ink-absorbing ability is apt to be reduced in an image-receiving layer, and there is shown a tendency affecting to a printing quality.
• the cationic (meth)acrylic copolymer (A-V) is preferably 70-100% by weight
• the saponified product (B) of a vinyl acetate copolymer is preferably 0-30% by weight (total of both is 100% by weight)
• the modifier (R) is preferably 0.2-10 parts by weight of based on 100 parts by weight of the total of the (A-V) and the (B).
• the (A-V) is 75-95% by weight
• the (B) is 5-25% by weight
• the modifier (R) is preferably 0.5-5 parts by weight of based on 100 parts by weight of the total of the (A-V) and the (B).
• the monomer (a 1 ) having a polyalkylene oxide group (a polyoxyalkylene group) which constructs the cationic (meth)acrylic copolymers (A-IV to A-V) there can be exemplified a (meth)acrylate monomer containing a polyalkyleneoxide group such as a monoester of a mono, di, tri, or polyalkylene glycol with a (meth)acrylic acid, which is a monomer copolymerizable with the monomer (a 2 ) having a hydrophilic group, a monomer (a 3 ) having a crosslinkable group, a cationic monomer (a 4 ), or a nonionic monomer (a 5 ).
• a (meth)acrylate monomer containing a polyalkyleneoxide group such as a monoester of a mono, di, tri, or polyalkylene glycol with a (meth)acrylic acid
• the mono, di, tri, or polyalkylene glycol for example, there can be preferably employed a vinyl monomer having an oxyalkylene group, etc. exemplified in the illustration of the constructing components for the saponified product (B) of a vinyl acetate copolymer.
• a (meth)acrylate which is a vinyl monomer in which the oxyalkylene group is an oxyethylene group, particularly, a polyoxyalkylene (meth)allyl ether (of those, a polyoxyethylene allyl ether).
• the vinyl monomers can be employed solely or in combination of two or more kinds.
• a structural formula of the alkyleneoxide group is shown by a general formula: -[(CHR 1 ) n -O] m -R 2 [In the formula, R 1 is a hydrogen atom, methyl group, or hydroxyl group, R 2 is a hydrogen atom or methyl group, "n” is an integer of 1-5, “m” is an integer of 1-20, “n and m” pieces of R 1 may be even identical to or different from each other]
• the monomer (a 2 ) having a hydrophilic group which constructs the cationic (meth)acrylic copolymers (A-IV to A-V) there can be employed the monomer having a hydrophilic group exemplified in the illustration of the above-described cationic (meth)acrylate copolymers (A-I to A-III) containing a crosslinkable group.
• a monomer having carboxylic group [a (meth)acrylic acid, etc.] and a monomer having hydroxyl group [2-hydroxyethyl(meth)acrylate and 2-hydroxypropyl(meth)acrylate, etc.].
• the monomer (a 3 ) having a crosslinkable group to be employed in the cationic (meth)acrylic copolymers (A-IV to A-V) there can be likewise employed the monomer having a crosslinkable group exemplified in the illustration of the above-described cationic (meth)acrylate copolymers (A-I to A-III) containing a crosslinkable group.
• a monomer having a crosslinkable group such as a monomer having a hydrolyzable condensible group, particularly, an alkoxysilyl group (a C 1-4 alkoxysilyl group such as methoxysilyl group and ethoxysilyl group, etc.).
• cationic monomer (a 4 ) which constructs the cationic (meth)acrylic copolymers (A-IV to A-V)
• cationic monomer (a-I to A-III) there can be likewise employed the cationic monomer exemplified in the illustration of the above-described cationic (meth)acrylate copolymers (A-I to A-III) containing a crosslinkable group.
• the monomers are employed in combination with the nonionic monomer (a 5 ) in addition to the above-described various monomers as the cationic (meth)acrylate copolymers (A-I to A-III) in order to adjust film-formability and film properties.
• nonionic monomer (a 5 ) there can be likewise employed the nonionic monomer exemplified in the illustration of the above-described cationic (meth)acrylate copolymers (A-I to A-III) containing a crosslinkable group.
• nonionic monomer (a 5 ) there can be usually employed a C 1-18 alkyl(meth)acrylate [particularly, a C 2-10 alkylacrylate and a C 1- 6 alkylmethacrylate], aromatic vinyls [particularly, styrene], and vinyl esters [particularly, vinyl acetate].
• the nonionic monomers (a 5 ) can be also employed solely or in combination of two or more kinds.
• use amount of the cationic monomers (a 4 ) and the monomer (a 3 ) having a crosslinkable group can be selected within a range in which water resistance and ink-absorbing ability are not deteriorated, and the cationic monomer (a 4 ) is preferably 0.1-50% by weight (for example, 1-45% by weight), more preferably 0.5-40% by weight (for example, 2-35% by weight), and most preferably 1-30% by weight (for example, 3-25% by weight) based on total monomers which construct the cationic acrylic copolymer (A-IV), and it is usually 2-25% by weight or so.
• use amount of the monomer (a 3 ) having a crosslinkable group is preferably 0.1-25% by weight, more preferably 0.2-20% by weight, and most preferably 0.5-15% by weight based on all monomers, and it is usually 0.3-10% by weight or so.
• proportion of the respective monomers can be selected in consideration of a preferred range of the respective components in the above-described (a 1 )-(a 5 ) which construct the (A-IV to A-V).
• the monomer (a 1 ) having a polyalkylene oxide group is preferably 0.1-40% by weight, more preferably 3-35% by weight, and most preferably 5-30% by weight
• the monomer (a 2 ) having a hydrophilic group is preferably 0.1-50% by weight, more preferably 2-45% by weight, and most preferably 5-40% by weight
• the monomer (a 3 ) having a crosslinkable group is preferably 0.5-20% by weight, more preferably 1-15% by weight, and most preferably 2-10% by weight
• the cationic monomer (a 4 ) is preferably 1-40% by weight, more preferably 3-35% by weight, and most preferably 5-30% by weight
• the hard monomer (a 6 ) is preferably 10-60% by weight, more preferably 20-55% by weight, and most preferably 25-50% by weight
• the soft monomer (a 7 ) is preferably 10-60% by weight, more preferably 15-50% by weight
• the monomer (a 1 ) having a polyalkylene oxide group is preferably 8-40% by weight, more preferably 12-30% by weight, and most preferably 15-25% by weight
• the monomer (a 2 ) having a hydrophilic group is preferably 1-30% by weight, more preferably 2-20% by weight, and most preferably 4-15% by weight
• the monomer (a 3 ) having a crosslinkable group is preferably 0.2-10% by weight, more preferably 0.4-6% by weight, and most preferably 0.7-3% by weight
• the cationic monomer (a 4 ) is preferably 10-50% by weight, more preferably 20-40% by weight, and most preferably 25-35% by weight
• the nonionic monomer (a 5 ) is preferably 10-80% by weight, more preferably 20-70% by weight, and most preferably 30-60% by weight.
• a weight average molecular weight is not particularly limited, and it is selected from a range of preferably 0.2x10 4 -100x10 4 , and more preferably 1x10 4 -50x10 4 .
• tackiness is apt to be caused by increased low molecular weight components.
• viscosity becomes high, and inconvenience is caused in view of production.
• the glass transition temperature in the cationic (meth)acrylic copolymers (A-IV to A-V) can be selected within a range in which film-formability is not deteriorated. For example, it is preferably -20 to 50°C, more preferably -10 to 40°C, particularly preferably 0 to 30°C or so.
• a polymer having such the glass transition temperature can be appropriately prepared in combination of the above-described cationic monomer (a 4 ), monomer (a 3 ) having a crosslinkable group, and other monomers.
• the monomers often usually construct a copolymer in combination with a hard monomer [for example, a monomer having a glass transition temperature of 80 to 120°C (particularly, 90 to 105°C) such as methyl(meth)acrylate and styrene which forms a homopolymer] which is the above-described nonionic monomer (a 5 ) and a soft monomer [for example, a monomer having a glass transition temperature of -85 to -10°C (particularly, -85 to -20°C) such as a C 2-10 alkylacrylate which forms a homopolymer].
• a hard monomer for example, a monomer having a glass transition temperature of 80 to 120°C (particularly, 90 to 105°C) such as methyl(meth)acrylate and styrene which forms a homopolymer
• a soft monomer for example, a monomer having a glass transition temperature of -85 to -10°C (particularly, -85 to -20
• Nos. IV and V there is not particularly limited a polymerization style for the cationic (meth)acrylic copolymers (A-IV to A-V) which are constructed by the above-described monomers, and a polymer obtained may be even any one of a random copolymer, a graft copolymer, and a block copolymer, etc.
• Form of the cationic (meth)acrylic copolymers (A-IV to A-V) may be even a solution such as an organic solvent solution and an aqueous solution, and it is usually a cationic emulsion (particularly, an aqueous emulsion).
• the cationic emulsion containing the cationic (meth)acrylic copolymers (A-IV to A-V) can be obtained by a commonly-used method, for example, a method in which the above-described monomers are emulsion-polymerized in an emulsion system containing a nonionicbased surface active agent and/or a cationic-based surface active agent, and a method in which a water-based emulsion is prepared by allowing to form a tertiary amine salt or a quaternary ammonium salt after polymerization of the above-described monomers.
• surface potential is +20 to +60 mV, preferably +12 to +55 mV (for example, +15 to +55 mV), and particularly preferably +20 to +55 mV or so.
• ⁇ potential is +20 to +60 mV, preferably +12 to +55 mV (for example, +15 to +55 mV), and particularly preferably +20 to +55 mV or so.
• Average particle diameter of polymer particles in the cationic emulsion is 1-200 nm, preferably 3-100 nm, and more preferably 5-50 nm or so.
• the cationic emulsion containing the cationic acrylic copolymers (A-IV to A-VI) can be obtained by a commonly-used method, for example, a method in which the above-described two or three monomers are emulsion-polymerized in an emulsion polymerization-system containing a nonionic surface active agent and/or a cationic surface active agent, or a method in which a water-based emulsion is prepared by allowing to form a tertiary amine salt or a quaternary ammonium salt after copolymerization of the monomers.
• the saponified product (B) of a vinyl acetate copolymer in the present inventions No. IV and No. V there can be preferably employed the saponified product (B) of a vinyl acetate copolymer illustrated in the present inventions No. I-III.
• Substance to be employed as the modifier (R) in the present inventions No. IV and No. V is a water-based polyurethane resin composition (C1) and/or a water-based polyester resin composition (E1).
• the water-based polyurethane resin composition (C1) and the water-based polyester resin composition (E1) are the same water-based polyurethane resin composition (C1) and water-based polyester resin composition (E1) as in the present invention No. III.
• a primary component in the composition (P) which constructs an ink-receiving layer is a polymerizable unsaturated monomer (A-VI) having a hydrolyzable silyl group prepared by copolymerization of monomers containing a polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group and a (meth)acrylic-based polymerizable unsaturated monomer (a 9 ).
• a polymerizable unsaturated monomer having a hydrolyzable silyl As the polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl, a polymerizable unsaturated monomer having a hydrolyzable silyl group shown by general formula (1) described below is enumerated.
• R 1 , R 2 and R 3 may be identical or different from each other, and any one of a halogen atom, an alkyl group, an aryl group, an aralkyl group, an a ⁇ lkoxy group, an aryloxy group, an acyloxy group, a hydroxyl group, an amino group, an aminoxy group, and an alkylthio group
• the R 1 , R 2 and R 3 which construct a silyl group shown by the general formula (1) can be selected from the above-described various groups and, usually, at least one thereof is preferably a halogen atom, an alkoxy group, and a hydroxyl group.
• the halogen atom described herein includes fluorine, chlorine, bromine, and iodine, and it is usually preferably chlorine atom.
• alkyl group there can be preferably exemplified a C 1-10 alkyl group such as methyl, ethyl, propyl, butyl, pentyl, and hexyl.
• aryl group there can be exemplified a C 6-10 aryl group such as phenyl group and, as the aralkyl group, there can be exemplified a C 6-10 aralkyl group such as benzyl group as a preferred group.
