WO2019049619A1 - 水分散性シート - Google Patents
水分散性シート Download PDFInfo
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- WO2019049619A1 WO2019049619A1 PCT/JP2018/030336 JP2018030336W WO2019049619A1 WO 2019049619 A1 WO2019049619 A1 WO 2019049619A1 JP 2018030336 W JP2018030336 W JP 2018030336W WO 2019049619 A1 WO2019049619 A1 WO 2019049619A1
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/42—Coatings with pigments characterised by the pigments at least partly organic
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/72—Coated paper characterised by the paper substrate
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/82—Paper comprising more than one coating superposed
- D21H19/828—Paper comprising more than one coating superposed two superposed coatings, the first applied being non-pigmented and the second applied being pigmented
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
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- 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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/41—Base layers supports or substrates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/28—Presence of paper
- C09J2400/283—Presence of paper in the substrate
Definitions
- the present invention relates to a water-dispersible sheet provided with an adhesive layer on one side, and to a water-dispersible sheet on the other side of which a coating layer such as a thermosensitive recording layer or an ink jet recording layer can be provided.
- Water-dispersed paper (also referred to as hydrolyzable paper or water-soluble paper), which disperses rapidly in water, is widely used for applications such as filter paper for cigarettes, confidential document paper, water-dispersible labels, etc. 1)
- the water dispersible label has a constitution in which a coating layer such as a thermosensitive recording layer or an ink jet recording layer is provided on the surface of the water dispersion paper so that printing and printing can be performed, and a water-soluble adhesive layer is provided on the back They are used by sticking to returnable containers etc. (Patent Document 2 etc.).
- water dispersion paper is made into the multilayered-structure, maintaining water dispersibility (patent documents 3, 4 etc.).
- Multi-layer structure in order to perform papermaking smoothly, a multi-layer structure in which the content of a paper strength agent (for example, fibrous carboxyalkyl cellulose salt) in a layer contacting with a dryer during paper making is reduced. It is set as a structure (patent document 4).
- a paper strength agent for example, fibrous carboxyalkyl cellulose salt
- Patent Document 5 An aqueous dispersion paper of 6 to 8 (neutral region) is disclosed (Patent Document 5).
- a water dispersible sheet having a paper surface pH of 6 to 8 (neutral region) is provided in order to impart good printability and the like on the water dispersible sheet.
- Patent Document 5 etc. a water dispersible material consisting of purified pulp with an ⁇ -cellulose content of 88% by weight or more
- the paper surface pH is 6 to 8 (neutral region)
- the water-dispersed paper can be provided, it was not possible to suppress the time-dependent deterioration of the tackiness of the adhesive layer while maintaining the water dispersibility (Comparative Examples 7, 8 and the like). Therefore, it is an object of the present invention to provide a water-dispersible sheet in which the time-dependent deterioration of the tackiness of the pressure-sensitive adhesive layer is suppressed while maintaining the water dispersibility.
- the inventors set the base paper of the water-dispersible sheet having an adhesive layer as a multilayer structure and do not contact the layer (surface layer) with which the adhesive layer contacts (inner layer). And a mixed pulp of refined pulp with an ⁇ -cellulose content of 88% by weight or more and wood pulp (for example, unrefined pulp), and the ratio thereof and the Canadian standard freeness of this blended pulp within a specific range. It has been found that the adhesive deterioration with time can be suppressed while maintaining the dispersibility, and the present invention has been completed.
- the present invention is a water-dispersible sheet having an adhesive layer on one surface layer (hereinafter referred to as "first surface layer") of a paper substrate comprising an inner layer and at least one surface layer,
- the first surface layer is composed of mixed pulp 1 consisting of wood pulp and refined pulp having an ⁇ -cellulose content of 88% by weight or more, and the Canadian standard freeness of the mixed pulp 1 is 450 to 600 ml CSF, and The content of the wood pulp in the mixed pulp 1 is 50 to 95% by weight
- the inner layer is composed of the mixed pulp 3 consisting of the wood pulp and the refined pulp having an alpha cellulose content of 88% by weight or more.
- It is a water dispersible sheet having a Canadian standard freeness of 3 of 600 to 750 ml CSF and a content of the wood pulp in the mixed pulp 3 of 50 to 95% by weight.
- the present invention is a mixed pulp comprising an inner layer and two surface layers respectively provided on both sides thereof, wherein the surface layers are each independently composed of wood pulp and refined pulp having an ⁇ -cellulose content of 88% by weight or more.
- the Canadian standard freeness of the mixed pulp is 450 to 600 ml CSF, and the content of the wood pulp in the mixed pulp is 50 to 95% by weight, and the inner layer is wood pulp and alpha cellulose
- the mixed pulp 3 is composed of a refined pulp having a content of 88% by weight or more, the Canadian standard freeness of the blended pulp 3 is 600 to 750 ml CSF, and the content of the wood pulp in the blended pulp 3 is 50 to 50 It is a paper substrate which is 95% by weight.
- the present invention is a method of producing a water-dispersible sheet consisting of (1) and (2).
- the mixed pulp comprises refined pulp having a content of 88% by weight or more, the Canadian standard freeness of the blended pulp is 450 to 600 ml CSF, and the content of the wood pulp in the blended pulp is 50 to 95% by weight
- the inner layer is composed of mixed pulp 3 consisting of wood pulp and refined pulp having an ⁇ -cellulose content of 88% by weight or more, the Canadian standard freeness of the mixed pulp 3 is 600 to 750 ml CSF, and the mixed Providing a paper base wherein the content of the wood pulp in the pulp 3 is 50 to 95% by weight, and (2) providing an adhesive layer on the first surface layer. 2) And (3) applying a water-based paint on the second surface layer or (3) providing a heat-sensitive recording layer or an ink
- the sheet (paper base) to be used for the water dispersible sheet has a multilayer structure, and the surface layer and the inner layer are composed of mixed pulp consisting of purified pulp and wood pulp (for example, unrefined pulp)
- mixed pulp consisting of purified pulp and wood pulp (for example, unrefined pulp)
- the water-dispersible sheet of the present invention comprises a paper base (hereinafter also referred to as “base paper”) and an adhesive layer, and the base paper comprises an inner layer and at least one surface layer.
- the water-dispersible sheet has a pressure-sensitive adhesive layer on one surface layer of the base paper (hereinafter also referred to as "first surface layer”).
- the water dispersible sheet may have a second surface layer on the side opposite to the first surface layer of the inner layer.
- the structure of the water-dispersible sheet of the present invention is shown in FIG.
- the inner layer and the surface layer (including the first surface layer and the second surface layer) constituting the base paper of the present invention are both wood pulp and purified pulp having an ⁇ -cellulose content of 88% by weight or more (hereinafter referred to as “ (Also referred to as refined pulp).
- wood pulp fibers or non-wood pulp fibers generally used for papermaking can be used, and the alpha cellulose content thereof is less than 88% by weight.
- the wood pulp include wood pulp fibers such as softwood kraft pulp and hardwood kraft pulp, non-wood pulp fibers such as flax pulp, manila hemp pulp and kenaf pulp.
- the average fiber length of wood pulp is 0.1 to 5 mm, preferably 0.5 to 3 mm, and more preferably 0.8 to 2 mm.
- the refined pulp used in the present invention is, for example, mercerized pulp or dissolved pulp made from non-wood such as softwood and hardwood wood, flax, linters etc. It is a pulp in which hemicellulose etc. is removed by chemical treatment after digestion to enhance the cellulose purity, and the pulp is refined to an ⁇ -cellulose content of 88% by weight or more.
- JP-A-2010-504376 divides the pulp into three grades according to the degree of refinement, and produces highly refined pulp “acetate grade”, refined pulp The content of each grade is described as “viscose grade” and unrefined pulp as “paper / fluff grade”.
- the "acetate grade” pulp is usually at least 95% by weight alpha cellulose and about 1 to 3% hemicellulose, and the “viscose grade” pulp is 88 to 95% by weight alpha cellulose and about 5 to 12% Is hemicellulose.
- the paper / fluff grade pulp is 80 to 88% by weight of ⁇ -cellulose and about 12 to 20% is hemicellulose. From the above, hemicellulose contained in the refined pulp used in the present invention is less than 12% by weight.
- pulp a general definition “aggregate of cellulose fibers obtained by mechanical or chemical treatment of wood and other plants” (Paper Pulp Dictionary, February 20, 2000 Japan Paper and Pulp Association) Defined as “Kinbara Publishing”.
- the mercerized pulp is a pulp obtained by immersing kraft pulp or sulfite pulp in a strong alkali solution and then washing with water to remove alkali.
- the dissolved pulp is a pulp with high cellulose purity obtained by sulfite cooking or prehydrolysis kraft cooking, and pulp with various cellulose purity can be obtained by combining post-digestion bleaching and selective treatment.
- the reason why the excellent dispersibility is obtained in the present invention is considered as follows.
- the purified pulp is considered to form a sheet having low strength and high bulkiness and high water dispersibility in an unbeaten state, since the refined pulp has an extremely small amount of hemicellulose which contributes to the swelling of fibers and sticking between fibers.
- the refined pulp when refined pulp is beaten, swelling and fibrillation of the fiber due to beating are suppressed and the water retention does not increase so much because the hemicellulose content is small, and the fiber is rigid and easily cut, and the short fiber content is It is considered to increase.
- the sheet formed from the refined refined pulp is increased in strength than in the unbeaten state and the bulk height is slightly impaired, the short fiber content contributing to the improvement of the water dispersibility is increased so that the water dispersibility is greatly impaired. It can not be considered.
- the alpha cellulose content is used as an index of the cellulose purity of the purified pulp.
- the ⁇ -cellulose content of the purified pulp is required to be 88% by weight or more, preferably 92% by weight or more, and more preferably 95% by weight or more. If the ⁇ -cellulose content of the purified pulp is less than 88% by weight, the dispersion in the form of monofilaments is difficult, and the dispersibility in water is reduced.
- the ⁇ -cellulose content is a value measured by ⁇ -cellulose specified in TAPPI Standard T203 om-83 (JIS P 8101-1994 (currently discontinued)).
- the hemicellulose content may be used as another indicator of the cellulose purity of the refined pulp in the present invention.
- the hemicellulose content of the purified pulp needs to be less than 12% by weight, preferably less than 8% by weight, and more preferably less than 5% by weight.
- the hemicellulose content of the purified pulp can be measured by acid hydrolysis of the purified pulp or non-purified pulp to convert it to a monosaccharide, and quantifying the composition of the monosaccharide by the alditol acetation method.
- the mixed pulp of the present invention does not contain regenerated cellulose fiber such as rayon, fibrous carboxyalkyl cellulose, fibrous carboxyalkyl cellulose salt (eg, CMC-Na salt).
- the regenerated cellulose fiber lacks in sheet strength and smoothness, resulting in poor printability.
- Fibrous carboxyalkyl cellulose is acidic, and the acidity adversely affects the use.