• alkoxy group there can be exemplified a C 1-16 alkoxy group such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, and dodecyloxy as a preferred group, and a C 1-4 alkoxy group is preferred, and methoxy and ethoxy groups are particularly preferred. It is to be noted that the alkoxy group also includes an alkoxy-alkoxy group such as methoxyethoxy group.
• aryloxy group a C 6-10 garyloxy group such as phenoxy group can be exemplified as a preferred group
• acyloxy group there can be exemplified a C 2-6 acyloxy group such as acetyloxy (acetoxy), propyonyloxy, and butyryloxy groups as a preferred group.
• amino group there is included an amino group which may have a substituted group such as dimethylamino group and, aminoxy group may have a substituted group such as dimethylaminoxy group, and dimethylaminoxy group and diethylaminoxy group can be exemplified as a preferred group.
• alkylthio group there can be exemplified a C 1-6 alkylthio group such as methylthio group and diethylthio group as a preferred group.
• the polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group includes, for example, the following monomers.
• polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group in addition to the examples, for example, there may be even a monomer containing a divinyl group such as divinyldimethoxy silane, divinyldiethoxy silane, and divinyldi( ⁇ -methoxyethoxy)silane.
• Such the monomer having a silyl group preferably includes, for example, a vinyl-based monomer containing an alkoxysilyl group from a viewpoint of a handling ability, profitability, and suppression of side reactions, etc.
• the composition (P) contains as a primary component the (meth)acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group prepared by a copolymerization of monomers containing the polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group and the (meth)acrylate-based polymerizable unsaturated monomer (a 9 ) described hereinafter.
• A-VI the (meth)acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group prepared by a copolymerization of monomers containing the polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group and the (meth)acrylate-based polymerizable unsaturated monomer (a 9 ) described hereinafter.
• the (meth)acrylate-based polymerizable unsaturated monomer (a 9 ) can be employed even solely or in combination of two or more kinds.
• the (meth)acrylate-based copolymerizable unsaturated monomer (a 9 ) includes, for example, a (meth)acrylate, (meth)acrylic amides, and a (meth)acrylonitrile, etc.
• an alkyl(meth)acrylate for example, C 1-18 alkyl(meth)acrylates such as methyl(meth)acrylate,ethyl(meth)acrylate,propyl(meth)acrylate, isopropyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth) acrylate, t-butyl(meth)acrylate, hexyl(meth)acrylate, octyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and lauryl(meth)acrylate], a cycloalkyl(meth)acrylate [for example, cyclohexyl(meth)acrylate, etc.], an aryl(meth)acrylate [for example, phenyl(meth)acrylate, etc.], an aralkyl(meth)acrylate [for example,
• (meth)acrylamides there can be exemplified (meth)acrylamide, ahydroxyalkyl(meth)acrylamide [for example, an N-hydroxy-C 1-4 alkyl(meth)acrylamide such as N-methylol(meth)acrylamide], an alkoxyalkyl(meth)acrylamide [for example, N-hydroxy-C 1-4 alkoxy-C 1-4 alkyl(meth)acrylamides such as N-methoxymethyl(meth)acrylamide], and diacetone(meth)acrylamide, etc.
• ahydroxyalkyl(meth)acrylamide for example, an N-hydroxy-C 1-4 alkyl(meth)acrylamide such as N-methylol(meth)acrylamide
• an alkoxyalkyl(meth)acrylamide for example, N-hydroxy-C 1-4 alkoxy-C 1-4 alkyl(meth)acrylamides such as N-methoxymethyl(meth)acrylamide
• diacetone(meth)acrylamide etc.
• a (meth)acrylic-based polymerizable unsaturated monomer (a 9 ) in relation to the present invention, there can be exemplified a (meth)acrylate [for example, a C 1- 18 alkyl(meth)acrylate, a hydroxy-C 2-4 alkyl(meth)acrylate, glycidyl (meth) acrylate, di-C 1-4 alkylamino-C 2-4 alkyl (meth) acrylate, etc.] and (meth)acrylamides, etc.
• a (meth)acrylate for example, a C 1- 18 alkyl(meth)acrylate, a hydroxy-C 2-4 alkyl(meth)acrylate, glycidyl (meth) acrylate, di-C 1-4 alkylamino-C 2-4 alkyl (meth) acrylate, etc.
• (meth)acrylamides etc.
• a more preferred (meth)acrylic-based monomer there can be enumerated a C 2- 10 alkylacrylate, C 2-10 alkylmethacrylate, a hydroxy-C 2-3 alkyl(meth)acrylate, glycidyl(meth)acrylate, and di C 1-3 alkylamino-C 2-3 alkyl(meth)acrylate.
• the (meth)acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group in relation to the present invention is obtained by a copolymerization of monomers containing the (a 8 ) and (a 9 ), and as the latter (a 9 ) or in addition to the (a 9 ), there may be often employed a hard monomer [for example, a monomer component which forms a homopolymer having a glass transition temperature of 80 to 120°C.
• a soft monomer for example, a monomer component which forms a homopolymer having a glass transition temperature of -85 to -10°C (particularly, -85 to -20°C) or so such as a C 2-10 alkylacrylate] in combination thereof.
• a copolymerizable unsaturated monomer which is further added is hereinafter represented as other copolymerizable unsaturated monomer (a 10 ).
• the (meth)acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group is constructed by the polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group, the (meth)acrylate-based polymerizable unsaturated monomer (a 9 ), and the other copolymerizable unsaturated monomer (a 10 ), use amount of respective monomer components is not limited.
• a respective preferred range of the (a 8 ) and (a 9 ) is a range described below (herein, total of the (a 8 ) and (a 9 ) is 100% by weight), and it is appropriately preferably selected in the range.
• a ratio of use amount between each other is not particularly limited, and a preferred range is a range (herein, total is 100% by weight) as described below, it is appropriately preferably selected in the range.
• the (meth)acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group which is one of primary components in the composition (P) in relation to the present invention, may be any one of embodiments of a water-based product such as an aqueous solution, a water-based emulsion (a water-based polymer emulsion), a nonaqueous solution such as an organic solvent solution and an organic solvent emulsion, and a solid powder, etc., and which are not problematic in use.
• the water-based product is preferred in view of handling, preparation, and handling in the preparation of the composition (P) from inorganic compound fine particles (G) of other primary components.
• the water-based product since it is constructed by a water-based resin component constructed from a copolymer of the polymerizable unsaturated monomer (a 8 ) having a hydrolyzable silyl group with the (meth)acrylate-based polymerizable unsaturated monomer (a 9 ) without using a crosslinked resin such as a crosslinked product of an acrylic silicone oligomer containing a hydrolyzable alkoxysilyl group, it can be readily handled.
• the average particle diameter in particles of the copolymer is selected from a range of 0.01-2 ⁇ m, preferably 0.01-1 ⁇ m, more preferably 0.01-0.5 ⁇ m, and further preferably 0.01-0.3 ⁇ m- or so, so that dispersion stability and adhesion are not deteriorated.
• a method for the preparation of the aqueous solution or water-based emulsion of the (meth)acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group it is not particularly limited, and commonly-used methods can be applied, for example, (1) a method in which the monomer containing a hydrolyzable silyl group represented by the above-described general formula (1) is copolymerized with a polymerizable unsaturated (meth)acrylate-based monomer having a functional group such as carboxylic group or amino group to prepare a copolymer, and the copolymer is dissolved or dispersed using an alkali (for example, an alkyl amine such as triethylamine, a cyclic amine such as morpholine, an alkanol amine such as triethanolamine, pyridine, and ammonia, etc.), an acid [for example, there can be exemplified an inorganic acid (for example, hydrochloric
• the copolymer may be prepared even by a solution-polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method, etc. It is to be noted that a style in the polymerization may be any one of a batchwise or continuous one.
• the polymerization may be conducted under the presence of organic solvents [for example, an alcohol (ethanol, isopropanol, and n-butanol, etc.), an aromatic hydrocarbon (benzene, toluene, and xylene, etc.), an aliphatic hydrocarbon (pentane, hexane, andheptane,, etc.), acycloaliphatic hydrocarbon (cyclohexane, etc.), an ester (ethyl acetate and n-butyl acetate, etc.), a ketone (acetone and methylethylketone, etc.), and an ether (diethylether, dioxane, and tetrahydrofran, etc.).
• organic solvent for example, an alcohol (ethanol, isopropanol, and n-butanol, etc.), an aromatic hydrocarbon (benzene, toluene, and xylene, etc.), an aliphatic hydrocarbon (p
• organic solvent there may be usually employed an alcohol such as isopropanol, an aromatic hydrocarbon such as toluene, and a ketone such as methylethylketone, etc.
• an alcohol such as isopropanol
• an aromatic hydrocarbon such as toluene
• a ketone such as methylethylketone
• a polymerization may be initiated by irradiation of an electron beam or an ultraviolet ray and heating, it is often initiated using a polymerization initiator.
• polymerization initiator there can be employed the polymerization initiators exemplified in the illustration of the polyurethane-based graft polymer mixture (D).
• Use amount of the polymerization initiator can be selected from, for example, a range of preferably 0.001-20% by weight, and more preferably 0.01-10% by weight (for example, 0.1-10% by weight) or so based on total amount of the monomers (the monomer having a silyl group and the copolymerizable components) and, usually, it is selected from such the range.
• Reaction temperature in the solution polymerization is preferably 50-150°C, and more preferably 70-130°C or so. Further, reaction time of period is preferably 1-10 hours, and more preferably 2-7 hours or so.
• a terminating point of the polymerization can be identified by disappearance in the absorption (for example, 1648 cm -1 ) by double bonds in infrared absorption spectra or a decrease of unreacted monomers using a gas chromatography.
• an emulsifier for example, an alkyl sulphate, an alkylaryl sulphonate, an alkyl phosphate or an anionic surface active agent such as a fatty acid salt, a cationic surface active agent such as an alkyl amine salt and an alkyl quaternary ammonium salt, a nonionic surface active agent such as a polyoxyethylene alkylarylether, a polyoxyethylene alkylether, or a pulronic-type nonionic surface active agent such as a polyoxyethylene-polyoxypropylene condensate which is a product by Asahi Denka, Ltd., or an ampholytic surface active agent such as a carboxylic acid salt-type (an amino acid-type or betaine-type) or a sulphonic acid salt-type agent.
• pH adjustment of the emulsifier for example, an alkyl sulphate, an alkylaryl sulphonate, an alkyl phosphate or an anionic surface active
• the polymer in modification for giving an aqueous property to the above-described copolymer, in the case that the polymer contains a cationic group such as a cation-formable group, amino group, and imide group, the polymer can be readily dissolved or emulsified because of an increase of hydrophilic property by the use of acids.
• a cationic group such as a cation-formable group, amino group, and imide group
• an inorganic acid hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid, etc.
• an organic acid a saturated aliphatic monocarboxylic acid such as formic acid, acetic acid, and propionic acid
• a saturated aliphatic polycarboxylic acid such as oxalic acid and adipic acid
• an unsaturated aliphatic monocarboxylic acid such as (meth)acrylic acid
• an unsaturated aliphatic polycarboxylic acid such as maleic acid and itaconic acid
• an aliphatic oxycarboxylic acid such as lactic acid and citric acid, etc.
• the polymer contains an acidic group such as carboxylic group
• the polymer can be readily dissolved or emulsified by the use of a base.
• a base for example, there can be included an organic base (an alkyl amine such as triethylamine, a cyclic amine such as morpholine, an alkanol amine such as triethanol amine, and pyridine, etc.) and an inorganic base (ammonia and a hydroxide of an alkali metal, etc.), etc.
• the polymer obtained by a solution polymerization can be emulsified under the presence or the absence of organic solvents.
• a water-soluble organic solvent for example, an alcohol such as isopropanol
• the organic solvent may be even removed by evaporation, etc. after emulsifying, and an emulsion may also contain the organic solvent.
• an organic solvent a ketone such as methylethylketone having a low boiling point is often employed.