- Fibrous carboxyalkyl cellulose salts have an adverse effect on alkaline compounds remaining in the base paper in some applications and are susceptible to discoloration. As described later, such a problem does not occur when the aqueous dispersion sheet is impregnated or coated with an aqueous solution of a neutral water-soluble polymer by size press coating or the like after paper making.
- the inner layer constituting the base paper of the present invention comprises a mixed pulp consisting of wood pulp and refined pulp having an ⁇ -cellulose content of 88% by weight or more, and the content of wood pulp in this mixed pulp is 50 to 95% by weight, Preferably, it is 40 to 70% by weight.
- the Canadian Standard Freeness of the mixed pulp used in this inner layer is 600-750 ml CSF, preferably 630-720 ml CSF. This Canadian standard freeness is measured according to JIS P8121-2 2012 (the same shall apply hereinafter). As the beating progresses (freeness decreases), fibrillation, cutting and internal swelling of the fibers increase, and while the density, strength and smoothness of the base paper increase, the water dispersibility decreases.
- the surface layer (including the first surface layer and the second surface layer) constituting the base paper of the present invention is composed of a mixed pulp comprising wood pulp and refined pulp having an ⁇ -cellulose content of 88% by weight or more,
- the Canadian standard freeness of mixed pulp is 450 to 600 ml CSF, preferably 500 to 575 ml CSF in the surface layer (first surface layer) on which the adhesive layer is provided, and the content of wood pulp in this mixed pulp Is 50 to 95% by weight, preferably 65 to 80% by weight.
- the paper surface pH of the surface layer of such a configuration is 6 to 8 (neutral region).
- the Canadian standard freeness of mixed pulp and the content of wood pulp in this mixed pulp in any surface layer (second surface layer) not provided with a pressure-sensitive adhesive layer thereon depend on the purpose of use. It may be set appropriately.
- the composition of the second surface layer may be, for example, the same as the composition of the first surface layer, or the same as the composition of the inner layer.
- the Canadian standard freeness of wood pulp and a refined pulp may be same or different.
- the mixed pulp may be one obtained by separately beating and mixing wood pulp and refined pulp, or one obtained by mixing and beating.
- the base paper has such a multilayer structure (two or three layers), and the surface layer (first surface layer) on which the adhesive layer is provided has the above-mentioned constitution, so that good water dispersibility is obtained.
- the surface layer (first surface layer) on which the adhesive layer is provided has the above-mentioned constitution, so that good water dispersibility is obtained.
- the basis weight of the base paper of the present invention is usually 10 to 200 g / m 2 , and particularly 50 g / m 2 or more, preferably 50 to 120 g / m 2 as a base paper of coated paper for printing and printing. Those in the range of are suitable.
- the basis weight of each layer is usually in the range of 5 to 100 g / m 2 , preferably 10 to 100 g / m 2 .
- the water-dispersible sheet of the present invention has a pressure-sensitive adhesive layer on one surface layer (first surface layer).
- a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer
- a water-soluble or water-redispersible pressure-sensitive adhesive particularly a water-soluble acrylic pressure-sensitive adhesive
- water-soluble acrylic adhesives include copolymers of alkoxyalkyl acrylate, styrene sulfonate and other copolymerizable monomers, and carboxyl group-containing vinyl monomers such as (meth) acrylic acid.
- Examples thereof include those containing, as a base polymer, a copolymer of a monomer, a hydroxyl group-containing monomer, and an optionally used copolymerizable other monomer.
- a water redispersible acrylic adhesive copolymerizable with (meth) acrylic acid alkyl ester, a carboxyl group-containing vinyl monomer, and a vinyl monomer having an alkoxy group is optionally used Based on a copolymer with another monomer, or a copolymer obtained by copolymerizing a carboxylated rosin ester-containing vinyl monomer, a carboxyl group-containing vinyl monomer, and a water-soluble vinyl monomer What contains as a polymer etc.
- the carboxyl group of these copolymers may be in the form of a salt that is partially or entirely neutralized with an alkali, if necessary, and an alkali metal salt, an amine salt or an alkanolamine salt is preferred as the alkali. Used for
- a crosslinking agent can be blended with this water-soluble acrylic pressure-sensitive adhesive for the purpose of adjusting the adhesive strength, water solubility or water dispersibility.
- a crosslinking agent Arbitrary things can be suitably selected and used from what is conventionally used as a crosslinking agent in the acrylic adhesive conventionally.
- isocyanate crosslinking agents such as 1,2-ethylene diisocyanate
- epoxy crosslinking agents such as diglycidyl ethers, melamine resins, urea resins, dialdehydes, methylol polymers, metal chelate compounds, metal alkoxides, Metal salts and the like can be mentioned.
- the acrylic pressure-sensitive adhesive if necessary, adjusts the properties and improves the performance, a conventionally known plasticizer, tackifier, coloring agent, thickener, antifoaming agent, leveling agent, plasticizing agent An agent, an antifungal agent, an antioxidant and the like can be appropriately blended.
- the plasticizer and the tackifier are preferably water-soluble or water-dispersible, and examples of the plasticizer include polyhydric alcohols such as sugar alcohols, polyether polyols, and alkanolamine salts of oxidized rosin.
- the tackifier for example, alkali metal salts such as rosin, disproportionated rosin, hydrogenated rosin, ammonium salts, polyether esters and the like can be mentioned.
- pressure-sensitive adhesives may be applied directly to one surface layer (first surface layer) of a base paper to provide a pressure-sensitive adhesive layer, or an adhesive may be applied to the release agent surface of a release sheet to cause adhesion. After providing the agent layer, this may be adhered to one surface layer (first surface layer) of the base paper, and the pressure-sensitive adhesive layer may be transferred. In any case, the pressure-sensitive adhesive layer may be used by laminating a release sheet to prevent unnecessary adhesion except at the time of use, and if desired, peeling off.
- the coating amount of the pressure-sensitive adhesive layer provided on the base paper is about 3 to 60 g / m 2 , preferably about 10 to 50 g / m 2 as solid content.
- the adhesive coating amount is less than 5 g / m 2 , the adhesion performance of the obtained adhesive sheet is insufficient, while when it exceeds 60 g / m 2 , the adhesive is likely to come out during the production of the adhesive sheet or in the post-processing step. Absent.
- the release sheet is not particularly limited, and conventionally known paper substrates, for example, paper substrates such as glassine paper, coated paper, cast coated paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates, or What apply
- the basis weight of the release sheet is not particularly limited, but is usually about 20 to 120 g / m 2 .
- the adhesive may be applied by a printing method, and may be applied in a pattern excluding edge portions etc.
- the release sheet used in this case is also partially applied with a release agent corresponding to the application pattern of the adhesive. You can also. Furthermore, the release agent is partially applied to the surface on the coated side of the water releasable coated paper of the present invention in a dot-like or rectangular discontinuous pattern, while on one surface layer (first surface layer)
- a pressure sensitive adhesive sheet which does not require a release sheet can also be formed by partially applying the pressure sensitive adhesive in a pattern corresponding to the release agent and superposing the pressure sensitive adhesive partial application surface and the release agent partial application surface.
- a water-soluble polymer may be impregnated or coated on the surface thereof.
- a neutral (pH 6 to 8) solution for example, a neutral aqueous solution
- the impregnation or coating method is not particularly limited, and methods such as size press coating (usually, 2 roll size press coating), transfer roll coating, spray coating, gravure coating, and curtain coating may be used. It can be used, and size press coating is preferred from the viewpoint of productivity.
- the inter-fiber voids of the base paper are filled with the water-soluble polymer, and the dry strength of the water-dispersible sheet As the water-soluble polymer present in the inter-fiber spaces swells upon contact with water and pushes the fibers apart, the fibers can be easily separated.
- the dry film is easily redissolved in water, and it is preferable to use a carboxylalkylcellulose salt, an alginate, a pectinate, a polyacrylate, a polymethacrylate, a carboxyalkylated starch, a phosphoric acid Esterified starch, anionic polymer electrolyte salt such as anionic polyacrylamide, methyl cellulose, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyalkylene oxide, polyvinyl ethyl ether, hydroxyethylated starch, oxidized starch, oxidized starch, etc.
- anionic polymer electrolyte salt such as anionic polyacrylamide, methyl cellulose, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyalkylene oxide, polyvinyl ethyl ether, hydroxyethylated starch, oxidized starch, oxidized star
- Water-soluble polysaccharides such as polymer electroless, guar gum, torto gum, xanthan gum, gum arabic, carrageenan, galactomannan, pullulan, dextran, dextrin, etc., gelatin, casein, etc. It can be exemplified the quality, etc., and these can be used in combination one kind or two kinds or more. Among them, it is preferable to use a carboxymethylcellulose salt from the viewpoint of improvement of water dispersibility and strength.
- an optional coating layer such as a thermosensitive recording layer or an ink jet recording layer may be provided on the surface of the water-dispersible sheet of the present invention opposite to the adhesive layer (that is, on the second surface layer).
- the coating layer in the present invention may be a single layer or a multilayer as long as it is a layer formed by coating and drying a water-based paint, and the coating method and the like are not limited.
- the constituent material of the coating layer suitable for a printing system (offset printing, gravure printing, etc.) or a printing system (ink jet printer, thermal printer, laser beam printer, etc.) can be selected suitably. Below, the example of the coating layer applied to a thermal printer, an inkjet printer, and gravure is shown.
- thermosensitive recording layers examples of coating layers (thermal recording layers) adapted to a thermal printer:
- a colorless or pale electron-donating leuco dye hereinafter also referred to as "leuco dye”
- a light-colored one on the second surface layer of the above-mentioned base paper is coated.
- a heat-sensitive recording layer is coated, which contains an electron-accepting developer (hereinafter also referred to as "developer") as a main component.
- developer electron-accepting developer
- an undercoat coating layer containing a pigment and a binder as main components may be provided between the base paper and the thermosensitive recording layer.
- the smoothness of the surface of the base paper on which the undercoat layer is applied is not particularly limited, but in general, a highly smooth surface is preferred, and a Yankee dryer contact surface and a calendered surface are preferably used.
- the undercoat layer is a heat-sensitive recording material that is coated to enhance the smoothness of the surface of the base paper to achieve the sharpness and high sensitivity of the image, and a known binder and various additives are appropriately selected and used. be able to.
- silica As pigments for the undercoat layer, silica, calcium carbonate, clay, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, aluminum hydroxide, magnesium carbonate, zinc oxide, aluminum oxide, magnesium hydroxide, barium sulfate, calcium sulfate Mineral fillers such as zinc sulfate, calcium silicate, aluminum silicate, magnesium silicate, sodium aluminosilicate, magnesium aluminosilicate, etc. or melamine resin fillers, urea-formalin resin fillers, organic powders such as polyethylene powder, nylon powder etc.
- a water-soluble resin or a water-dispersible resin is preferable, and specifically, starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, sodium alginate, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, Examples thereof include polyacrylamides, acrylamide / acrylate copolymers, styrene / maleic anhydride copolymers and alkali salts thereof, ethylene / maleic anhydride copolymers and alkali salts thereof, sodium polyacrylate and the like.