• the polymer obtained by solution polymerization is emulsified under the presence of organic solvents
• it can be emulsified by adding water after adding an additive (for example, an emulsifier, a pH regulator, and an acid, etc.) to an organic solution containing the polymer.
• an additive for example, an emulsifier, a pH regulator, and an acid, etc.
• Emulsifying is preferably carried out at a low temperature, for example, it can be selected from a range of not more than 70°C (for example, 5-70°C), and preferably not more than 50°C or so (for example, 10-50°C).
• removal of the organic solvents is often carried out at, for example, not more than 80°C (for example, 5-80°C) and an ordinary or reduced pressure (for example, 0.0001-1 normal atmosphere or so).
• the copolymer is obtained by conducting the emulsion polymerization of the respective monomers ((a 8 ) and (a 9 ), (a 8 ), (a 9 ), and (a 10 )) in relation to the present invention
• a commonly-used method can be applied and, for example, there can be applied a method for collectively-feeding the respective monomers (for example, a method in which the respective monomers are collectively fed into a water-based medium to allow to copolymerize) and a method for adding monomers (a method in which the respective monomers are separately fed while mixing into a water-based medium to allow to polymerize).
• the monomers may be prepared as a pre-emulsion which is in advance emulsified.
• emulsifying may be even conducted using a polymerizable emulsifier and may be emulsified using an emulsifier.
• the polymerizable emulsifier for example, commonly-used various polymerizable emulsifiers [compounds which contain (meth)allyl group or (meth)acrylic group as a polymerizable group and contain a cationic group such as a quaternary ammonium salt, a tertiary amine salt, amino group, and imide group, an anionic group such as a sulfonic acid salt and a carboxylic acid salt, a nonionic group such as an ethyleneoxide group, etc. as a emulsifying-functional group] can be employed.
• use amount of the emulsifier can be appropriately selected from a range of, for example, preferably 0.1-20% by weight, and more preferably 0.5-10% by weight based on total amount of monomers.
• the polymerization initiator to be employed in the emulsion polymerization of the polymerization initiators exemplified in the above-described polyurethane-based graft polymer mixture (D), there can be employed the water-soluble polymerization initiators such as inorganic peroxides, and water-soluble redox-type polymerization initiator-system may be also employed.
• emulsifiers As the emulsifier to be employed in the emulsion polymerization, there are enumerated emulsifiers, etc. which can be employed in the case of emulsifying the above-described solution polymer. Further, for the purpose of stabilizing the emulsion polymerization, a protective colloidal agent (a partially-saponified polyvinyl alcohol, a carboxymethyl cellulose, a methyl cellulose, a hydroxyethyl cellulose, and a hydroxypropyl cellulose,) may be employed. It is to be noted that a pH controlling agent may be employed in emulsifying.
• a protective colloidal agent a partially-saponified polyvinyl alcohol, a carboxymethyl cellulose, a methyl cellulose, a hydroxyethyl cellulose, and a hydroxypropyl cellulose,
• a pH controlling agent may be employed in emulsifying.
• conditions such as temperature may be same conditions as in the solution polymerization described hereinabove.
• a chain transfer agent in order to adjust a molecular weight of the copolymer, for example, such as alcohols such as catechol, thiols, mercaptans (n-lauryl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 3-mercaptopropyl trimethoxy silane, 3-mercaptopropyl methyldimethyl silane).
• nonionic property is preferred and, of those, an anionic property is more preferred.
• the (meth)acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group is a water-based resin
• a variety of additives in order to elevate weatherability of a recorded picture image, for example, which includes a lubricant such as a fluorine resin, a silicone resin, an organic sulphonate compound, an organic phosphate compound, and an organic carboxylate compound, a stabilizer such as an antioxidant, an ultraviolet ray absorbent, and a thermal stabilizer, a variety of additives such as a radical scavenger, a delustering agent, an antistatic agent, a plasticizer, a thickener, and a defoaming agent.
• a radical scavenger such as a fluorine resin, a silicone resin, an organic sulphonate compound, an organic phosphate compound, and an organic carboxylate compound
• a stabilizer such as an antioxidant, an ultraviolet ray absorbent, and a thermal stabilizer
• composition (P) which constructs an ink-receiving layer in relation to the present invention primarily contains the (meth)acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group and inorganic compound-based fine particles (G).
• the inorganic compound-based fine particles (G) for example, there are enumerated fine particles composed of silica, alumina, white carbon, a calcine diatomaceous, and an oxide (including a composite oxide and a hydrate) such as titanium oxide; a hydroxide such as aluminum hydroxide, calcium hydroxide, and magnesium hydroxide; a carbonate such as calcium bicarbonate, a heavy calcium carbonate, a light calcium carbonate, and magnesium carbonate; a sulphate such as calcium sulphate; calcium silicate, magnesium silicate, talc, kaoline, delami kaoline, clay, bentonite, smectite, zeolite, a silicate or alumino silicate such as magnesium alumino silicate and celicite; and clay minerals, etc. which are an inorganic compound or a mixture thereof.
• the inorganic compounds to be employed in the present invention are not particularly limited and, as preferred inorganic compound-based fine particles, there are inorganic-based fine particles such as silica and alumina, and of those, silica is preferred. Particularly, there is preferred a colloidal silica dispersed in water which is connected in a rosary-state.
• the colloidal silica dispersed in water which is connected in a rosary-state is a colloidal suspension of a silicone dioxide or a hydrate thereof, and usually, it is obtained by allowing to react an aqueous solution of a silicate with a diluted hydrochloric acid, and even colloidal silica by any methods for the preparation can be employed.
• Average primary particle diameter in the inorganic compound-based fine particles is preferably 1-200 nm, more preferably 5-100 nm, and most preferably 15-50 nm. Secondary particle diameter is preferably 10-1000 nm, more preferably 20-500 nm, and most preferably 100-300 nm.
• composition of the composition (P) Composition of the composition (P)
• weight ratio (%) of the (A-VI) with the (G) which construct an ink-receiving layer and which is a primary component in the (P) since there are possibly a case that the (A-VI) is water-soluble and a case that it is a colloidal silica in which the (G) is dispersed in water, respective components are preferably represented based on a solid component value (weight), and the (A-VI)/(G) preferably ranges in (1-50)/(50-99) (respective values are % by weight, and total is 100% by weight).
• the composition (P) is preferably a water-based liquid, and it is preferably a water-based liquid adjusted to 10-50% by weight.
• the method for the preparation of the composition (P) comprises the (A-VI) and the (G) is not particularly limited and, in the case that both of the components (A-VI) and (G) are a solid, the (A-VI) and the (G) are preferably dispersed into water by a homogenizer, etc. after having crushed the (A-VI) and the (G), respectively.
• the (A-VI) is a colloidal silica in which a water-based emulsion (G) is dispersed in water and it is connected in a rosary-state, there is preferably a method in which mixing is conducted by agitating as it is.
• any one of the components (A-VI) and (G) is a solid and another one is water-based
• the solid is added to the water-based component after having crushed, followed by dispersing by a homogenizer, etc.
• Resin or resin composition to be employed for the ink-receiving layer is not particularly limited and, there is preferably employed a resin composition containing a mixture of at lest one resin selected from the group consisting of the (meth)acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group, a mixture of the (meth) acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group, the saponified product (B) of a vinyl acetate-based copolymer, and the water-based polyurethane-based graft polymer mixture (D), and the water-based polyester-based graft polymer mixture (E).
• the resin alone or a resin composition of the resin with the above-described other resins.
• the resin containing a cationic group there can be preferably exemplified a dicyan-based resin (a dicyandiamide-formaldehyde polycondensate, etc.), a polyamine-based resin [a condensate (a dicyandiamide-diethylenetriamine polycondensate, etc.) of an aliphatic polyamine such as diethylenetriamine, triethylenetetramine, an aromatic polyamine such as phenylene diamine, or a condensed product (a dicyandiamide-diethylenetriamine polycondensate, etc.) of dicyan diamide with a polyC 2-4 alkylene polyamine], and a polycationc-based resin, etc.
• a dicyan-based resin a dicyandiamide-formaldehyde polycondensate, etc.
• a polyamine-based resin a condensate (a dicyandiamide-diethylenetriamine polycondensate, etc.) of
• an epichlorohydrin-diC 1-4 alkylamine-added polymer an epichlorohydrin-dimethylamine-added polymer, etc.
• a polymer of an alkylamine or a salt thereof a polymer of polyallylamine or a hydrochloric acid salt thereof, etc.
• a polymer of a diallylC 1-4 alkylamine or a salt thereof a polymer of a dialkylmethylamine or a hydrochloric acid salt thereof, etc.
• a polymer of a diallyldiC 1-4 alkyl ammonium salt a polymer of a diallyldimethyl ammonium chloride, etc.
• a copolymer of diallylamine or a salt thereof with sulphur dioxide a diallylamine hydrochloric acid salt-sulphur dioxide copolymer, etc.
• the resins containing a cationic group can be employed solely or in combination of two or more kinds.
• a cationic group-contained resin having a crosslinkable reactive group is preferably employed.
• the resin there can be enumerated a copolymer in which there is employed a monomer having a cationic group or a monomer producing a cationic property by acid neutralization in the above-described (meth)acrylate-based copolymer (A-VI) containing a hydrolyzable silyl group.
• the saponified product (B) of a vinyl acetate-based copolymer to be employed in the present invention No. VI there can be preferably employed the saponified product (B) of a vinyl acetate-based copolymer in relation to the present invention Nos. I-III.
• proportion of the copolymerizable monomer can be selected within a range in which clearness and water resistance of an image are not deteriorated, and it is preferably 0.1-50% by mol, more preferably 1-30% by mol, and further preferably 2.5-25% by mol, particularly, preferably 3-20% by mol based on total monomers to be employed for constructing the copolymer.
• the saponified product (B) of a vinyl acetate-based copolymer can be employed solely or in combination of a plurality of the products and, in addition, the other hydrophilic polymer (described hereinabove) may be even formulated depending upon purposes.
• water-based polyurethane-based resin to be employed in the present invention No. VI there can be preferably employed the water-based polyurethane-based resin (C) and/or the water-based polyurethane-based graft polymer mixture (D) in relation to the present invention Nos. I-III.
• the resin composition for recording in relation to the present invention No. VII contains 100 parts by weight of a resin (total of both is 100% by weight) composed of
• the resin composition for recording in relation to the present invention No. VII may be a resin composition for recording in which the cellulose derivative (H) is a cellulose acetate, a resin composition for recording in which proportion of the weak solvent (K) for the cellulose derivative (H) is 50-150 parts by weight, and a resin composition for recording in which the good solvent (I) for the cellulose derivative is at least one selected from the group consisting of ketones, esters, ethers, cellosolves, cellosolve acetates, halogenated hydrocarbons, and nitro compounds, and which has a boiling point of 35-160°C.
• it may be a resin composition for recording in which a melting point of the organic acid (J) is not less than 60°C, a resin composition for recording in which the weak solvent (K) for the cellulose derivative is at least one selected from esters, alcohols, ketones, and ethers, and which has a boiling point of 100-300°C, and a resin composition for recording in which the good solvent (I) for the cellulose derivative is at least one of a C 1- 5 dialkyl ketone, a C 1-4 dialkyl acetate, a C 4-6 Cyclic or linear chain ether, a C 1-4 dialkyl cellosolve, and a C 1-4 dialkyl cellosolve acetate, and the weak solvent (K) for the cellulose derivative is at least one of a C 1-4 alkyl formate, a C 1-4 alkyl benzoate, a C 4- 8 cycloalkanol, a C 6-10 dialkyl ketone, and a C 7-10 ether.
• the present invention may be a resin composition for recording in which the difference (TK-TI) of a boiling point is 10°C ⁇ (TK-TI) ⁇ 200°C in the good solvent (I) and the weak solvent (K) for the cellulose derivative (H), and may be even a resin composition for recording in which solubility to the organic acid (J) to water is not more than 2 g/100 ml at 20°C.
• cellulose esters for example, organic acid esters such as a cellulose acetate, a cellulose propionate, a cellulose butylate, a cellulose acetate propionate, and a cellulose acetate butylate, inorganic acid esters such as a cellulose nitrate, a cellulose sulphate, and a cellulose phosphate, mixed acid esters such as a cellulose nitrate-acetate, cellulose ethers, for example, a methyl cellulose, an ethyl cellulose, an isopropyl cellulose, a butyl cellulose, a benzyl cellulose, a hydroxyethyl cellulose, a carboxymethyl cellulose, a carboxyethyl cellulose, and a cyanoethyl cellulose, etc.
• organic acid esters such as a cellulose acetate, a cellulose propionate, a cellulose butylate, a cellulose acetate propionate, and
• the cellulose esters further, the cellulose acetate are preferably employed. These may be employed solely or in combination. Further, other polymers may be optionally added.
• the good solvent (I) for the cellulose derivative for example, there can be exemplified C 1-5 dialkyl ketones such as acetone, methylethyl ketone, methylpropyl ketone, methylbutyl ketone, methylisobutyl ketone, and ketones such as cyclohexanone, a C 1-4 alkyl formate such as ethyl formate, a C 1-4 alkyl acetate such as methyl acetate, ethyl acetate, and butyl acetate, esters such as ethyl propionate and ethyl lactate, ethers such as a cyclic or linear chain C 4-6 ether including 1,4-dioxane, tetrahydrofran, tetrahydropyran, diethylether, diisopropylether, and dimethoxyethane, cellosolves such as a C 1-4 cellosolve including methyl
• the good solvents for example, lower alcohols (a C 1-4 alkyl alcohol such as methanol, ethanol, isopropanol, and butanol, diacetone alcohol, etc.), and cycloalkanol (a C 4-8 alkanol such as cyclopentanol, cyclohexanol, methylcyclohexanol, and dimethylcyclohexanol which is substituted with a C 1-4 alkyl group), etc. occasionally become a weak solvent depending upon a kind of the resins.
• the good solvent may even contain a nitro compound (nitromethane, nitroethane, and nitropropane, etc.).
• a preferred good solvent is acetone, methylethyl ketone, ethyl acetate, dioxane, dimethoxyethane, methyl cellosolve, methyl cellosolve acetate, and a mixture thereof.
• the weak solvent (K) means a solvent which does not have solubility to the cellulose derivatives to be employed, or which have a lower solubility than the good solvents to be employed and, if it has a higher boiling point than the good solvents to be employed in combination, it is not particularly limited.
• the weak solvent (K) for the cellulose derivative there can be exemplified, for example, water, esters (a C 5-8 alkyl formate such as amyl formate, isoamyl formate, an aliphatic C 6-10 alkyl C 2-4 carboxylate which may have C 1-4 alkoxyl group such as amyl acetate, hexyl acetate, octyl acetate, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, butyl propionate, 3-methoxybutyl propionate, a C 1-4 alkyl benzoate such as methyl benzoate, ethyl benzoate, and propyl benzoate, etc.), alcohols (C 6-10 alcohols such as amyl alcohol and heterocyclic alcohols, etc.), aliphatic polyvalent alcohols (ethylene glycol, diethylene glycol, propylene glycol, a polyethylene glycol, and glycerine, etc.),
• cyclohexanol As preferred weak solvents, there are enumerated amyl formate, cyclohexanol, methyl cyclohexanol, ethyl benzoate, or a mixture thereof, and cyclohexanol is particularly preferred. Moreover, there is further preferred a solvent having a boiling point of 100-300°C.
• organic acid (J) there can be enumerated formic acid, acetic acid, propionic acid, lactic acid, citric acid, oxalic acid, benzoic acid, sulphamic acid, fumaric acid, maleic acid, phthalic acids (phthalic acid and isophthalic acid), and paratoluene sulphonic acid, etc.
• phthalic acids and derivatives thereof are particularly preferred.
• organic acid having a melting point of not less than 60°C.
• the combination of the good solvent with the weak solvent there is preferred a combination of the good solvent (I) including at least one of the C 1-5 dialkyl ketone, the C 1-4 alkyl acetate, the cyclic or linear chain C 4-6 ether, the C 1-4 alkyl cellosolve, and the C 1-4 alkyl cellosolve acetate with the weak solvent (K) for the cellulose derivative including at least one of the C 5-8 alkyl formate, the C 1-4 alkyl benzoate, the C 4-8 cycloalkanol, the C 1-5 dialkyi ketones, and the C 7-10 ether.
• the good solvent (I) including at least one of the C 1-5 dialkyl ketone, the C 1-4 alkyl acetate, the cyclic or linear chain C 4-6 ether, the C 1-4 alkyl cellosolve, and the C 1-4 alkyl cellosolve acetate
• the weak solvent (K) for the cellulose derivative including at least one of the C
• the additives include, for example, a defoaming agent, an improving agent for coatability, a thickener, a thermal stabilizer, a lubricant, an ultraviolet ray absorbent, a light stabilizer, an antistatic agent, a crosslinking agent, and an antiblocking agent, etc.
• a coating method onto a base sheet of the resin composition for recording is not particularly limited, and there can be employed a roll coating, an air knife-coating, a blade-coating, a bar-coating comma-coating, and a gravure coating methods which are a publicly-known method.
• a recording sheet is obtained in which an image-receiving layer is formed on a body to be recorded.
• Drying method is not particularly limited and, in the case that a dry phase-conversion method is employed, first of all, temperature and vapor pressure, etc. are controlled so that the good solvent is evaporated to produce micelles themselves of the cellulose derivative, subsequently, the micelles themselves are brought into contact with each other by evaporation of the weak solvent to produce a network structure.
• the resin composition of the present invention No. VIII is comprised a polymer (L) represented by general formula (14) described below and a hot-melt adhesive resin (M),
• the polymer (L) may be constructed by the monomer of at least one selected from the formula (14) [hereinafter, referred to as "(poly)alkyleneoxide-modified monomer"], a monomer containing a cationic functional group, a monomer containing a crosslinkable group, and a monomer containing a hydrophilic group.
• the vinyl monomer component having an oxyalkylene group employed for the above-described product (B) of a vinyl acetate-based copolymer.
• the monomer containing a cationic functional group to be employed in the present invention there can be likewise employed the cationic monomer employed in the above-described cationic (meth)acrylate-based copolymers (A-I to A-III) having a crosslinkable group.
• the monomer containing a crosslinkable group to be employed in the present invention there can be likewise employed the monomer containing a crosslinkable group employed in the above-described cationic (meth)acrylate-based copolymers (A-I to A-III) having a crosslinkable group.
• the monomer containing a hydrophilic group to be employed in the present invention there can be likewise employed the monomer containing a hydrophilic group employed in the above-described cationic (meth)acrylate-based copolymers (A-I to A-III) having a crosslinkable group.
• the cationic functional group-contained monomer, the monomer containing a crosslinkable group, and the monomer containing a hydrophilic group can be employed solely or in combination of two or more kinds.
• a preferred combination of the monomers is a s follows.
• R 1 is -H or -CH 3
• R 2 is -H
• R 3 is -H
• the monomer containing a cationic functional group a dic 1- 4 alkylamino-C 2-8 alkyl(meth)acrylate or a quaternary salt thereof.
• the monomer containing a crosslinkable group a (meth)acryoxy-C 2-8 alkyltriC 1-8 alkoxy silane.
• the monomer containing a hydrophilic group an unsaturated carboxylic acid.
• the monomers are usually employed in combination with a nonionic monomer in order to adjust a film-formability and a coating layer property.
• nonionic monomer there can be likewise employed the nonionic monomer employed in the above-described cationic (meth)acrylate-based copolymers (A-I to A-III) having a crosslinkable group.
• a polymerization style thereof is not particularly limited, for example, there may be a random copolymer, a graft copolymer, and a block copolymer, etc.
• Content of the monomer of the formula (14) is preferably 1-40% by mol, more preferably 5-30% by mol, and most preferably 15-25% by mol based on total monomers in the polymer (L).
• Content of the monomer containing a cationic functional group is preferably 1-50% by mol, and more preferably 5-45% by mol based on total monomers in the polymer (L).
• Content of the monomer containing a crosslinkable group is preferably 0.1-20% by mol, more preferably 0.1-10% by mol, and most preferably 1-5% by mol based on total monomers in the polymer (L).
• Content of the monomer containing a hydrophilic group is preferably 0.1-30% by mol, more preferably 0.1-20% by mol, and most preferably 0.5-15% by mol based on total monomers in the polymer (L).
• Residual components are the nonionic monomer, and preferably 10-80% by mol, more preferably 20-70% by mol or so.
• the monomer containing a cationic functional group is preferably 5-300 parts by weight, and more preferably 10-250 parts by weight
• the monomer containing a crosslinkable group is preferably 1-30 parts by weight, and more preferably 5-20 parts by weight
• the monomer containing a hydrophilic group is preferably 5-80 parts by weight, and more preferably 10-60 parts by weight or so, respectively, based on 100 parts by weight of the (poly)alkylene oxide-modified monomer of the formula (14).
• the glass transition temperature (Tg) of the copolymer which constructs the polymer (L) can be selected within a range in which a film-formability, etc. is not deteriorated, and it is preferably -85 to 30°C, more preferably -60 to 0°C, and most preferably -50 to -10°C or so.
• the polymer having such the glass transition temperature can be prepared by appropriately combining the monomer containing a cationic functional group and the monomer containing a crosslinkable group with the monomer containing a hydrophilic group and the nonionic monomer.
• the monomers preferably construct the copolymer in combination of, usually, a hard monomer, for example, a monomer component which forms a homopolymer having a glass transition temperature of 80 to 120°C, particularly, 90 to 105°C or so such as methyl(meth)acrylate and styrene and a soft monomer, for example, a monomer (soft monomer) which forms a homopolymer having a glass transition temperature of -85 to -10°C, particularly, -85 to -20°C or so such as a C 2-10 alkylacrylate.
• a hard monomer for example, a monomer component which forms a homopolymer having a glass transition temperature of 80 to 120°C, particularly, 90 to 105°C or so such as methyl(meth)acrylate and styrene
• a soft monomer for example, a monomer (soft monomer) which forms a homopolymer having a glass transition temperature of -85 to -10°C, particularly
• the hot-melt adhesive resin (M) to be employed in the present invention there can be exemplified a variety of resins, for example, an olefinic-based resin such as a polyethylene, an ethylene-propylene copolymer, and an atactic polypropylene, an ethylene copolymer resin such as an ethylene-vinyl acetate copolymer, an ethylene-(meth)acrylic acid copolymer, an ethylene-ethylacrylate copolymer, and an ionomer, a nylon-based resin, a polyester-based resin, a polyurethane-based resin, an acrylic-based resin, and a rubber, etc.
• an olefinic-based resin such as a polyethylene, an ethylene-propylene copolymer, and an atactic polypropylene
• an ethylene copolymer resin such as an ethylene-vinyl acetate copolymer, an ethylene-(meth)acrylic acid copolymer,
• the hot-melt adhesive resins can be employed solely or in combination of two or more kinds.
• the hot-melt adhesive resins are usually water-insoluble.
• the hot-melt adhesive resins may be even a reactive hot-melt adhesive resin having a reactive group such as carboxylic groups, hydroxyl groups, amino groups, isocyanate groups, and silyl groups at terminals thereof.
• a preferred resin for giving a heat transfer property and durability (washing resistance) is a nylon-based resin, a polyester-based resin, and a polyurethane-based resin, etc.
• a hot-melt adhesive resin constructed by the nylon-based resin in the case that a body to be transferred is clothes, can give an excellent washing resistance to a picture image transferred, water resistance, and a high feeling.
• a nylon-based hot-melt adhesive resin there are included a polyamide resin (for example, a homopolyamide such as a nylon 11 and nylon 12, a nylon 6/11, a nylon 6/12, a nylon 66/12, etc.) containing at least one unit selected from a nylon 11 and nylon 12, a copolyamide such as a copolymer of a dimer acid with a diamine and laurolactam or amino undecanoic acid, and a polyamide resin produced by a reaction of a dimer acid with a diamine, etc.