- starches which are water-soluble resins, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, sodium alginate, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone are used as the main component of the binder Is desirable.
- the binder of the undercoat layer is usually 5 to 100 parts by weight in solid content with respect to 100 parts by weight of the pigment.
- the undercoat layer in addition to the pigment and the binder, various commonly used additives can be used in combination.
- various additives include pigment dispersants, antifoaming agents, lubricants, UV absorbers, sizing agents, sensitizers, fluorescent dyes, preservatives and the like.
- the undercoat layer is obtained by coating a coating obtained by dispersing and mixing the above-mentioned pigment and binder with other additives in one or more layers by a coating machine, and drying by heating with a dryer or the like.
- the coating amount of the undercoat layer is usually 0.5 to 50 g / m 2 , preferably 3 to 15 g / m 2 as solid content.
- the coating machine include an air knife coater, a bar coater, a roll coater, a blade coater, a curtain coater, a chamber coater, and a gravure coater.
- known leuco dyes can be used singly or in combination of two or more, and in particular, triphenylmethane, fluoran, phenothiazine, auramine, spiropyran, indolinophthalide Leuco compounds of dyes such as dyes are preferably used.
- leuco dyes include 3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also called crystal violet lactone), 3 , 3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3 -Cyclohexylamino-6-chlorofluoran, 3-dimethylamino-5,7-dimethylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7,8 -Benzfluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3- ( -P
- 3-diethylamino-6 is a more safe leuco dye among them.
- phenols, organic acids or inorganic acids or esters or salts thereof can be used as a developer to be contained together with the leuco dye in the thermosensitive recording layer.
- organic acids or inorganic acids or esters or salts thereof include gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-di- ⁇ -methylbenzylsalicylic acid, 4,4'-isopropylyl.
- 2-hydroxy-p-toluic acid zinc 3,5-di-tert-butyl salicylate, tin 3,5-di-tert-butyl salicylate, tartaric acid, oxalic acid, maleic acid, citric acid, succinic acid, stearic acid, 4-hydroxyphthalic acid, boric acid, thiourea derivative, 4-hydroxythiophenol derivative, bis (4-hydroxyphenyl) acetic acid, ethyl bis (4-hydroxyphenyl) acetate, n-propyl bis (4-hydroxyphenyl) acetate , N-butyl bis (4-hydroxyphenyl) acetate, phenyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, phenethyl bis (4-hydroxyphenyl) acetate, bis (3-methyl-4acetate -Hydroxyphenyl) acetic acid, bis (3-methyl-4-hydroxyphenyl) vinegar Methyl,
- the water-dispersible sheet of the present invention may be used as an application to be washed out to a drain after use, in consideration of the environment, among these, as a safer developer, 4,4 ' -Dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, benzyl parahydroxybenzoate, 4-hydroxy-4'-propoxydiphenylsulfone, 3- ⁇ [(phenylamino) ) Carbonyl] amino ⁇ benzene sulfonamide, N- (4'-hydroxyphenylthio) acetyl-2-hydroxyaniline, N- (4'-hydroxyphenylthio) acetyl-4-hydroxyaniline and N- (4'-hydroxy) 1: 1 mixture with phenylthio) acetyl-2-hydroxyaniline, 4,4'-bis (3- (phenoxycarbonylamino) methylphenylureido)
- a well-known binder can be used for a thermosensitive recording layer.
- Specific examples thereof include polyvinyl alcohol such as completely saponified polyvinyl alcohol and partially saponified polyvinyl alcohol, carboxy modified polyvinyl alcohol, amide modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, modified polyvinyl alcohol such as butyral modified polyvinyl alcohol, hydroxy Ethylcellulose, Methylcellulose, Carboxymethylcellulose, Starches, Gelatin, Casein, Sodium Alginate, Polyvinylpyrrolidone, Polyacrylamide, Acrylamide / Acrylate Copolymer, Alkali Salt of Styrene / Maleic Anhydride Copolymer, Ethylene / Maleic Anhydride Copolymer Water-soluble resins such as polymer alkali salts, styrene-butadiene copolymer, acrylonitrile / butadiene copolymer, Methyl methacrylate /
- starches which are water-soluble resins, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, sodium alginate, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, as a main component of the binder It is desirable to use.
- auxiliary additives such as sensitizers, pigments, metal salts of p-nitrobenzoic acid (Ca, Zn) or monobenzyl phthalate Stabilizers such as ester metal salts (Ca, Zn), mold release agents such as fatty acid metal salts, lubricants such as waxes, pressure color inhibitors, benzophenone type and triazole type ultraviolet absorbers, water resistant agents such as glyoxal, A dispersing agent, an antifoamer, etc. can be used together.
- auxiliary additives such as sensitizers, pigments, metal salts of p-nitrobenzoic acid (Ca, Zn) or monobenzyl phthalate Stabilizers such as ester metal salts (Ca, Zn)
- mold release agents such as fatty acid metal salts
- lubricants such as waxes
- pressure color inhibitors such as waxes
- benzophenone type and triazole type ultraviolet absorbers water resistant agents such as glyoxal
- a heat fusible substance is used as a sensitizer for improving heat responsiveness, and a heat fusible organic compound having a melting point of about 50 to 200 ° C. can be used.
- a heat fusible organic compound having a melting point of about 50 to 200 ° C. include stearic acid amide, palmitic acid amide, N-hydroxymethyl stearic acid amide, N-stearyl stearic acid amide, ethylenebisstearic acid amide, N-stearyl urea, benzyl-2-naphthyl ether, m-terphenyl 4-benzylbiphenyl, 2,2'-bis (4-methoxyphenoxy) diethyl ether, ⁇ , ⁇ '-diphenoxyxylene, bis (4-methoxyphenyl) ether, diphenyl adipate, dibenzyl oxalate, dioxalate (4-Chlorobenzyl), dimethyl terephthalate, dibenz
- the water-dispersible sheet of the present invention may be used as an application to be washed out to drains after use, from the environmental aspect, stearic acid amide, as a more safe sensitizer among these, Palmitic acid amide, ethylenebisstearic acid amide, benzyl p-benzyloxybenzoate, 4-biphenyl-p-tolyl ether, di (p-methylbenzyl) oxalate, di (4-chlorobenzyl) oxalate, 4-benzyl Biphenyl, 1,2-bis (phenoxymethyl) benzene, diphenyl sulfone, ⁇ -benzyloxynaphthalene, paraphenylacetophenone, 1,2-bis- (3-methylphenoxy) ethane and the like are preferably used.
- silica calcium carbonate, clay, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, aluminum hydroxide, magnesium carbonate, zinc oxide, aluminum oxide, magnesium hydroxide, barium sulfate, calcium sulfate, zinc sulfate, Inorganic fillers such as calcium silicate, aluminum silicate, magnesium silicate, sodium aluminosilicate, magnesium aluminosilicate, etc. or melamine resin fillers, urea-formalin resin fillers, organic pigments such as polyethylene powder, nylon powder and the like.
- the amounts of developers, leuco dyes, sensitizers, and the types and amounts of other various components are determined according to the required performance and recording suitability, and are not particularly limited, but usually 1 part by weight of leuco dye 0.5 to 10 parts by weight of a developer and 0.5 to 10 parts by weight of a sensitizer are used, and the binder is suitably 5 to 50% by weight in the total solid content.
- the above-mentioned organic developer, leuco dye and optionally added materials are micronized to a particle size of several microns or less by a grinder such as a ball mill, attritor, sand grinder or a suitable emulsifying device, a binder and Add various additives according to the purpose to make a paint.
- the method of forming the heat-sensitive recording layer is not particularly limited. For example, various printing methods such as lithography, air knife coating, rod blade coating, bar coating, blade coating, gravure coating, curtain coating, etc. It is formed by the method of coating-drying on a base paper by a method. Also, the coating amount of the heat-sensitive recording layer, usually 2 ⁇ 12g / m 2 as a solid content, preferably in the range of about 3 ⁇ 10g / m 2.
- thermosensitive recording layer by optionally applying a protective layer on the thermosensitive recording layer, it is possible to improve the matching property of a thermal head or the like and the recorded image storage property.
- the binder used for the protective layer may be the same as the binder of the heat-sensitive recording layer.
- polyvinyl alcohol such as completely saponified polyvinyl alcohol and partially saponified polyvinyl alcohol, carboxy modified polyvinyl alcohol, amide modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, modified polyvinyl alcohol such as butyral modified polyvinyl alcohol, hydroxy Ethylcellulose, Methylcellulose, Carboxymethylcellulose, Starches, Gelatin, Casein, Sodium Alginate, Polyvinylpyrrolidone, Polyacrylamide, Acrylamide / Acrylate Copolymer, Alkali Salt of Styrene / Maleic Anhydride Copolymer, Ethylene / Maleic Anhydride Copolymer Water-soluble resins such as polymer alkali salts, styrene-butadiene copolymer, acrylonitrile / butadiene copolymer, Methyl methacrylate / butadiene copolymer, acrylonitrile / butadiene copoly
- starches which are water-soluble resins, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, sodium alginate, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, as a main component of the binder It is desirable to use.
- the protective layer can be obtained by coating a coating obtained by dispersing and mixing various additives into the above-mentioned binder in one or more layers by a coating machine, and heating and drying with a dryer.
- the coating amount of the protective layer is usually 0.2 to 10 g / m 2 , preferably 0.5 to 5 g / m 2 as solid content.
- the coating machine is not particularly limited, and known coating machines such as an air knife coater, a bar coater, a roll coater, a blade coater, a curtain coater, a chamfer coater, and a gravure coater can be used. There is no limit.
- the surface smoothness of the heat-sensitive recording layer side of the water-dispersible sheet of the present invention is enhanced by using a smoothing device such as a calender, super calender or soft nip calender.
- a smoothing device such as a calender, super calender or soft nip calender.
- the Bekk smoothness of the heat-sensitive recording layer side surface is preferably 50 to 2000 s, more preferably 100 to 2000 s. If the Beck's smoothness is less than 50 s, the improvement in image sharpness and sensitivity is poor. On the other hand, when the Beck's smoothness exceeds 2000 s, the decrease in water dispersibility due to the density improvement of the base paper becomes noticeable, which is not preferable.
- Example of the coating layer (ink jet recording layer) adapted to the ink jet printer When the water dispersible sheet of the present invention is applied to the printing of an ink jet printer, a pigment coated layer containing a pigment and an aqueous binder as main components, or a cationic resin and / or an aqueous binder on the second surface layer of base paper. It is preferable to provide a clear coat layer as the main component, and as the pigment, binder and various additives, known ones can be appropriately selected and used, and the compounding amount can be appropriately adjusted according to the required quality. In addition, since the base paper has a porous layer (a layer having high ink absorbability) containing a purified pulp having an ⁇ -cellulose content of 88% by weight or more, the ink absorbability is improved.
- a porous layer a layer having high ink absorbability
- silica, alumina, calcined kaolin, calcium carbonate and the like are preferably used from the viewpoint of ink absorbability and color development.
- a water-soluble resin or a water-dispersible resin is preferable.