• a polyamide resin for example, a homopolyamide such as a nylon 11 and nylon 12, a nylon 6/11, a nylon 6/12, a nylon 66/12, etc.
• polyester-based hot-melt adhesive resin there are included a homopolyester resin or a copolyester resin in which an aliphatic diol is employed.
• a homopolyester resin there is included a saturated aliphatic polyester resin produced by a reaction of a C 2-10 alkylene diol such as ethylene glycol, propylene glycol, 1,4-butane diol, and 1,6-hexane diol, an aliphatic diol such as diethylene glycol which is a polyoxyC 2-10 alkylene glycol with an aliphatic dicarboxylic acid such as adipic acid, sberic acid, azelaic acid, sebasic acid, and dodecanoic dicarboxylic acid, and, optionally, a lactone.
• a copolyester resin there is included a saturated polyester resin in which constructing components composed of a polyethylene terephthalate or polybutylene terephthalate are partially substituted with other diols such as a C 2-6 alkylene glycol including ethylene glycol, propylene glycol, and 1,4-butane diol or a dicarboxylic acid including the above-described aliphatic dicarboxylic acid, an asymmetric aromatic dicarboxylic acid such as phthalic acid and isophthalic acid, or a lactone.
• diols such as a C 2-6 alkylene glycol including ethylene glycol, propylene glycol, and 1,4-butane diol or a dicarboxylic acid including the above-described aliphatic dicarboxylic acid, an asymmetric aromatic dicarboxylic acid such as phthalic acid and isophthalic acid, or a lactone.
• polyurethane-based hot-melt adhesive resin there is included a polyester resin in which there is employed a polyester diol corresponding to the polyester-based hot-melt adhesive resin and, as a diisocyanate component, there can be employed an aromatic, aromatic-aliphatic, and cycloaliphatic or aliphatic diisocyanate.
• the hot-melt adhesive resin may optionally contain, for example, commonly-used additives described hereinafter and waxes.
• a melting point can be selected from a range of preferably 70-250°C, more preferably 70-200°C, and most preferably 100-150°C.
• the hot-melt adhesive resin is employed as powder or particles.
• the hot-melt adhesive resin is usually constructed by a powder- or particle-state resin having larger average particle diameter than thickness of an ink-receiving layer in order to effectively show a hot-melt adhesive property by projecting from surface of the ink-receiving layer.
• the larger average particle diameter is, for example, preferably 1-100 ⁇ m, more preferably 3-80 ⁇ m, and most preferably 5-50 ⁇ m or so.
• the powder- or particles in the hot-melt adhesive resin may be even a porous body.
• the resin composition of the present invention can be obtained by the using the hot-melt adhesive resin in preferably 10-1500 parts by weight, more preferably 10-900 parts by weight, and particularly preferably 80-900 parts by weight based on 100 parts by weight of the polymer (L) (the above-described copolymer).
• a curing agent (a curing catalyst or a curing accelerator) may be even added in order to accelerate a curing reaction.
• an organic tin compound dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, dibutyltin diacetate, dibutyltin dimethoxide, tributyltin sulphide, dibutyltin thioglycolate, and tin octylate, etc.
• an organic aluminum compound aluminum isopropylate, aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetatealuminum diisopropylate, etc.
• an organic titanium compound isopropyltrisstearoyl titanate, tetraisopropyl bis(dioctylphosphite)titanate, bis(dioctylpyrophosphate)oxy
• the curing agents can be employed solely or in combination of two or more kinds.
• Use amount of the curing agents is a range in which curing can be accelerated, for example, preferably 0.01-10 parts by weight, and more preferably 0.1-5 parts by weight with respect to 100 parts by weight of the resin composition constructed by the cationic acrylic copolymers (A-I to A-VI) containing a crosslinkable group and a hydrophilic polymer compound such as the saponified product (B) of a vinyl acetate-based copolymer based on solid components.
• a dye-fixing agent particularly, a polymeric dye-fixing agent.
• the dye-fixing agent usually has a cationic group (particularly, a strong cationic group such as guanidyl group and a quaternary ammonium salt type) in the molecule.
• the dye-fixing agent may be water-soluble.
• the dye-fixing agent there can be exemplified, for example, a dicyan-based fixing agent (dicyandiamide-formalin polycondensate, etc.), a polyamine-based fixing agent [a condensate (a dicyan diamide-diethylenetriamine polycondensate, etc.) of an aliphatic polyamine such as diethylenetriamine, triethylene tetramine, dipropylene triamine, a polyallylamine, an aromatic polyamine such as phenylene diamine, and dicyandiamide with a polyC 2-4 alkylene polyamine], and a polycationic-based fixing agent, etc.
• a dicyan-based fixing agent (dicyandiamide-formalin polycondensate, etc.)
• a polyamine-based fixing agent a condensate (a dicyan diamide-diethylenetriamine polycondensate, etc.) of an aliphatic polyamine such as diethylenetriamine, triethylene tetramine, diprop
• an epiclorohydrin-diC 1-4 alkyl amine-added polymer an epiclorohydrin-dimethyl amine-added polymer, etc.
• a polymer of allyl amine or a salt thereof a polymer of a polyallylamine or a hydrochloric acid salt thereof, for example, PA-10C, PAA-HCL-3L, and PAA-HCL-10L by Nittoboseki, Ltd.
• a polymer of a diallylC 1-4 alkyl amine or salt thereof a polymer of a diallylmethyl amine or a hydrochloric acid salt thereof, for example, PAS-M-1, etc.
• a polymer of a diallyldiC 1-4 alkyl ammonium salt (a polymer of a diallyldimethyl ammonium chloride, for example, PAS-H-5L and PAS-H-10L, etc.
• the dye-fixing agent can be also employed solely or in combination of two or more kinds.
• Use amount of the dye-fixing agent is a range in which ink-fixing ability can be elevated, for example, preferably 0.1-40 parts by weight, more preferably 1-30 parts by weight and, further preferably 2-20 parts by weight with respect to 100 parts by weight of the resin composition prepared by addition of the saponified product (B) of a vinyl acetate-based copolymer, the water-based polyurethane resin composition (C) and, in the case of the invention No. III, further, the block isocyanate (D) to the cationic acrylic copolymers (A-I to A-VI) containing a crosslinkable group based on solid components.
• Nos. IV and V it can be selected from a range of preferably 0.1-40 parts by weight, more preferably 1-30 parts by weight and, further preferably 2-20 parts by weight or so with respect to 100 parts by weight of the resin composition constructed by the cationic (meth)acrylic copolymers (A-IV to A-V), the saponified product (B) of a vinyl acetate-based copolymer, and the modifier (R).
• A-IV to A-V the cationic (meth)acrylic copolymers
• B saponified product
• R modifier
• 60°-glossiness is preferably not less than 30%, more preferably not less than 50%, and further preferably not less than 70%.
• a porous layer there may be optionally formed a porous layer, a blocking protecting layer, a slipping layer, and an antistatic agent layer on the image-receiving layer.
• the recording sheets in relation to the present invention Nos. I-VII are useful as a recording sheet by an ink-jet style in which small droplets of an ink are sprayed, and can be also utilized as a printing sheet (particularly, an sheet for a water-based ink) for an offset printing and a flexo printing, etc.
• the ink jet recording sheet in relation to the present invention is obtained by coating the above-described resin composition onto a base material for the recording sheet and, the image-receiving layer formed by coating may optionally contain other components, for example, a water-based emulsion (for example, an acrylic resin emulsion, an ethylene-vinyl acetate copolymer emulsion, and a vinyl acetate emulsion, etc.) containing a polymer not having a crosslinkable group and polymer particles.
• a water-based emulsion for example, an acrylic resin emulsion, an ethylene-vinyl acetate copolymer emulsion, and a vinyl acetate emulsion, etc.
• the image-receiving layer may even further contain powder and particles (pigments, etc.).
• the powder and particles there are enumerated inorganic powder and particles (mineral powder and particles, etc. such as white carbon, a fine particle-state calcium silicate, zeolite, magnesium aluminosilicate, calcined diatomaceous, a fine particle-state magnesium carbonate, a fine particle-state alumina, silica, talc, kaoline, delamikaoline, clay, heavy calcium carbonate, light calcium carbonate, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, calcium sulphate, celicite, bentonite, and smectite), organic powder and particles (organic powder and particles such as a crosslinked or noncrosslinked organic fine particles such as a polystyrene resin, an acrylic resin, a urea resin, a melamine resin, a benzoguanamine resin, etc., and
• Proportion of the powder and particles with respect to the binder resin is not particularly limited and, the powder and particles are preferably 0.1-80 parts by weight, and more preferably 0.2-50 parts by weight.
• the additives include, for example, a defoaming agent, an improving agent for coatability, a thickener, a surface active agent, a lubricant, a stabilizer (an antioxidant, an ultraviolet ray absorbent, and a thermal stabilizer, etc.), an antistatic agent, and an antiblocking agent, etc.
• the ink-receiving layer in the heat transfer sheet of the present invention No. VIII is constructed by the above-described resin composition.
• the ink-receiving layer may even contain a plasticizer in order to give a high ductility to a transferred picture image.
• a phthalic acid-based plasticizer such as ethyl phthalate, butyl phthalate, hexyl phthalate, octyl phthalate, 2-ethylhexyl phthalate, and lauryl phthalate
• an aliphatic dicarboxylic acid-based plasticizer such as 2-ethylhexyl adipate, dibutyl sebacate, and 2-ethylhexyl sebacate
• a glycol-based plasticizer such as ethyl-phthallyl ethyl glycolate and a polyethylene glycol ester
• a phosphate-based plasticizer such as triphenyl phosphate, tricresyl phosphate, and 2-ethylhexyl phosphate
• a polyester-based plasticizer such as an epoxide-based plasticizer such as an epoxy fatty acid ester, etc.
• the plasticizer can be employed solely or in combination
• the plasticizer for example, preferably 0.1-30 parts by weight, more preferably 1-25 parts by weight, and particularly preferably 1-20 parts by weight with respect to 100 parts by weight of total amount of the resins such as a polymer constructing the ink-receiving layer and the hydrophilic polymer, the hot-melt adhesive resin, the cationic polymer, and the polyurethane-based polymer resin.
• the ink-receiving layer may even contain a dye-fixing agent independently or together with the above-described plasticizer in order to elevate a fixing ability of a coloring agent (a dye).
• the recording sheet of the present invention possesses the above-described receiving layer, an ink-absorbing ability and ink-fixing ability are high and water resistance, printing quality, and a roll mark-adhering problem are especially improved.
• a letters-printing portion or a picture image portion is formed by a water-based ink without causing inferiority in a picture image such as beading and roll mark-adhering owing to an ink-jet recording method, and when a dried printing portion or a picture image portion is immersed in water of 30°C for 1 minute, retention ratio of color concentration is not less than 80% (for example, 85-100% or so), and preferably not less than 85% (for example, 90-99% or so).
• the recording sheet of the present invention can be prepared by forming an image-receiving layer composed of the resin composition for recording on at least one surface of the above-described base material.
• Ink-absorbing layer can be prepared by coating a coating liquid which is prepared using an appropriate solvent (water, a hydrophilic solvent which may be water-soluble, a hydrophobic solvent or a mixture thereof) on a supporting material.
• a resin composition containing the cationic (meth)acrylic copolymers (A-I to A-VI) having a crosslinkable group is a from of a water-based emulsion, a water-based coating liquid is employed.
• the coating liquid is coated by common coating methods including a casting-coating method, for example, on at least one surface of the base material by a roll coater, air-knife coater, blade coater, rod coater, bar coater, comma coater, gravure coater, and silk-screen coater method, etc.
• a casting-coating method for example, on at least one surface of the base material by a roll coater, air-knife coater, blade coater, rod coater, bar coater, comma coater, gravure coater, and silk-screen coater method, etc.
• the image-receiving layer can be formed by coating a liquid containing the above-described respective components onto at least one surface of a base material, followed by drying. Further, after coating the coating liquid, there may be optionally formed an ink-absorbing layer crosslinked by heating at an appropriate temperature selected from a range of 50-150°C or so.
• thickness can be selected depending upon uses, and it is preferably 3-50 ⁇ m, more preferably 6-30 ⁇ m, and usually 5-30 ⁇ m or so.
• the ink jet recording sheet obtained using the resin composition in relation to the present invention possesses an image-receiving layer, an ink-absorbing ability and ink-fixing ability are high, and water resistance and printing quality are especially improved and, even though it is employed in a printing machine having a large printing speed, there can be obtained a clear and sharp image without beading.
• a letters-printing portion or an image portion is formed by a water-based ink without causing inferiority in an image such as beading and roll mark-adhering owing to an ink-jet recording method, and when a dried printing portion or a picture image portion is immersed in water of 30°C for 1 minute, retention ratio of color concentration is preferably not less than 80% (for example, 85-100% or so), and more preferably not less than 85% (for example, 90-99% or so).
• a porous layer there may be optionally formed a porous layer, a blocking protecting layer, a slipping layer, and an antistatic agent layer on the ink-receiving layer.
• the recording sheet of the present invention is useful as a recording sheet by an ink-jet style in which small droplets of an ink are sprayed, and it can be also utilized as a printing sheet (particularly, an sheet for a water-based ink) for an offset printing and a flexo printing, etc.
• a dye-fixing agent particularly, a polymeric dye-fixing agent.
• the dye-fixing agent usually has a cationic group (particularly, a strong cationic group such as guanidyl group and a quaternary ammonium salt type) in the molecule.
• the dye-fixing agent may be even water-soluble.
• a protecting layer is formed on the ink-receiving layer.
• the protecting layer can be stripped from the base material, and it protects the ink-receiving layer. So far as quality of a picture image transferred is not largely disturbed, there can be employed a variety of thermoplastic resins and thermosetting resins, particularly, a polymer having a film-formability.
• thermoplastic resins there can be exemplified a polyamide resin such as nylon 11, nylon 12, and nylon 612, a polyester resin such as a PET based-copolyester and a PBT based-copolyester, a styrene-based resin such as a styrene-(meth)acrylic acid ester resin, a polyolefine-based resin such as a polyethylene, a polypropylene, an ethylene-propylene resin, a polyvinyl acetate-based resin such as an ethylene-vinyl acetate-based copolymer, an acrylic-based resin such as a poly(meth)acrylic acid ester, a polyacetal resin, a vinyl chloride-based resin such as a polyvinyl chloride-vinyl acetate copolymer, and a fluorine-based resin, etc.
• a polyamide resin such as nylon 11, nylon 12, and nylon 612
• a polyester resin such as a PET based
• thermoplastic resins can be employed solely or in combination of two or more kinds.
• thermosetting resins there can be exemplified a variety of resins such as a urethane resin, an epoxy resin, a phenol resin, a xylilene resin, a melamine resin, a urea resin, and a silicone resin.
• the protecting layer is advantageously constructed by a soft polymer, particularly, a nonsticking polymer.
• the soft polymer may be even a nonelastomer, it is preferably an elastomer.
• elastomer means a polymer having a rubber elasticity in addition to rubbers such as a natural rubber and synthetic rubber.
• the elastomer there are enumerated at least one polymers selected from the synthetic rubber, natural rubber, and a thermoplastic elastomer.
• the synthetic rubber there can be exemplified, for example, a variety of rubbers which include a diene-based rubber such as a styrene-butadiene rubber, a butadiene rubber, an isoprene rubber, a chloroprene rubber, and an acrylonitrile-butadiene rubber, for example, a butyl rubber, an ethylene-propylene rubber such as an EPM and an EPDM, an olefine-based rubber such as a fluorine rubber, an acrylic rubber, an ethylene-acrylic rubber, and a chlorosulphonated ethylene rubber, and other rubbers (for example, a silicone rubber, a urethane rubber, an ethylene-vinyl acetate copolymer, and a polynorbornene rubber, etc.).
• a diene-based rubber such as a styrene-butadiene rubber, a butadiene rubber, an isoprene rubber, a chloro
• thermoplastic elastomer there are enumerated a variety of elastomers which include an elastomer constructed by a hard segment (or a block) and a soft segment (or a block), for example, a polystyrene-based elastomer which is a block copolymer such as a polybutadiene/polystyrene elastomer and a polyisoprene/polystyrene elastomer, a polyurethane-based elastomer which is a block copolymer such as a polyester or polyether-based polyurethane elastomer, a polyamide elastomer which is a block copolymer such as a polyester or polyether-based polyamide elastomer, a polyolefine-based elastomer such as an EPR/polypropylene elastomer, an EPDM/polypropylene elastomer, and a
• the protecting layer and the ink-receiving layer can flexibly follow even though the body to be transferred are expanded and contracted, resulting in that there is prevented generation of micro cracks in an image to be transferred and, for that reason, it is preferred that the protecting layer is constructed by the synthetic rubber, a natural rubber, and the thermoplastic elastomer.
• the elastomer may be even vulcanized by sulphur and a peroxide, etc.
• a preferred protecting layer can be constructed by an elastomer having Young's modulus of preferably 0.1-100 MPa (for example, 1-100 MPa), and more preferably 0.1-50 MPa (for example, 1-50 MPa).
• a polymer for the protecting layer there can be employed an elastomer selected from a range of an extension ratio of not less than 300% (for example, 300-1000% or so) and, particularly, preferably not less than 400% (for example, 400-1000% or so), and the extension ratio is usually 400-900% or so in the polymer.
• a glass transition temperature is preferably -100 to 100°C, more preferably -50 to 50°C and, particularly preferably -30 to 30°C.
• a glass transition temperature in the elastomer is preferably not more than -10°C (for example, -100 to -10°C or so), more preferably not more than -15°C (for example, -100 to -15°C or so) and, particularly preferably not more than -20°C (for example, -100 to -20°C or so), and the polymer is not preferably tacky at room temperatures (for example, -10 to 30°C or so).
• the polymer which constructs the protecting layer may even optionally contain a variety of additives employed for the image-receiving layer.
• Thickness of the protecting layer is, for example, preferably 1-90 ⁇ m or so, and more preferably 3-70 ⁇ m or so, and it is usually 5-50 ⁇ m or so (for example, 5-30 ⁇ m or so).
• the heat transfer sheet of the present invention No. VIII can be prepared by forming an ink-receiving layer which can be stripped from a base material on at least one surface of a strippable base material.
• the ink-receiving layer can be prepared by coating a coating agent constructed by the polymer (L) containing at least the monomer units represented by the formula (14), the hot-melt adhesive resin (M), and optionally other components on a releasible surface of the base material.
• the polymer (L) can be usually employed in a form of a water-based solution or an emulsion
• the hot-melt adhesive resin (M) can be employed in a form of powder and particles.
• the water-based solution or the emulsion of the polymer (L) and the powder and particles of the hot-melt adhesive resin (M) are optionally mixed with other components to prepare the coating agent for the ink-receiving layer.
• Solvent for the water-based solution or the emulsion may be water alone, or may optionally contain hydrophilic solvents such as alcohols.
• a coating liquid for the protecting layer constructed by an elastomer, etc., and it is optionally dried to prepare a protecting layer, and the ink-receiving layer may be even formed on the protecting layer as described hereinabove.
• the coating liquid for the protecting layer can be prepared using an organic solvent and water-based solvent depending upon the kind of the polymer, and it may be even a form of an aqueous solution or an emulsion.
• the coating liquid can be coated by the common methods (described hereinabove).
• the ink-receiving layer and the protecting layer can be formed by drying a coating layer at 50-150°C (preferably 80-120°C) or so.
• ink-receiving layer is appropriate for forming a picture image by an ink-jet method in which small droplets of an ink (particularly, a water-based ink) are sprayed.
• Picture image to be recorded can be smoothly transferred or moved by compressing at an appropriate temperature (for example, preferably 140-250°C, and more preferably 140-200°C) and a pressure of 0.5-50 kPa (5-500 gf/cm 2 or so) for an appropriate time of period and stripping the ink-receiving layer from the base material.
• a body to be transferred including a picture image transferred may be optionally even crosslinked by heating.
• materials to be transferred there can be utilized a two dimensional or three dimensional structural material formed by a variety of materials such as fibers, paper, woods, plastics, ceramics, and metals.
• materials to be transferred there can be utilized plastic films, plastic sheet, paper, ad clothes as the materials to be transferred.
• an ink-receiving layer which is strippable from a base material at one surface of a base material, it can be utilized using the resin composition, for example, as a heat transfer sheet for an ink-jet recording in which a picture image is recorded by an ink-jet recording method, and the picture image is transferred onto the materials to be transferred to form a picture image transferred and, even though it is transferred onto an expansible and shrinkable material to be transferred, the picture image recorded can excellently follow an expansion and shrinkage, and micro cracks are not produced in the picture image.
• the heat transfer sheet of the present invention is useful as an ink-receiving sheet (particularly, a sheet for a water-based ink) by an ink-jet method in which recording is conducted by spraying small droplets of an ink, and it can be also utilized also as a heat transfer sheet for an offset printing and a flexo printing.
• evaluation methods of a variety of properties are as follows in relation to recording sheets obtained in the Examples and Comparative Examples, and items which cannot be normalized are illustrated in the respective inventions.
• An ink-jet printer (PM-770C manufactured by Seiko Epson, Ltd.) was employed, and a recorded picture image was formed by printing a color pattern using colors such as cyan, yellow, magenta, and black in a photoglossy paper mode on recording sheets obtained in Examples and Comparative Examples.
• An ink-jet printer (BJ-410J manufactured by Canon, Ltd.) was employed, and a recorded picture image was formed by printing a color pattern using colors such as cyan, yellow, magenta, and black in an HQ mode on recording sheets obtained in Examples and Comparative Examples.
• Printed portion was immersed in water of 30°C for 1 hour and, it was vertically pulled up, and water was sufficiently removed and dried. After having dried, water resistance was visually evaluated by the following standard.
• Printed portion was immersed in water of 30°C for 1 hour and, it was vertically pulled up, and water was sufficiently removed and dried. After having dried, water resistance was visually evaluated by the following standard.
• a 2000 ml reaction vessel equipped with an agitator, a reflux condenser, a dropping funnel, a tube for introducing nitrogen, and a thermometer was charged with 219 parts of isopropylalcohol (IPA), and 1.23 part of azobisisobutylonitrile (AIBN) was added while agitating to dissolve, followed by heating to 80°C.
• IPA isopropylalcohol
• AIBN azobisisobutylonitrile
• MMA methylmethacrylate
• BA n-butylacrylate
• DEAEMA diethylaminoethyl methacrylate
• trimethoxysilane propylmethacrylate A-174 manufactured by Nihon Unicar, Ltd.
• HUX-670 As the water-based polyurethane resin, HUX-670 was employed which is manufactured by Asahi Denka Kogyo, Ltd.
• composition in which 100-60% by weight of a hydrophilic monomer was graft-polymerized with 0-40% by weight of a copolymerizable monomer in an aqueous solution or an aqueous dispersion in which the water-based polyurethane resin are mixed with the saponified product of a vinyl acetate-based copolymer.
• NS-141LX which is a water-based polyester resin composition manufactured by Takamatsu Yushi Kogyo, Ltd.
• composition in which 100-60% by weight of a hydrophilic monomer was graft-polymerized with 0-40% by weight of a copolymerizable monomer in an aqueous solution or an aqueous dispersion in which the water-based polyester resin are mixed with the saponified product of a vinyl acetate-based copolymer.
• NS-141LX which is a water-based polyester resin composition manufactured by Takamatsu Yushi Kogyo, Ltd.
• the water-based coating liquid was coated on an adhesive-treated polyethylene terephthalate film having the thickness of 100 ⁇ m (Merinex 705 manufactured by ICI Japan, Ltd., hereinafter, it is occasionally referred to as merely PET film), and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet I-1.