- polyvinyl alcohol, modified polyvinyl alcohol and the like are preferably used from the viewpoint
- Examples of various additives include cationic resins (dye fixing agents), pigment dispersants, antifoaming agents, lubricants, ultraviolet light absorbers, sizing agents, fluorescent dyes, preservatives and the like. Among them, it is desirable to use a cationic resin in combination since it significantly improves the water resistance and color development of the image area.
- the coating machine is not particularly limited, and an air knife coater, a bar coater, a roll coater, a blade coater, a curtain coater, a cast coater, a chample coater, a gravure coater, a two roll coater, a transfer roll coater, etc. are used. Ru.
- coated layers adapted to gravure printing When the water-dispersible sheet of the present invention is adapted to gravure printing, a pigment coat layer mainly composed of a pigment and an aqueous binder, or a clear coat layer mainly composed of an aqueous binder, on the second surface layer of base paper It is preferable to provide, and as the pigment, the binder and various additives, known ones can be appropriately selected and used. In addition, since the base paper has a porous layer (a layer having high cushioning properties) containing a purified pulp having an ⁇ -cellulose content of 88% by weight or more, the ink receptivity is improved.
- pigment calcium carbonate, clay, kaolin, calcined kaolin, diatomaceous earth, talc, titanium oxide, aluminum hydroxide, magnesium carbonate, zinc oxide, aluminum oxide, magnesium hydroxide, barium sulfate, calcium sulfate, zinc sulfate, silicic acid Inorganic filler or melamine resin filler such as calcium, aluminum silicate, magnesium silicate, sodium aluminosilicate, magnesium aluminosilicate, silica, colloidal silica, calcium carbonate composite silica, urea-formalin resin filler, polyethylene powder, nylon powder, styrene, Styrene-acrylic, organic pigments such as acrylic can be mentioned.
- a water-soluble resin or a water-dispersible resin is preferable. Specifically, starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, sodium alginate, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl pyrrolidone, polyacrylamide, acrylamide / Acrylate ester copolymer, styrene / maleic anhydride copolymer and its alkali salt, ethylene / maleic anhydride copolymer and its alkali salt, styrene / butadiene copolymer, sodium polyacrylate, sodium vinyl acetate, ethylene Vinyl acetate, acrylic acid copolymer, methacrylic acid copolymer, acrylic acid / methacrylic acid copolymer, and the like.
- water soluble resin starch hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, sodium alginate, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone as a binder .
- Examples of various additives include cationic resins (printability improving agents), pigment dispersants, antifoaming agents, lubricants, ultraviolet light absorbers, sizing agents, fluorescent dyes, preservatives and the like.
- the coating machine is not particularly limited, and an air knife coater, a bar coater, a roll coater, a blade coater, a curtain coater, a cast coater, a chample coater, a gravure coater, a two roll coater, a transfer roll coater, etc. are used. Ru.
- the water-dispersible sheet of the present invention obtained in this manner can be easily removed from the adherend only by washing with water after being attached to the adherend such as a container or a returnable container.
- Example 1 (Preparation of base paper) Mixed pulp comprising 70% by weight of softwood-bleached kraft pulp as wood pulp ( ⁇ -cellulose content 85.6% by weight) and 30% by weight of hardwood-dissolving pulp (98.3% by weight ⁇ -cellulose) as purified pulp Softwood bleached kraft pulp ( ⁇ -cellulose content: 85.6% by weight) 15% by weight and hardwood bleached kraft pulp as wood pulp on both sides of the inner layer consisting of a papermaking material beaten to a standard freeness of 675 ml CSF and its inner layer Paper made from a mixed pulp consisting of 55% by weight of ⁇ -cellulose content 86.0% by weight and 30% by weight of hardwood-dissolving pulp (98.3% by weight ⁇ -cellulose) as refined pulp to a Canadian freeness of up to 500 ml CSF
- the three layers were hand-laminated to make a three-layered hand-made paper.
- the paper pH was 6.7.
- carboxymethyl cellulose sodium salt trade name Sunrose, manufactured by Nippon Paper Industries Co., Ltd., viscosity of a 2% by weight aqueous solution at 20 ° C. is 5 mPa ⁇ s) (hereinafter also referred to as “CMC-Na”) as a water-soluble polymer.
- Aqueous solution (pH 7.1) was press-coated on a hand-made paper at a size of 8% by weight to prepare a water-dispersible sheet.
- thermosensitive recording layer paint Color developer dispersion (Liquid A) 36.0 parts Leuco dye dispersion (Liquid B) 9.2 parts Sensitizer dispersion (Liquid C) 12.0 parts
- This heat-sensitive recording layer coating is used as one of the base paper
- the surface (second surface layer) was coated at a solid content of 6 g / m 2 and dried (50 ° C.) to form a thermosensitive recording layer, whereby a recording paper was obtained.
- the recording paper was subjected to a smoothing treatment so as to have a Beck smoothness of 500 to 1000 seconds.
- the adhesive paint of the following composition was prepared. ⁇ Adhesive paint> Water soluble acrylic adhesive (Big Technos Co., Ltd., trade name "Liquidine AR-2410, solid content concentration 42% by weight) 100 parts by weight Hardener (Big Technos Co., Ltd., trade name” Sun Pasta HD- 5013 " 0.1 parts by weight
- the adhesive paint was applied on a release-treated surface of a commercially available release sheet coated with a silicone release agent at a solid content of 25 g / m 2 and dried to form an adhesive layer.
- the pressure-sensitive adhesive layer and the surface (first surface layer) opposite to the thermosensitive recording layer of the recording paper were laminated to prepare a water-dispersible sheet.
- thermosensitive recording paper printing tester equipped with a thermal head manufactured by Kyocera
- Gradation pattern printing was performed by increasing every 0.015 mJ / dot to / dot. Printing was possible without unevenness in printing, and the definition of the printing portion was good.
- Example 2 A water dispersible sheet was produced in the same manner as in Example 1 except that the mixed pulp blended in the surface layer was beaten to a Canadian standard freeness of 600 ml CSF.
- Example 3 A water dispersible sheet was produced in the same manner as in Example 1 except that the mixed pulp blended in the surface layer was beaten to a Canadian standard freeness of 500 ml CSF.
- Example 4 A water-dispersible sheet was produced in the same manner as in Example 1 except that the heat-sensitive recording layer was not coated.
- Example 5 Softwood bleached kraft pulp ( ⁇ -cellulose content: 85.6% by weight) 70% by weight as mixed pulp mixed with the surface layer as wood pulp and hardwood-dissolved pulp ( ⁇ -cellulose content: 98.3% by weight) as purified pulp 30% by weight
- a water dispersible sheet was produced in the same manner as in Example 1 except that the mixed pulp was replaced by a mixed pulp consisting of%.
- Example 6 A water dispersible sheet was produced in the same manner as in Example 1 except that the second surface layer was not provided.
- Example 7 A water-dispersible sheet was produced in the same manner as in Example 1 except that the second surface layer was not provided and the heat-sensitive recording layer was not provided.
- Example 8 A water dispersible sheet was produced in the same manner as in Example 2 except that the second surface layer was not provided, size press coating was not performed, and the heat sensitive recording layer was not provided.
- Example 9 A water dispersible sheet was produced in the same manner as in Example 2 except that the size press was not applied and the heat sensitive recording layer was not applied.
- Example 11 In the size press coating in Example 1, instead of the aqueous solution of carboxymethylcellulose sodium salt, an enzyme-modified dextrin (manufactured by Sanwa Starch Co., Ltd., viscosity of 2 wt% aqueous solution at 20 ° C. is 2 mPa ⁇ s) aqueous solution (pH 7.3) A water dispersible sheet was produced in the same manner as in Example 1 except that the above was used.
- an enzyme-modified dextrin manufactured by Sanwa Starch Co., Ltd., viscosity of 2 wt% aqueous solution at 20 ° C. is 2 mPa ⁇ s) aqueous solution (pH 7.3)
- a water dispersible sheet was produced in the same manner as in Example 1 except that the above was used.
- Example 12 In the size press coating in Example 1, instead of the aqueous solution of carboxymethylcellulose sodium salt, an aqueous solution (pH 7.4) of a calcined dextrin (manufactured by Nichired Chemical Co., Ltd., viscosity of 2 wt% aqueous solution at 20 ° C. is 2 mPa ⁇ s) A water dispersible sheet was produced in the same manner as in Example 1 except that it was used.
- Comparative Example 1 A water dispersible sheet was produced in the same manner as in Example 1 except that the mixed pulp blended in the surface layer was beaten to a Canadian standard freeness of 650 ml CSF. Comparative example 2 A water dispersible sheet was produced in the same manner as in Example 1 except that the mixed pulp blended in the surface layer was beaten to a Canadian standard freeness of 400 ml CSF. Comparative example 3 Softwood bleached kraft pulp ( ⁇ -cellulose content: 85.6% by weight) 8.6% by weight and broadleaf bleached kraft pulp ( ⁇ -cellulose content: 86.0% by weight) as wood pulp mixed with the mixed pulp in the surface layer 31.
- a water dispersible sheet was produced in the same manner as in Example 1 except that it was replaced by a mixed pulp consisting of 4% by weight and 60% by weight of hardwood-dissolving pulp ( ⁇ -cellulose content 98.3% by weight) as purified pulp.
- Comparative example 4 Softwood bleached kraft pulp ( ⁇ -cellulose content 85.6% by weight) 21.4% by weight and hardwood bleached kraft pulp ( ⁇ -cellulose content 86.0% by weight) as wood pulp mixed with the surface layer.
- a water dispersible sheet was produced in the same manner as in Example 1 except that it was replaced by a mixed pulp consisting of 6% by weight and containing no purified pulp.
- Comparative example 5 Softwood bleached kraft pulp ( ⁇ -cellulose content: 85.6% by weight) 40% by weight as mixed pulp mixed with the inner layer as wood pulp, and hardwood-dissolved pulp ( ⁇ -cellulose content: 98.3% by weight) 60 as purified pulp
- a water dispersible sheet was produced in the same manner as in Example 1 except that the mixed pulp was replaced with a mixed pulp consisting of% by weight. Peeling of the surface layer and the inner layer occurred during size press coating, and a water dispersible sheet was not obtained. It is considered that the blending of refined pulp in the inner layer is increased and the interfiber bonding is weakened.
- Comparative example 6 The same procedure as in Example 1 was repeated except that the mixed pulp blended in the inner layer was replaced by a mixed pulp composed of softwood bleached kraft pulp (a content of ⁇ -cellulose 85.6% by weight) as wood pulp and not containing purified pulp. A water dispersible sheet was prepared. Comparative example 7 The same procedure as in Example 1 was carried out except that a single layer sheet was prepared using only the papermaking raw material compounded in the surface layer without providing the inner layer, and the heat sensitive recording layer and the pressure sensitive adhesive layer were provided directly on both surfaces of the surface layer. A water dispersible sheet was prepared.