• an adhesive-treated polyethylene terephthalate film having the thickness of 100 ⁇ m (Merinex 705 manufactured by ICI Japan, Ltd., hereinafter, it is occasionally referred to as merely PET film)
• it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet I-1.
• Example I-2 The same procedures were followed as in the Example I-1, except that the NS-120X (D-I) manufactured by Takamatsu Yushi Kogyo, Ltd. was employed in place of the HUX-670 (C-I) manufactured by Asahi Denka Kogyo, Ltd. to obtain a recording sheet I-2.
• D-I NS-120X
• C-I HUX-670
• Example I-1 The same procedures were followed as in the Example I-1, except that the NS-141LX (E-I) manufactured by Takamatsu Yushi Kogyo, Ltd. was employed in place of the HUX-670 (C-I) manufactured by Asahi Denka Kogyo, Ltd. to obtain a recording sheet I-3.
• E-I NS-141LX
• C-I HUX-670
• Example I-1 The same procedures were followed as in the Example I-1, except that the PVA-205 (B-I) was employed in place of the PVA-405 manufactured by Kuraray, Ltd. to obtain a recording sheet I-4.
• Example I-5 The same procedures were followed as in the Example I-1, except that the PVA-420 (B-I) was employed in place of the PVA-405 manufactured by Kuraray, Ltd. to obtain a recording sheet I-5.
• Example I-6 The same procedures were followed as in the Example I-1, except that the PVA-217 (B-I) was employed in place of the PVA-405 manufactured by Kuraray, Ltd. to obtain a recording sheet I-6.
• the cationic acrylic copolymer (A-I) containing a crosslinkable group obtained in the above-described step was coated on a PET film having the thickness of 100 ⁇ m, and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet I-7.
• An aqueous solution of the PVA-217 (B-I) manufactured by Kuraray, Ltd. was coated on the PET film having the thickness of 100 ⁇ m, and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet I-8.
• the HUX-670 (C-I) manufactured by Asahi Denka Kogyo, Ltd. was coated on the PET film having the thickness of 100 ⁇ m, and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet I-9.
• the NS-120X (D-I) manufactured by Takamatsu Yushi Kogyo, Ltd. was coated on the PET film having the thickness of 100 ⁇ m, and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet I-10.
• Example No. Sheet No. Uniformity of Picture image A Uniformity of Picture image B Clearness Water Resistance
• the saponified product (B-II) of a vinyl acetate-based copolymer As the saponified product (B-II) of a vinyl acetate-based copolymer, the PVA-210 manufactured by Kuraray, Ltd. was employed.
• the water-based polyurethane resin (C-II) As the water-based polyurethane resin (C-II), the HUX-670 manufactured by Asahi Denka Kogyo, Ltd. was employed.
• composition in which 100-60 wt% of a hydrophilic vinyl monomer is graft-polymerized with 0-40 wt% of a copolymerizable vinyl monomer in an aqueous solution or an aqueous dispersion in which the water-based polyurethane resin are mixed with the saponified product of a vinyl acetate-based copolymer.
• NS-120X which is a water-based polyester resin composition manufactured by Takamatsu Yushi Kogyo, Ltd.
• composition in which 100-60% by weight of a hydrophilic monomer was graft-polymerized with 0-40% by weight of a copolymerizable monomer in an aqueous solution or an aqueous dispersion in which the water-based polyester resin are mixed with the saponified product of a vinyl acetate-based copolymer.
• NS-141LX which is a water-based polyester resin composition manufactured by Takamatsu Yushi Kogyo, Ltd.
• the water-based coating liquid was coated on an adhesive-treated polyethylene terephthalate film having the thickness of 100 ⁇ m (Merinex 705 manufactured by ICI Japan, Ltd., hereinafter, it is occasionally referred to as merely PET film), and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet II-1.
• an adhesive-treated polyethylene terephthalate film having the thickness of 100 ⁇ m (Merinex 705 manufactured by ICI Japan, Ltd., hereinafter, it is occasionally referred to as merely PET film)
• it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet II-1.
• Example II-1 The same procedures were followed as in the Example II-1, except that the NS-120X which is the component (D-II) manufactured by Takamatsu Yushi Kogyo, Ltd. was employed in place of the HUX-670 which is the component (C-II) manufactured by Asahi Denka Kogyo, Ltd. to obtain a recording sheet II-2.
• the NS-120X which is the component (D-II) manufactured by Takamatsu Yushi Kogyo, Ltd.
• HUX-670 which is the component (C-II) manufactured by Asahi Denka Kogyo, Ltd.
• Example II-1 The same procedures were followed as in the Example II-1, except that the NS-141LX which is the component (E-II) manufactured by Takamatsu Yushi Kogyo, Ltd. was employed in place of the HUX-670 which is the component (C-II) manufactured by Asahi Denka Kogyo, Ltd. to obtain a recording sheet II-3.
• the NS-141LX which is the component (E-II) manufactured by Takamatsu Yushi Kogyo, Ltd.
• HUX-670 which is the component (C-II) manufactured by Asahi Denka Kogyo, Ltd.
• the cationic acrylic copolymer (A-II) containing a crosslinkable group obtained in the above-described step was coated on the PET film having the thickness of 100 ⁇ m, and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet II-4.
• the PVA-210 which is the component (B-II) manufactured by Kuraray, Ltd. was coated on the PET film having the thickness of 100 ⁇ m, and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet II-5.
• the HUX-670 which is the component (C-II) manufactured by Asahi Denka Kogyo, Ltd. was coated on the PET film having the thickness of 100 ⁇ m, and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet II-6.
• the NS-120X which is the component (D-II) manufactured by Takamatsu Yushi Kogyo, Ltd. was coated on the PET film having the thickness of 100 ⁇ m, and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet II-7.
• the NS-141LX which is the component (E-II) manufactured by Takamatsu Yushi Kogyo, Ltd. was coated on the PET film having the thickness of 100 ⁇ m, and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet II-8.
• a cationic (meth)acrylic copolymer (A-III-1) containing a crosslinkable group there was employed the same one as in the cationic (meth)acrylic copolymer (A-I-1) containing a crosslinkable group.
• the NS-120X manufactured by Takamatsu Yushi Kogyo, Ltd. was employed.
• the water-based coating liquid was coated on an adhesive-treated polyethylene terephthalate film having the thickness of 100 ⁇ m (Merinex 705 manufactured by Dupon't, Ltd., hereinafter, it is occasionally referred to as merely PET film), and it was dried at 120°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain a recording sheet III-1.
• an adhesive-treated polyethylene terephthalate film having the thickness of 100 ⁇ m (Merinex 705 manufactured by Dupon't, Ltd., hereinafter, it is occasionally referred to as merely PET film)
• Example III-1 The same procedures were followed as in the Example III-1, except that there were employed 30 parts (based on solid components) of the cationic acrylic copolymer (A-III-1) containing a crosslinkable group, 40 parts (based on solid components) of the saponified product of a vinyl acetate-based copolymer (B-III), and 30 parts (based on solid component) of the water-based polyurethane resin (C-III): NS-120X to obtain a recording sheet III-2.
• A-III-1 cationic acrylic copolymer
• B-III vinyl acetate-based copolymer
• C-III water-based polyurethane resin
• Example III-1 The same procedures were followed as in the Example III-1, except that the block isocyanate compound (F-III) was changed to 0 part to obtain a recording sheet III-3.
• Example III-1 The same procedures were followed as in the Example III-1, except that the block isocyanate compound (F-III) was changed to 5 parts to obtain a recording sheet III-4.
• Example III-1 The same procedures were followed as in the Example III-1, except that the cationic acrylic copolymer (A-III-1) containing a crosslinkable group was changed to 0 part, the saponified product of a vinyl acetate-based copolymer (B-III): OKS-7158G was change to 100 parts, the water-based polyurethane resin (C-III): NS-120X was changed to 0 part, and the block isocyanate compound (F-III) was changed to 0 part to obtain a recording sheet III-5.
• Example III-1 The same procedures were followed as in the Example III-1, except that a block isocyanate compound (D-III) was changed to the same amount of isophorone diisocyanate to obtain a recording sheet III-6.
• composition for recording of the present invention and the recording sheet having a picture image-receiving layer on at least one surface of a base material prepared therefrom, there can be largely improved water resistance while improving an ink-absorbing ability and a printing quality.
• a 2000 ml reaction vessel equipped with an agitator, a reflux condenser, a dropping funnel, a tube for introducing nitrogen, and a thermometer was charged with 219 parts of isopropylalcohol (IPA), and 1.23 part of azobisisobutylonitrile (AIBN) was added while agitating to dissolve, followed by heating to 80°C.
• IPA isopropylalcohol
• AIBN azobisisobutylonitrile
• MMA methylmethacrylate
• BA n-butylacrylate
• DEAEMA diethylaminoethyl methacrylate
• A-174 trimethoxysilane propylmethacrylate
• a water-based polyurethane resin was employed.
• HUX-670 was employed which is manufactured by Asahi Denka Kogyo, Ltd.
• the water-based coating liquid was coated on an adhesive-treated polyethylene terephthalate film having the thickness of 100 ⁇ m (Merinex 705 manufactured by Dupon't, Ltd., hereinafter, it is occasionally referred to as merely PET film), and it was dried at 100°C for 3 minutes to form an ink-absorbing layer having the thickness of 15 ⁇ m and to obtain the samples for evaluation.
• a recorded picture image was formed by printing a color pattern using colors such as cyan, yellow, magenta, and black in a photoprint mode on the recording sheets obtained in Examples and Comparative Examples.
• Printed portion was immersed in water of 30°C for 1 hour and, it was vertically pulled up, and water was sufficiently removed and dried. After having dried, there was measured retention of color concentration in the picture image remained after drying.
• the water-based coating liquid was coated on an adhesive-treated polyethylene terephthalate film having the thickness of 100 ⁇ m (Merinex 705 manufactured by Dupon't, Ltd.), and it was dried at 100°C for 3 minutes to form an ink-absorbing layer which is an image-receiving layer having the thickness of 15 ⁇ m and to obtain a recording sheet IV-1.
• a water-based coating liquid composed of a resin composition was obtained by formulating a cationic acrylic copolymer containing a crosslinkable group, a saponified product of a vinyl acetate, and a water-based urethane in a formulating proportion shown in Table IV-1. It was likewise coated and dried as in the Example IV to form an ink-absorbing layer which is an image-receiving layer having the thickness of 15 ⁇ m and to obtain respective recording sheets IV-1.
• Table IV-1 shows formulating proportion of components in the respective resin composition and evaluation results in the recording sheets obtained.
• the resin composition for an ink-jet recording sheet of the present invention in which there is employed the resin composition for an ink-jet recording sheet of the present invention and which has an image-receiving layer on at least one surface of a base material, there can be improved water resistance, an ink-absorbing ability, and a printing quality even though under a circumstance in which a high resolution and a change to a high speed are required. Further, in the present invention, water resistance and an ink-absorbing ability are successfully consistent with each other while improving a printing quality to a same level as a photographic image quality, which are a contrary characteristic each other.
• a 2000 ml (milliliter) reaction vessel equipped with an agitator, a reflux condenser, a dropping funnel, a tube for introducing nitrogen, and a thermometer was charged with 219 parts of isopropylalcohol (IPA), and 1.23 part of azobisisobutylonitrile (AIBN) was added while agitating to dissolve, followed by heating to 80°C.
• IPA isopropylalcohol
• AIBN azobisisobutylonitrile
• AIBN which is an additional catalyst was dissolved in 25 parts by weight of IPA, and it was added dropwise into the reaction vessel, and reaction was further continued for 2 hours.
• 16 parts by weight of acetic acid was added into the reaction vessel, and 705 parts by weight of water was added dropwise over approximately 2 hours while agitating, followed by evaporating a solvent using a rotary evaporator to obtain the cationic methacrylic copolymer (A-V-1).