- Comparative Example 8 A single-layer sheet was prepared using only the papermaking raw material blended in the inner layer without providing the surface layer, and the same procedure as in Example 1 was carried out except that the thermosensitive recording layer and the pressure-sensitive adhesive layer were provided directly on both sides of the inner layer. A water dispersible sheet was prepared.
- the following evaluation was performed 14 days after applying an adhesive.
- the evaluation of tackiness with time was also performed on the first day (first day) after the application of the pressure-sensitive adhesive.
- the evaluation was performed after peeling the release sheet at the time of the water dispersibility test.
- the water dispersion time (the time when the test piece breaks into two or more and becomes floc) is within 9 seconds without the thermosensitive recording layer, within 10 seconds with the thermosensitive recording layer, and the water dispersion time (the test piece is It can be judged that the water dispersibility is good as long as the time to completely unravel the fibers into fibers is 150 seconds or less with the thermosensitive recording layer.
- Table 1 shows the configuration of the produced water-dispersible sheet and the evaluation results.
- Table 1 shows that the water-dispersible sheet of the structure of this invention is a water-dispersible sheet which suppressed the time-dependent deterioration of the adhesiveness of the adhesion layer, maintaining water dispersibility.
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Abstract
Description
また、水分散紙は、水分散性を保ちつつ、多様な用途に合わせて多様な性能を付加するために、多層構造にしたものが開発されている(特許文献3,4等)。例えば、水分散紙にピグメントコート層や感熱記録層を塗工する際に、その印刷・印字適性を良好にするために、水分散紙をアルカリ化した繊維状カルボキシアルキルセルロースと製紙用水分散性繊維から成る多層構造としたり(特許文献3)、抄紙をスムースに行うために、抄紙時に乾燥機との接触する層の紙力増強剤(例えば、繊維状カルボキシアルキルセルロース塩)の含量を少なくした多層構造としている(特許文献4)。
また、木材パルプとαセルロース含有率88重量%以上の精製パルプからなる基紙に水溶性高分子を付与することで、迅速な水分散性及び高い強度(印刷適性)を有し、紙面pHが6~8(中性領域)である水分散紙が開示されている(特許文献5)。
そのため、本願発明は、水分散性を保ちながら、粘着層の粘着性の経時劣化を抑えた水分散性シートを提供することを目的とする。
即ち、本発明は、内部層及び少なくとも一つの表面層から成る紙基材の一つの表面層(以下「第1の表面層」という。)上に粘着剤層を有する水分散性シートであって、該第1の表面層が、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプ1から成り、該混合パルプ1のカナダ標準ろ水度が450~600mlCSFであり、かつ該混合パルプ1中の該木材パルプの含有量が50~95重量%であり、該内部層が、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプ3から成り、該混合パルプ3のカナダ標準ろ水度が600~750mlCSFであり、かつ該混合パルプ3中の該木材パルプの含有量が50~95重量%である水分散性シートである。
(1)内部層及びその両面にそれぞれ設けた第1の表面層及び第2の表面層から成り、該第1の表面層及び第2の表面層が、それぞれ独立して、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプから成り、該混合パルプのカナダ標準ろ水度が450~600mlCSFであり、かつ該混合パルプ中の該木材パルプの含有量が50~95重量%であり、該内部層が、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプ3から成り、該混合パルプ3のカナダ標準ろ水度が600~750mlCSFであり、かつ該混合パルプ3中の該木材パルプの含有量が50~95重量%である紙基材を提供する段階、及び(2)該第1の表面層上に粘着層を設ける段階
また、(1)と(2)との間に、更に(3)前記第2の表面層上に水系塗料を塗工する段階や(3)前記第2の表面層上に感熱記録層やインクジェット記録層を設ける段階、を行ってもよい。
本発明で用いる木材パルプとして、一般に製紙用に用いられている木材パルプ繊維又は非木材系パルプ繊維を使用でき、そのαセルロース含有率は88重量%未満である。この木材パルプとして、例えば、針葉樹クラフトパルプ、広葉樹クラフトパルプ等の木材パルプ繊維、亜麻パルプ、マニラ麻パルプ、ケナフパルプ等の非木材系パルプ繊維等を挙げることができる。木材パルプの平均繊維長としては、0.1~5mm、好ましくは0.5~3mm、さらに好ましくは0.8~2mmである。
パルプのαセルロース含有率とヘミセルロース含有率の関係について、特表2010-504376号公報には、パルプを精製度に応じて3グレードに分け、高度に精製されたパルプを「アセテートグレード」、精製パルプを「ビスコースグレード」、無精製パルプを「紙/フラッフグレード」として、各グレードの含有率を記載している。「アセテートグレード」のパルプはαセルロースが通常95重量%以上で、約1~3%がヘミセルロースであり、「ビスコースグレード」のパルプはαセルロースが88~95重量%で、約5~12%がヘミセルロースである。また、「紙/フラッフグレード」のパルプはαセルロースが80~88重量%で、約12~20%がヘミセルロースであるとしている。
以上のことから、本発明に用いられる精製パルプに含まれるヘミセルロースは12重量%未満となっている。
なお、本発明では、パルプについて、一般的な定義である「木材その他の植物を機械的又は化学的処理によって抽出したセルロース繊維の集合体」(紙パルプ辞典 平成12年2月20日 紙パルプ協会編 金原出版)と定義する。
溶解パルプは、亜硫酸塩蒸解や前加水分解クラフト蒸解で得られるセルロース純度の高いパルプで、蒸解後の漂白、精選処理を組み合わせることでさまざまなセルロース純度のパルプが得られる。
本発明における精製パルプのセルロース純度の別種の指標としてヘミセルロース含有率を用いてもよい。その場合、精製パルプのヘミセルロース含有率は12重量%未満であることが必要であり、好ましくは8重量%未満であり、さらに好ましくは5重量%未満である。精製パルプのヘミセルロース含有率が12重量%以上の場合、単繊維状に分散し難くなるため、水への分散性が低下する。なお、本発明において、ヘミセルロース含有率は、精製パルプ又は無精製パルプを酸加水分解して単糖に変え、単糖類の組成をアルジトールアセテート化法によって定量することにより測定できる。即ちパルプの加水分解により得られる単糖類を水素化ホウ酸ナトリウムで還元し相当するアルジトールアセテートに変え、無水酢酸とピリジンでアセチル化し、アルジトールアセテート誘導体とした後、アルジトールアセテート誘導体をガスクロマトグラフィーにより分析して構成糖を同定、定量する。
なお、精製パルプと無精製パルプが配合された紙についても、各パルプ単独の場合と同様にして紙のαセルロース含有率とヘミセルロース含有率を測定することができる。さらに、パルプの繊維形態を観察して精製パルプと無精製パルプの配合割合を求めれば、精製パルプと無精製パルプのそれぞれについてαセルロース含有率とヘミセルロース含有率を算出することができる。
再生セルロース繊維はシート強度や平滑性が不足して印刷適性が不良となる。繊維状カルボキシアルキルセルロースは酸性であり、用途により酸性が悪影響を及ぼす。繊維状カルボキシアルキルセルロース塩は、用途によっては基紙中に残存するアルカリ性化合物が悪影響を及ぼし、また変色し易い。
なお、後述のように、抄紙後に、水分散シートに、サイズプレス塗工等により中性の水溶性高分子の水溶液を含浸又は塗工する場合には、このような問題は生じない。
この内部層で用いられる混合パルプのカナダ標準ろ水度は、600~750mlCSF、好ましくは630~720mlCSFである。このカナダ標準ろ水度は、JIS P8121-2 2012に従って測定されたものである(以下同様)。
叩解が進む(ろ水度は低くなる)と、繊維のフィブリル化、切断、内部膨潤が多くなり、基紙の密度、強度、平滑度が高くなる一方で、水分散性は下がる。
このような構成の表面層の紙面pHは6~8(中性領域)である。
一方、その上に粘着剤層を設けない任意の表面層(第2の表面層)中の、混合パルプのカナダ標準ろ水度とこの混合パルプ中の木材パルプの含有量は、使用目的に応じて適宜設定すればよい。第2の表面層のこれら組成は、例えば、第1の表面層の組成と同一であってもよいし、内部層の組成と同一であってもよい。
なお、上記内部層及び表面層に用いる混合パルプのカナダ標準ろ水度を上記範囲にするために、木材パルプ及び精製パルプのカナダ標準ろ水度は同じであっても異なっていてもよい。また、この混合パルプは、木材パルプ及び精製パルプを別個に叩解して混合したものでも、混合して叩解したものでもよい。
また、各層の坪量は通常5~100g/m2、好ましくは10~100g/m2の範囲である。
この粘着剤層を構成する粘着剤としては、水溶性又は水再分散性を有する粘着剤、特に水溶性アクリル系粘着剤が好適に用いられる。
水溶性アクリル系粘着剤の例としては、アクリル酸アルコキシアルキルとスチレンスルホン酸塩と他の共重合性単量体とからなる共重合体や、(メタ)アクリル酸などのカルボキシル基含有ビニル系単量体と水酸基含有単量体と場合により用いられる共重合可能な他の単量体との共重合体をベースポリマーとして含有するものなどを挙げることができる。また、水再分散性アクリル系粘着剤の例としては、(メタ)アクリル酸アルキルエステルとカルボキシル基含有ビニル系単量体とアルコキシ基を有するビニル系単量体と場合により用いられる共重合可能な他の単量体との共重合体や、カルボキシル化ロジンエステル含有ビニル系単量体とカルボキシル基含有ビニル系単量体と水溶性ビニル系単量体が共重合されてなる共重合体をベースポリマーとして含有するものなどを挙げることができる。なお、これらの共重合体のカルボキシル基は、必要に応じ一部又は全部がアルカリにより中和された塩型であってもよく、このアルカリとして、アルカリ金属塩、アミン塩、アルカノールアミン塩が好適に用いられる。
また、粘着剤の塗布を印刷方式で行い、エッジ部分等を除いてパターン状に塗布してもよく、この場合に用いる剥離シートも粘着剤の塗布パターンに対応して剥離剤を部分塗布することもできる。更に、本発明の水剥離性塗工紙の塗工面側の表面に、点状や矩形状の非連続パターンで剥離剤を部分塗布し、一方、一つの表面層(第1の表面層)に剥離剤と対応するパターンで粘着剤を部分塗布し、粘着剤部分塗布面と剥離剤部分塗布面とを重ね合わせることにより、剥離シートが不要の粘着シートを形成することもできる。
この含浸又は塗工の方法としては、特に限定されないが、サイズプレス塗工(通常、2ロールサイズプレス塗工)、トランスファーロール塗工、スプレー塗工、グラビア塗工、カーテン塗工などの方法を使用でき、生産性の観点からサイズプレス塗工が好ましい。
上記本発明の構成の水分散性シートの表面層に、水溶性高分子を含浸又は塗工することで、水溶性高分子で基紙の繊維間空隙が充填され、水分散性シートの乾燥強度が高まるとともに、繊維間空隙に存在している水溶性高分子が水との接触により膨潤し、繊維間を押し広げるため、繊維が容易に分離することができる。
本発明における塗工層は、水系塗料を塗工・乾燥して形成された層であれば単層、多層でも良く、塗工方式などに制限はない。また、印刷方式(オフセット印刷、グラビア印刷など)あるいは印字方式(インクジェットプリンター、感熱プリンター、レーザービームプリンターなど)に適した塗工層の構成材料を適宜選択することができる。以下に、感熱プリンター、インクジェットプリンター、グラビア印刷に適応した塗工層の例を示す。
本発明の水分散性シートを感熱プリンターによる印字に適応させる場合、上記基紙の第2の表面層上に、無色ないし淡色の電子供与性ロイコ染料(以下、「ロイコ染料」ともいう。)及び電子受容性顕色剤(以下、「顕色剤」ともいう。)とを主成分として含有する感熱記録層を塗設する。また、基紙と感熱記録層との間に、顔料及びバインダーを主成分として含有するアンダーコート塗工層を設けてもよい。上記基紙はαセルロース含有率88重量%以上の精製パルプが含有されているポーラスな層(断熱効果の高い)を有しているため、カス付着性、スティッキング性が改善される。
アンダーコート層を塗設する基紙表面の平滑性は特に限定されないが、一般的には高平滑な表面が好まれ、ヤンキードライヤー接触面、カレンダリング処理面が好適に用いられる。
アンダーコート層は、感熱記録体において、基紙表面の平滑性を高めて画像のシャープネスと高感度を達成するために塗設されるもので、公知のバインダーや各種添加剤を適宜選択して用いることができる。
アンダーコート層のバインダーとしては水溶性樹脂又は水分散性樹脂が好ましく、具体的にはデンプン類、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、ゼラチン、カゼイン、アルギン酸ナトリウム、ポリビニルアルコール、変性ポリビニルアルコール、ポリビニルピロリドン、ポリアクリルアミド、アクリルアミド/アクリル酸エステル共重合体、スチレン/無水マレイン酸共重合体及びそのアルカリ塩、エチレン/無水マレイン酸共重合体及びそのアルカリ塩、ポリアクリル酸ソーダ等が挙げられる。これらの中でも水剥離性の観点から、水溶性樹脂であるデンプン類、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、ゼラチン、カゼイン、アルギン酸ナトリウム、ポリビニルアルコール、変性ポリビニルアルコール、ポリビニルピロリドンをバインダーの主成分として使用することが望ましい。
アンダーコート層のバインダーは、通常、顔料100重量部に対して固形分で5~100重量部である。
アンダーコート層は、前記顔料及びバインダーにその他の添加剤を分散混合して得られる塗料を、塗工機によって一層あるいは多層に分けて塗工し、ドライヤー等で加熱乾燥することによって得られる。
アンダーコート層の塗工量は、固形分として通常0.5~50g/m2、好ましくは3~15g/m2である。塗工機としては、エアナイフコーター、バーコーター、ロールコーター、ブレードコーター、カーテンコーター、チャンプレックスコーター、グラビアコーター等が挙げられる。
ロイコ染料の具体例としては、3,3-ビス(p-ジメチルアミノフェニル)-フタリド、3,3-ビス(p-ジメチルアミノフェニル)-6-ジメチルアミノフタリド(別名クリスタルバイオレットラクトン)、3,3-ビス(p-ジメチルアミノフェニル)-6-ジエチルアミノフタリド、3,3-ビス(p-ジメチルアミノフェニル)-6-クロルフタリド、3,3-ビス(p-ジブチルアミノフェニル)フタリド、3-シクロヘキシルアミノ-6-クロルフルオラン、3-ジメチルアミノ-5,7-ジメチルフルオラン、3-ジエチルアミノ-7-クロロフルオラン、3-ジエチルアミノ-7-メチルフルオラン、3-ジエチルアミノ-7,8-ベンズフルオラン、3-ジエチルアミノ-6-メチル-7-クロルフルオラン、3-(N-p-トリル-N-エチルアミノ)-6-メチル-7-アニリノフルオラン、3-ピロリジノ-6-メチル-7-アニリノフルオラン、2-{N-(3'-トリフルオルメチルフェニル)アミノ}-6-ジエチルアミノフルオラン、2-{3,6-ビス(ジエチルアミノ)-9-(o-クロルアニリノ)キサンチル安息香酸ラクタム}、3-ジエチルアミノ-6-メチル-7-(m-トリクロロメチルアニリノ)フルオラン、3-ジエチルアミノ-7-(o-クロルアニリノ)フルオラン、3-ジ-n-ブチルアミノ-7-(o-クロルアニリノ)フルオラン、3-N-メチル-N,n-アミルアミノ-6-メチル-7-アニリノフルオラン、3-N-メチル-N-シクロヘキシルアミノ-6-メチル-7-アニリノフルオラン、3-ジエチルアミノ-6-メチル-7-アニリノフルオラン、3-(N,N-ジエチルアミノ)-5-メチル-7-(N,N-ジベンジルアミノ)フルオラン、ベンゾイルロイコメチレンブルー、6'-クロロ-8'-メトキシ-ベンゾインドリノ-スピロピラン、6'-ブロモ-3'-メトキシ-ベンゾインドリノ-スピロピラン、3-(2'-ヒドロキシ-4'-ジメチルアミノフェニル)-3-(2'-メトキシ-5'-クロルフェニル)フタリド、3-(2'-ヒドロキシ-4'-ジメチルアミノフェニル)-3-(2'-メトキシ-5'-ニトロフェニル)フタリド、3-(2'-ヒドロキシ-4'-ジエチルアミノフェニル)-3-(2'-メトキシ-5'-メチルフェニル)フタリド、3-(2'-メトキシ-4'-ジメチルアミノフェニル)-3-(2'-ヒドロキシ-4'-クロル-5'-メチルフェニル)フタリド、3-(N-エチル-N-テトラヒドロフルフリル)アミノ-6-メチル-7-アニリノフルオラン、3-N-エチル-N-(2-エトキシプロピル)アミノ-6-メチル-7-アニリノフルオラン、3-N-メチル-N-イソブチル-6-メチル-7-アニリノフルオラン、3-モルホリノ-7-(N-プロピル-トリフルオロメチルアニリノ)フルオラン、
前述の有機顕色剤、ロイコ染料並びに必要に応じて添加する材料は、ボールミル、アトライター、サンドグラインダーなどの粉砕機あるいは適当な乳化装置によって数ミクロン以下の粒子径になるまで微粒化し、バインダー及び目的に応じて各種の添加材料を加えて塗料とする。
感熱記録層の形成方法については特に限定されず、例えば、平版等の各種印刷方式をはじめ、エアナイフ塗工、ロッドブレード塗工、バー塗工、ブレード塗工、グラビア塗工、カーテン塗工等の方法によって塗料を基紙上に塗工乾燥する方法で形成される。また、感熱記録層の塗工量については、固形分として通常2~12g/m2、好ましくは3~10g/m2程度の範囲である。
保護層に用いるバインダーは前記感熱記録層のバインダーと同種のものが使用できる。具体例としては、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール等のポリビニルアルコール類、カルボキシ変性ポリビニルアルコール、アマイド変性ポリビニルアルコール、スルホン酸変性ポリビニルアルコール、ブチラール変性ポリビニルアルコール等の変性ポリビニルアルコール類、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、デンプン類、ゼラチン、カゼイン、アルギン酸ナトリウム、ポリビニルピロリドン、ポリアクリルアミド、アクリルアミド/アクリル酸エステル共重合体、スチレン/無水マレイン酸共重合体のアルカリ塩、エチレン/無水マレイン酸共重合体のアルカリ塩等の水溶性樹脂、スチレン-ブタジエン共重合体、アクリロニトリル/ブタジエン共重合体、アクリル酸メチル/ブタジエン共重合体、アクリロニトリル/ブタジエン/スチレン三元共重合体、エチルセルロース、アセチルセルロースのようなセルロース誘導体、ポリ塩化ビニル、ポリ酢酸ビニル、酢酸ビニル/アクリル酸エステル共重合体、エチレン/酢酸ビニル共重合体、ポリアクリル酸エステル、スチレン/アクリル酸エステル共重合体、ポリウレタン樹脂、ポリビニルブチラール、ポリスチロール及びそれらの共重合体、ポリアミド樹脂、シリコン樹脂、石油樹脂、テルペン樹脂、ケトン樹脂、クマロン樹脂等の水分散性樹脂を例示することができる。これらは水、アルコール、ケトン、エステル、炭化水素等の溶剤に溶かして使用するほか、水又は他の媒体中に乳化又はペースト状に分散した状態で使用し、要求品質に応じて併用することも出来る。これらの中でも水剥離性の観点から、水溶性樹脂であるデンプン類、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、ゼラチン、カゼイン、アルギン酸ナトリウム、ポリビニルアルコール類、変性ポリビニルアルコール類、ポリビニルピロリドンをバインダーの主成分として使用することが望ましい。
保護層は、前記バインダーに各種添加剤を分散混合して得られる塗料を、塗工機によって一層あるいは多層に分けて塗工し、ドライヤーで加熱乾燥することによって得られる。
保護層の塗工量は、固形分として通常0.2~10g/m2、好ましくは0.5~5g/m2である。塗工機としては、特に限定されるものではなく、エアナイフコーター、バーコーター、ロールコーター、ブレードコーター、カーテンコーター、チャンプレックスコーター、グラビアコーター等の公知の塗工機を使用することができ、特に制限されることはない。
本発明の水分散性シートをインクジェットプリンターの印字に適応させる場合、基紙の第2の表面層上に顔料及び水系バインダーを主成分としたピグメントコート層、あるいはカチオン性樹脂及び/又は水系バインダーを主成分としたクリアーコート層を設けることが好ましく、顔料、バインダー、各種添加剤は公知のものを適宜選択して用いることができ、配合量は要求される品質により適宜調整することができる。また、上記基紙はαセルロース含有率88重量%以上の精製パルプが含有されているポーラスな層(インク吸収性の高い層)を有しているため、インク吸収性が向上する。
塗工機としては、特に限定されるものではなく、エアナイフコーター、バーコーター、ロールコーター、ブレードコーター、カーテンコーター、キャストコーター、チャンプレックスコーター、グラビアコーター、2ロールコーター、トランスファーロールコーター等が使用される。
本発明の水分散性シートをグラビア印刷に適応させる場合、基紙の第2の表面層上に顔料及び水系バインダーを主成分としたピグメントコート層、あるいは水系バインダーを主成分としたクリアーコート層を設けることが好ましく、顔料、バインダー、各種添加剤は公知のものを適宜選択して用いることができる。また、上記基紙はαセルロース含有率88重量%以上の精製パルプが含有されているポーラスな層(クッション性の高い層)を有しているため、インキ着肉性が向上する。
塗工機としては、特に限定されるものではなく、エアナイフコーター、バーコーター、ロールコーター、ブレードコーター、カーテンコーター、キャストコーター、チャンプレックスコーター、グラビアコーター、2ロールコーター、トランスファーロールコーター等が使用される。
実施例1
(基紙の作製)
木材パルプとして針葉樹晒クラフトパルプ(αセルロース含有率85.6重量%)70重量%、及び精製パルプとして広葉樹溶解パルプ(αセルロース含有率98.3重量%)30重量%から成る混合パルプを、カナダ標準ろ水度675mlCSFまで叩解した抄紙原料からなる内部層と、その内部層の両面に、木材パルプとして針葉樹晒クラフトパルプ(αセルロース含有率85.6重量%)15重量%及び広葉樹晒クラフトパルプ(αセルロース含有率86.0重量%)55重量%、並びに精製パルプとして広葉樹溶解パルプ(αセルロース含有率98.3重量%)30重量%から成る混合パルプをカナダ標準ろ水度500mlCSFまで叩解した抄紙原料からなる表面層を、重量比が表面層:内部層:表面層=1:4:1となるように抄き合せ接合で積層し、三層構造の手抄き紙を作製した。紙面pHは6.7であった。