• the water-based coating liquid was coated on an art paper having the thickness of 190 ⁇ m (NK Whitone Gloss 180.0), and it was dried at 110°C for 3 minutes to form an ink-absorbing layer which is a picture image receiving layer having the thickness of 15 ⁇ m and to obtain a recording sheet V-1.
• the above formulation ratio is based on solid components.
• Example V-2 The same procedures were followed as in the Example V-1, except that the PVA-405 manufactured by Kuraray, Ltd. was not added to obtain a recording sheet V-2.
• Example V-1 The same procedures were followed as in the Example V-1, except that there was employed a water-based polyurethane resin (C-V) (HUX-670 manufactured by Asahi Denka Kogyo, Ltd.) in which the amount of a cationic group is smaller than in the HUX-670-M2 in place of the water-based polyurethane resin (C-V) (HUX-670-M2 manufactured by the same company) having a characteristics that the amount of a cationic group is larger employed in the Example V-1.
• C-V water-based polyurethane resin
• Example V-4 The same procedures were likewise followed as in the Example V-1, except that there was not added the HUX-670-M2 (C-V) manufactured by Asahi Denka Kogyo, Ltd. to obtain a recording sheet V-4.
• Example V-1 The same procedures were likewise followed as in the Example V-1, except that the components (A-V-1) and (B-V) employed in the Example V-1 were changed to 20 parts by weight and 80 parts by weight, respectively, to obtain a recording sheet V-5.
• a recorded picture image was visually observed, and adherence conditions of an embossed roll mark were judged according to the following standards.
• Glossiness in a recorded picture image was measured using a gloss meter according to JIS Z8741.
• Picture images for evaluation were formed in relation to sheets for recording obtained in Examples VI and Comparative Examples VI using a dye-ink jet printer (PM-770 manufactured by Seiko Epson, Ltd.) and a pigment-ink jet printer (ENCAD NOVAJET Pro).
• a model picture image was printed by cyan, magenta, yellow, and black and, further, red, green, and blue which are a mixed color from yellow, etc., and a PPC copy paper was placed on a letters-printed portion at an every fixed time.
• the copy paper was stripped after the loading (500 g/cm 2 ) was charged for 5 minutes, and conditions of ink-movement to the copy paper were visually observed according to the following standards.
• a model picture image was printed by cyan, magenta, yellow, and black and, further, red, green, and blue which are a mixed color from yellow, etc., and water droplet was dropped on a picture image after an ink was dried and, the water droplet was wiped after having placed for 1 minute, and there were visually observed a picture image in a wiped portion and conditions of an image-receiving layer according to the following standards.
• a 2000 ml (milliliter) reaction vessel equipped with an agitator, a reflux condenser, a dropping funnel, a tube for introducing nitrogen, and a thermometer was charged with 219 parts by weight of isopropylalcohol and 1.23 part by weight of azobisisobutylonitrile which is a catalyst while agitating to dissolve, followed by heating to 80°C.
• copolymerizable components there were mixed 93.7 parts by weight of methylmethacrylate, 98.7 parts by weight of n-butyl acrylate, 5.0 parts by weight of acrylic acid, and 4.93 parts by weight of 3-methacryloxy propyltrimethoxysilane (A-174 manufactured by Nihon Unicar, Ltd.), followed by adding dropwise into the reaction vessel over approximately 4 hours. After the completion of the dropwise addition, there was added dropwise into the reaction vessel a solution composed of 0.25 part by weight of azobisisobutylonitrile which is an additional catalyst and 25 parts by weight of isopropylalcohol, and reaction was further continued for 2 hours to complete polymerization.
• azobisisobutylonitrile which is an additional catalyst and 25 parts by weight of isopropylalcohol
• a 2000 ml reaction vessel equipped with an agitator, a reflux condenser, a dropping funnel, a tube for introducing nitrogen, and a thermometer was charged with 219 parts by weight of isopropylalcohol and 1.23 part of azobisisobutylonitrile which is a catalyst while agitating to dissolve, followed by heating to 80°C.
• copolymerizable components there were mixed 93.7 parts by weight of methylmethacrylate, 98.7 parts by weight of n-butyl acrylate, 49.3 parts by weight of diethylaminoethyl methacrylate, and 4.93 parts by weight of 3-methacryloxy propyltrimethoxysilane (A-174 manufactured by Nihon Unicar, Ltd.), followed by adding dropwise into the reaction vessel over approximately 4 hours. After the completion of the dropwise addition, there was added dropwise into the reaction vessel a solution composed of 0.25 part by weight of azobisisobutylonitrile which is an additional catalyst and 25 parts by weight of isopropylalcohol, and reaction was further continued for 2 hours.
• azobisisobutylonitrile which is an additional catalyst and 25 parts by weight of isopropylalcohol
• a mixed product containing 55.2 parts by weight (solid content of 20 parts by weight) of the resin A-VI-1 containing a crosslinkable group and 400 parts by weight (solid content of 80 parts by weight) of a rosary-state colloidal silica (Snowtex PS-M manufactured by Nissan Kagaku, Ltd.) was coated on a white-colored PET sheet having a density of 140 g/m 2 (thickness of 100 ⁇ m), so that thickness in dryness becomes 15 ⁇ m to obtain a recording sheet VI-1. Evaluation results of the recording sheet are shown in Table VI-1.
• a resin B-VI containing a cationic group was coated on the white-colored PET sheet employed in the Example VI-1, so that thickness in dryness becomes 30 ⁇ m to form an ink-fixing layer.
• Example VI-1 the mixed product employed in the Example VI-1 was likewise coated on the layer to obtain a recording sheet VI-2.
• Example VI-1 The same procedures were followed as in the Example VI-1, except that an acrylate resin (A-VI-2) was employed in place of the acrylate resin (A-VI-1) containing a crosslinkable group employed in the Example VI-1 to obtain a recording sheet VI-4. Evaluation results of the recording sheet are shown in Table VI-1.
• Example VI-1 The same procedures were likewise followed as in the Example VI-1, except that a spherical colloidal silica (Snowtex ST-20 manufactured by Nissan Kagaku, Ltd.) was employed in place of the rosary-state colloidal silica employed in the Example VI-1 to obtain a recording sheet VI-5. Evaluation results of the recording sheet are shown in Table VI-1.
• a spherical colloidal silica Snowtex ST-20 manufactured by Nissan Kagaku, Ltd.
• Example VI-2 The same procedures were likewise followed as in the Example VI-2, except that an ink-fixing layer was likewise formed as in the Example VI-2 and an ink-receiving layer was not formed to obtain a recording sheet VI-6. Evaluation results of the recording sheet are shown in Table VI-1.
• Example VI-1 ⁇ ⁇ Not more than 30 seconds ⁇ ⁇ ⁇ 70
• Example VI-2 ⁇ ⁇ Not more than 3 seconds ⁇ ⁇ ⁇ 73
• Example VI-3 ⁇ ⁇ Not more than 3 seconds ⁇ ⁇ ⁇ 7 1
• Comparative Example VI-1 ⁇ ⁇ Not more than O 30 seconds ⁇ ⁇ ⁇ 69
• Comparative Example VI-2 ⁇ ⁇ Not more than 3 seconds ⁇ ⁇ ⁇ 3 4
• Comparative Example VI-3 ⁇ ⁇ Not less than 3 minutes ⁇ ⁇ ⁇ 7 1
• Example VII In relation to recording sheets obtained in Example VII and Comparative Example VII, an ink-absorbing ability, water resistance, dissolution of a picture image, and blocking resistance were evaluated as shown below.
• a model letter-printing was conducted by a pigment-type water-based ink (cyan, magenta, and yellow, respectively) to form a recorded picture image on recording sheets obtained in Examples and Comparative Examples.
• a PPC copy paper was placed on a letters-printed portion at an every fixed time. The copy paper was stripped after the loading 24.5 kPa (250 gf/cm 2 ) was charged for 10 seconds, and conditions of ink-movement to the copy paper were visually observed, and there was measured a time of period through which ink-movement to a back surface becomes not observed.
• Example VII Using an ink-jet printer (MasterJet-JC2008 manufactured by Graphtec Ltd.), a magenta line of a yellow base (width of 100 ⁇ m) was printed on recording sheets obtained in Example VII and Comparative Example VII, followed by observing 50 times-enlarged dots using a microscope, and evaluation was conducted according to the following standards.
• Example VII Two recording sheets obtained in Example VII and Comparative Example VII were put one upon another and, placed at 40°C and 90% RH for 1 day while loading 3.92 kPa (40 gf/cm 2 ), and evaluated according to the following standards.
• the resin composition VII-a for recording shown in the Example VII-1 was coated on one surface of a synthetic paper having thickness of 110 ⁇ m (Yupo FPG110 manufactured by Ohji Yuka Paper manufacturing, Ltd.), and it was dried at 80°C for 5 minutes to obtain a recording sheet having a porous image-receiving layer having thickness of 7 ⁇ m, in which pores of an average pore diameter of 1 ⁇ m exist in a high density.
• Table VII-1 shows evaluation results of the recording sheet.
• Example VII-1 Not more than 1 minute ⁇ o ⁇ o ⁇
• Example VII-2 Not more than 1 minute ⁇ o ⁇ o ⁇
• Example VII-3 Not more than 1 minute ⁇ o ⁇ o ⁇ Comparative Example VII-1 3 minutes ⁇ ⁇ ⁇
• a body to be recorded or a recording sheet which is excellent in an ink-absorbing ability, blocking resistance, color reproducibility, water resistance in a recorded picture image or letters, and weatherability and, moreover, which has a surface glossiness.
• a 2000 ml reaction vessel equipped with an agitator, a reflux condenser, a dropping funnel, a tube for introducing nitrogen, and a thermometer was charged with 219 parts of isopropyl alcohol, and 1.23 part of azobisisobutylonitrile was added while agitating to dissolve, followed by heating to 80°C.
• copolymerizable components there were mixed 93.7 parts of methylmethacrylate, 98.7 parts of n-butylacrylate, 49.3 parts by weight of diethylaminoethyl methacrylate, 49.3 parts by weight of a polyethylene glycol methacrylate (Blemmer PE200 manufactured by Nihon Yushi, Ltd.), 24.7 parts of acrylic acid, and 4.93 parts of trimethoxysilane propylmethacrylate (A-174 manufactured by Nihon Unicar, Ltd.), followed by adding dropwise into the reaction vessel using the dropping funnel over approximately 4 hours.
• M-VIII As a hot-melt adhesive resin (M-VIII), there was employed a nylon-based powder 430-P1 manufactured by Da ⁇ icel-Huels, Ltd.
• Printing method Using an ink-jet printer (PM-770C manufactured by Seiko Epson Co. Ltd.), color patterns using cyan, magenta, yellow, and black, respectively, were set up at an iron print paper and printed on the recording sheets obtained in the Examples and Comparative Examples.
• washing resistance 1 g of a commercially supplied cleaning agent was added to 1 liter of water of temperature of 40°C, and there was immersed a T-shirt sample (5x10 cm) on which a picture image is transferred, followed by agitating at rotating speed of 600 rpm for 20 minutes using an agitator (Three-one motor). After having agitated, the sample was taken out, and water was completely removed, and a picture image transferred was observed, and washing resistance was evaluated according to the following standards.
• the polymer (L-VIII-1) and the polymer (L-VIII-2) were mixed with the hot-melt adhesive resin (M-VIII) in proportion of a solid content shown in Table VIII-1 to obtain a water-based coating liquid having 30% of nonvolatile components.
• the water-based coating liquid was coated on a base material (a releasing paper) having thickness of 100 ⁇ m using a barcoater to obtain heat transfer sheets. Amount of the coated resin was 40 gf m 2 .
• Table VIII-1 shows results evaluated using the transfer sheets.
• the resin composition of the present invention is constructed by the polymer (L) and the hot-melt adhesive resin (M), there can be largely improved a microcrack resistance, durability, water resistance, washing resistance in a picture image transferred by preparing the picture image on a strippable base material and by transferring to an elastic body, and there can be largely improved an ink-absorbing ability in the formation of a picture image.

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