この手抄き紙に、水溶性高分子としてカルボキシメチルセルロースナトリウム塩(商品名サンローズ、日本製紙社製品、20℃における2重量%水溶液の粘度が5mPa・s)(以下「CMC-Na」ともいう。)の水溶液(pH7.1)を、手抄き紙に対して8重量%サイズプレス塗工して水分散性シートを作製した。
下記配合の顕色剤分散液(A液)、ロイコ染料分散液(B液)および増感剤分散液(C液)を、それぞれ別々にサンドグラインダーで平均粒子径1.0μmになるまで湿式磨砕を行った。
顕色剤分散液(A液)
4-ヒドロキシ-4'-イソプロポキシジフェニルスルホン(日本曹達株式
会社製D8) 6.0部
完全ケン化型ポリビニルアルコール水溶液(クラレ社製、商品名:PVA
117、固形分10%) 18.8部
水 11.2部
ロイコ染料分散液(B液)
3-ジ-n-ブチルアミノ-6-メチル-7-アニリノフルオラン(山本
化成社製、ODB-2) 2.0部
完全ケン化型ポリビニルアルコール水溶液(PVA117) 4.6部
水 2.6部
増感剤分散液(C液)
4-ビフェニル-p-トリルエーテル(日華化学株式会社製) 4.0部
完全ケン化型ポリビニルアルコール水溶液(PVA117) 5.0部
水 3.0部
<感熱記録層用塗料>
顕色剤分散液(A液) 36.0部
ロイコ染料分散液(B液) 9.2部
増感剤分散液(C液) 12.0部
この感熱記録層用塗料を基紙の一方の表面(第2の表面層)に固形分として6g/m2になるように塗工し、乾燥(50℃)させて感熱記録層を形成し、記録紙を得た。この記録紙に、ベック平滑度が500~1000秒となるように平滑化処理を行った。
下記配合の粘着剤塗料を調製した。
<粘着剤塗料>
水溶性アクリル系粘着剤(ビッグテクノス(株)製、商品名「リキダイン
AR-2410」、固形分濃度42重量%) 100重量部
硬化剤(ビッグテクノス(株)製、商品名「サンパスタHD-5013」
) 0.1重量部
この粘着剤塗料をシリコーン剥離剤を塗布した市販の剥離シートの剥離処理面に固形分として25g/m2塗布し、乾燥して粘着剤層を設けた。この粘着剤層と上記記録紙の感熱記録層とは反対の表面(第1の表面層)とを貼り合せ、水分散性シートを作製した。
表面層に配合した混合パルプを、カナダ標準ろ水度600mlCSFまで叩解した以外は、実施例1と同様にして水分散性シートを作製した。
実施例3
表面層に配合した混合パルプを、カナダ標準ろ水度500mlCSFまで叩解した以外は、実施例1と同様にして水分散性シートを作製した。
実施例4
感熱記録層を塗設しないこと以外は、実施例1と同様にして水分散性シートを作製した。
実施例5
表面層に配合した混合パルプを、木材パルプとして針葉樹晒クラフトパルプ(αセルロース含有率85.6重量%)70重量%及び精製パルプとして広葉樹溶解パルプ(αセルロース含有率98.3重量%)30重量%から成る混合パルプに代えた以外は、実施例1と同様にして水分散性シートを作製した。
第2の表面層を設けない以外は、実施例1と同様にして水分散性シートを作製した。
実施例7
第2の表面層を設けず、感熱記録層を塗設しない以外は、実施例1と同様にして水分散性シートを作製した。
実施例8
第2の表面層を設けず、サイズプレス塗工せず、感熱記録層を塗設しない以外は、実施例2と同様にして水分散性シートを作製した。
実施例9
サイズプレス塗工せず、感熱記録層を塗設しない以外は、実施例2と同様にして水分散性シートを作製した。
実施例10
内部層と表面層の重量比が表面層:内部層:表面層=1:2:1となるように抄き合せ接合で積層する以外は、実施例1と同様にして水分散性シートを作製した。
実施例1におけるサイズプレス塗工において、カルボキシメチルセルロースナトリウム塩の水溶液の代わりに酵素変性デキストリン(三和澱粉工業社製、20℃における2重量%水溶液の粘度が2mPa・s)水溶液(pH7.3)を用いた以外は、実施例1と同様にして水分散性シートを作製した。
実施例12
実施例1におけるサイズプレス塗工において、カルボキシメチルセルロースナトリウム塩の水溶液の代わりに焙焼デキストリン(日澱化学社製、20℃における2重量%水溶液の粘度が2mPa・s)水溶液(pH7.4)を用いた以外は、実施例1と同様にして水分散性シートを作製した。
表面層に配合した混合パルプを、カナダ標準ろ水度650mlCSFまで叩解した以外は、実施例1と同様にして水分散性シートを作製した。
比較例2
表面層に配合した混合パルプを、カナダ標準ろ水度400mlCSFまで叩解した以外は、実施例1と同様にして水分散性シートを作製した。
比較例3
表面層に配合した混合パルプを、木材パルプとして針葉樹晒クラフトパルプ(αセルロース含有率85.6重量%)8.6重量%及び広葉樹晒クラフトパルプ(αセルロース含有率86.0重量%)31.4重量%、並びに精製パルプとして広葉樹溶解パルプ(αセルロース含有率98.3重量%)60重量%から成る混合パルプに代えた以外は、実施例1と同様にして水分散性シートを作製した。
比較例4
表面層に配合した混合パルプを、木材パルプとして針葉樹晒クラフトパルプ(αセルロース含有率85.6重量%)21.4重量%及び広葉樹晒クラフトパルプ(αセルロース含有率86.0重量%)78.6重量%から成り、精製パルプを含まない混合パルプに代えた以外は、実施例1と同様にして水分散性シートを作製した。
内部層に配合した混合パルプを、木材パルプとして針葉樹晒クラフトパルプ(αセルロース含有率85.6重量%)40重量%、及び精製パルプとして広葉樹溶解パルプ(αセルロース含有率98.3重量%)60重量%から成る混合パルプに代えた以外は、実施例1と同様にして水分散性シートを作製した。サイズプレス塗工時に表面層と内部層の剥離が起こり、水分散性シートが得られなかった。内部層の精製パルプの配合が多くなり、繊維間結合が弱くなったためと考えられる。
比較例6
内部層に配合した混合パルプを、木材パルプとして針葉樹晒クラフトパルプ(αセルロース含有率85.6重量%)から成り、精製パルプを含まない混合パルプに代えた以外は、実施例1と同様にして水分散性シートを作製した。
比較例7
内部層を設けず、表面層に配合した抄紙原料のみを用いて単層シートを作製し、表面層の両面に直接感熱記録層と粘着剤層を設けたこと以外は、実施例1と同様にして水分散性シートを作製した。
比較例8
表面層を設けず、内部層に配合した抄紙原料のみを用いて単層シートを作製し、内部層の両面に直接感熱記録層と粘着剤層を設けたこと以外は、実施例1と同様にして水分散性シートを作製した。
23℃、50%RHの雰囲気で24時間以上保管した水分散性シート試料から3cm角の試験片5枚を作製した。次に300mlビーカーに脱イオン水300mlを入れてスターラーで650rpmに撹拌しながら上記試験片1枚を投入した。試験片が2つ以上に千切れ、フロック状になる時間と試験片が完全に繊維一本一本にほぐれ、繊維状になる時間をストップウォッチで求め、5回の測定の平均値を水分散時間(秒)とした。なお、水分散時間が短いほど水分散性は優れている。水分散時間(試験片が2つ以上に千切れ、フロック状になる時間)が、感熱記録層無しで9秒以内、感熱記録層有りで10秒以内であり、かつ水分散時間(試験片が完全に繊維一本一本にほぐれ、繊維状になる時間)が、感熱記録層有りで150秒以内であれば、水分散性は良好と判断できる。
JIS Z0237に準じ、幅25mm×長さ170mmの試験片を3本切り出し、剥離紙を剥がして粘着剤塗工面をステンレス板(100×150mm)の上に置き、重量3kgのゴムローラーを2往復ころがして圧着した。
ステンレス板を引張試験機の下部チャックに挟み、試料粘着加工品の一端を上部チャックに挟んで引張速度300mm/分で180°引き剥がし試験を行い、粘着力(g/25mm)を測定した。初日(1日目)の粘着力に対する14日目の粘着力の比率が60%以上であれば、経時の粘着性は良好と判断できる。
Claims (18)
- 内部層及び少なくとも一つの表面層から成る紙基材の一つの表面層(以下「第1の表面層」という。)上に粘着剤層を有する水分散性シートであって、該第1の表面層が、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプ1から成り、該混合パルプ1のカナダ標準ろ水度が450~600mlCSFであり、かつ該混合パルプ1中の該木材パルプの含有量が50~95重量%であり、該内部層が、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプ3から成り、該混合パルプ3のカナダ標準ろ水度が600~750mlCSFであり、かつ該混合パルプ3中の該木材パルプの含有量が50~95重量%である水分散性シート。
- 前記第1の表面層において、前記混合パルプ1のカナダ標準ろ水度が500~575mlCSFである請求項1に記載の水分散性シート。
- 前記内部層の前記第1の表面層とは反対面上に第2の表面層を有し、該第2の表面層が、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプ2から成り、該混合パルプ2のカナダ標準ろ水度が450~600mlCSFである請求項1又は2に記載の水分散性シート。
- 前記第2の表面層において、前記混合パルプ2中の該木材パルプの含有量が50~95重量%である、請求項3に記載の水分散性シート。
- 前記第2の表面層上に感熱記録層を設けた請求項3又は4に記載の水分散性シート。
- 前記第2の表面層上に水系塗料が塗工された請求項3又は4に記載の水分散性シート。
- 前記第1の表面層の組成と前記第2の表面層の組成が同一である請求項3~6のいずれか一項に記載の水分散性シート。
- 前記混合パルプ1~3が、その抄紙時に、再生セルロース繊維、繊維状カルボキシメチルセルロース又は繊維状カルボキシメチルセルロース塩を含まない請求項1~7に記載の水分散性シート。
- 前記第1の表面層の紙面pHが6~8である請求項1~8に記載の水分散性シート。
- 内部層及びその両面にそれぞれ設けた2つの表面層から成り、該表面層が、それぞれ独立して、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプから成り、該混合パルプのカナダ標準ろ水度が450~600mlCSFであり、かつ該混合パルプ中の該木材パルプの含有量が50~95重量%であり、該内部層が、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプ3から成り、該混合パルプ3のカナダ標準ろ水度が600~750mlCSFであり、かつ該混合パルプ3中の該木材パルプの含有量が50~95重量%である紙基材。
- 前記2つの表面層の少なくとも一方の表面層中の混合パルプのカナダ標準ろ水度が500~575mlCSFである請求項10に記載の紙基材。
- 前記2つの表面層の一方の上に感熱記録層を設けた請求項10又は11に記載の紙基材。
- 前記2つの表面層の組成が同一である請求項10~12のいずれか一項に記載の紙基材。
- (1)及び(2)から成る水分散性シートを製造する方法。
(1)内部層及びその両面にそれぞれ設けた第1の表面層及び第2の表面層から成り、該第1の表面層及び第2の表面層が、それぞれ独立して、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプから成り、該混合パルプのカナダ標準ろ水度が450~600mlCSFであり、かつ該混合パルプ中の該木材パルプの含有量が50~95重量%であり、該内部層が、木材パルプ及びαセルロース含有率88重量%以上の精製パルプから成る混合パルプ3から成り、該混合パルプ3のカナダ標準ろ水度が600~750mlCSFであり、かつ該混合パルプ3中の該木材パルプの含有量が50~95重量%である紙基材を提供する段階、及び
(2)該第1の表面層上に粘着層を設ける段階 - (1)と(2)との間に、更に
(3)前記第2の表面層上に水系塗料を塗工する段階、
を有する請求項14に記載の方法。 - (1)と(2)との間に、更に
(3)前記第2の表面層上に感熱記録層を設ける段階、
を有する請求項14に記載の方法。 - 前記第1の表面層及び第2の表面層の少なくとも一方の表面層中の、前記混合パルプのカナダ標準ろ水度が500~575mlCSFである請求項14~16のいずれか一項に記載の方法。
- 前記第1の表面層の組成と前記第2の表面層の組成が同一である請求項14~17のいずれか一項に記載の方法。
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WO2020196408A1 (ja) * | 2019-03-28 | 2020-10-01 | 日本製紙パピリア株式会社 | 水分散紙 |
US11376879B2 (en) | 2019-11-22 | 2022-07-05 | Appvion, Llc | Water-dispersible direct thermal or inkjet printable media |
WO2022230886A1 (ja) * | 2021-04-26 | 2022-11-03 | 日本たばこ産業株式会社 | 非燃焼加熱型香味吸引器用たばこシート及びその製造方法、非燃焼加熱型香味吸引器、並びに非燃焼加熱型香味吸引システム |
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JP6789311B2 (ja) * | 2016-11-09 | 2020-11-25 | 日本製紙パピリア株式会社 | 水分散性シート |
JP6670981B2 (ja) * | 2017-09-05 | 2020-03-25 | 日本製紙パピリア株式会社 | 水分散性シート |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6381036A (ja) * | 1986-09-24 | 1988-04-11 | 新神戸電機株式会社 | 積層板の製造法 |
JPH04370300A (ja) | 1991-06-12 | 1992-12-22 | Uni Charm Corp | 多層構造の水解紙及びその製造方法 |
JPH0949188A (ja) | 1995-08-09 | 1997-02-18 | Mishima Seishi Kk | 水分散性シート並びにこれを用いたたばこ |
JPH10310960A (ja) * | 1997-03-04 | 1998-11-24 | Oji Paper Co Ltd | 水解性不織布およびその製造方法 |
JP2000170100A (ja) * | 1998-12-02 | 2000-06-20 | Mishima Paper Co Ltd | 水分散性包装用紙及び包装紙 |
JP2004314623A (ja) | 2003-03-31 | 2004-11-11 | Lintec Corp | 水崩壊性感熱記録紙及びそれを用いた水崩壊性粘着シート |
JP2006299498A (ja) | 2005-03-22 | 2006-11-02 | Nippon Paper Industries Co Ltd | 水剥離性塗工紙及びその製造方法 |
JP2008297668A (ja) * | 2007-05-31 | 2008-12-11 | Oji Paper Co Ltd | 印刷用紙 |
JP2010504376A (ja) | 2006-09-19 | 2010-02-12 | セラニーズ アセテート,エルエルシー | セルロースエステルポリマーの製造法及びセルロースエステルポリマーを製造するためのセルロース前処理 |
WO2010143736A1 (ja) * | 2009-06-11 | 2010-12-16 | ユニ・チャーム株式会社 | 水解性繊維シート |
WO2012014970A1 (ja) | 2010-07-28 | 2012-02-02 | 日本製紙パピリア株式会社 | 水分散性紙 |
JP2015163742A (ja) * | 2014-02-28 | 2015-09-10 | 日本製紙株式会社 | 衛生用紙 |
WO2018088179A1 (ja) * | 2016-11-09 | 2018-05-17 | 日本製紙パピリア株式会社 | 水分散性シート |
JP2018104860A (ja) * | 2016-12-28 | 2018-07-05 | エステー株式会社 | 消臭効果を有する水分散シート |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3839144A (en) | 1970-09-21 | 1974-10-01 | W Lounden | Paper having 60{14 97 percent hydrated cellulosic fibers and 3{14 40 percent unhydrated cellulosic fibers |
US7176151B2 (en) | 2003-12-08 | 2007-02-13 | Wausau Paper Corp. | Laminate product, method for manufacturing, and article |
JP4721432B2 (ja) | 2006-03-10 | 2011-07-13 | 日本製紙株式会社 | 情報記録用紙 |
US9418576B2 (en) | 2008-05-14 | 2016-08-16 | Avery Dennison Corporation | Dissolvable thermal direct adhesive label and label assembly including the same |
JP2012061612A (ja) | 2010-09-14 | 2012-03-29 | Nippon Paper Industries Co Ltd | 水溶性感熱記録体 |
JP2014185407A (ja) * | 2013-03-25 | 2014-10-02 | Nippon Paper Papylia Co Ltd | アルカリ分散性シート及びそれを用いた容器 |
CN105431587B (zh) * | 2013-07-19 | 2019-07-30 | 旭化成株式会社 | 微细纤维素纤维片 |
JP7138092B2 (ja) * | 2017-03-30 | 2022-09-15 | 日本製紙パピリア株式会社 | 水分散紙 |
WO2018221016A1 (ja) * | 2017-05-30 | 2018-12-06 | 日本製紙パピリア株式会社 | 水分散性シート |
JP6670981B2 (ja) * | 2017-09-05 | 2020-03-25 | 日本製紙パピリア株式会社 | 水分散性シート |
WO2019130968A1 (ja) * | 2017-12-25 | 2019-07-04 | 日本製紙パピリア株式会社 | 水分散性シート |
JP7141965B2 (ja) * | 2019-03-07 | 2022-09-26 | 日本製紙パピリア株式会社 | 水分散紙 |
-
2018
- 2018-08-15 JP JP2019540854A patent/JP6670981B2/ja active Active
- 2018-08-15 CA CA3074968A patent/CA3074968C/en active Active
- 2018-08-15 EP EP18854637.8A patent/EP3670741A4/en active Pending
- 2018-08-15 US US16/644,732 patent/US11649380B2/en active Active
- 2018-08-15 WO PCT/JP2018/030336 patent/WO2019049619A1/ja unknown
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6381036A (ja) * | 1986-09-24 | 1988-04-11 | 新神戸電機株式会社 | 積層板の製造法 |
JPH04370300A (ja) | 1991-06-12 | 1992-12-22 | Uni Charm Corp | 多層構造の水解紙及びその製造方法 |
JPH0949188A (ja) | 1995-08-09 | 1997-02-18 | Mishima Seishi Kk | 水分散性シート並びにこれを用いたたばこ |
JPH10310960A (ja) * | 1997-03-04 | 1998-11-24 | Oji Paper Co Ltd | 水解性不織布およびその製造方法 |
JP2000170100A (ja) * | 1998-12-02 | 2000-06-20 | Mishima Paper Co Ltd | 水分散性包装用紙及び包装紙 |
JP2004314623A (ja) | 2003-03-31 | 2004-11-11 | Lintec Corp | 水崩壊性感熱記録紙及びそれを用いた水崩壊性粘着シート |
JP2006299498A (ja) | 2005-03-22 | 2006-11-02 | Nippon Paper Industries Co Ltd | 水剥離性塗工紙及びその製造方法 |
JP2010504376A (ja) | 2006-09-19 | 2010-02-12 | セラニーズ アセテート,エルエルシー | セルロースエステルポリマーの製造法及びセルロースエステルポリマーを製造するためのセルロース前処理 |
JP2008297668A (ja) * | 2007-05-31 | 2008-12-11 | Oji Paper Co Ltd | 印刷用紙 |
WO2010143736A1 (ja) * | 2009-06-11 | 2010-12-16 | ユニ・チャーム株式会社 | 水解性繊維シート |
WO2012014970A1 (ja) | 2010-07-28 | 2012-02-02 | 日本製紙パピリア株式会社 | 水分散性紙 |
JP2015163742A (ja) * | 2014-02-28 | 2015-09-10 | 日本製紙株式会社 | 衛生用紙 |
WO2018088179A1 (ja) * | 2016-11-09 | 2018-05-17 | 日本製紙パピリア株式会社 | 水分散性シート |
JP2018104860A (ja) * | 2016-12-28 | 2018-07-05 | エステー株式会社 | 消臭効果を有する水分散シート |
Non-Patent Citations (2)
Title |
---|
"Paper Pulp Dictionary", 20 February 2000, KANEHARA PUBLISHING |
See also references of EP3670741A4 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020196408A1 (ja) * | 2019-03-28 | 2020-10-01 | 日本製紙パピリア株式会社 | 水分散紙 |
JP2020158938A (ja) * | 2019-03-28 | 2020-10-01 | 日本製紙パピリア株式会社 | 水分散紙 |
JP7215949B2 (ja) | 2019-03-28 | 2023-01-31 | 日本製紙パピリア株式会社 | 水分散紙 |
US11802378B2 (en) | 2019-03-28 | 2023-10-31 | Nippon Paper Papylia Co., Ltd. | Water-dispersible paper |
US11376879B2 (en) | 2019-11-22 | 2022-07-05 | Appvion, Llc | Water-dispersible direct thermal or inkjet printable media |
WO2022230886A1 (ja) * | 2021-04-26 | 2022-11-03 | 日本たばこ産業株式会社 | 非燃焼加熱型香味吸引器用たばこシート及びその製造方法、非燃焼加熱型香味吸引器、並びに非燃焼加熱型香味吸引システム |
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JPWO2019049619A1 (ja) | 2020-06-11 |
EP3670741A1 (en) | 2020-06-24 |
CA3074968A1 (en) | 2019-03-14 |
CA3074968C (en) | 2021-11-09 |
EP3670741A4 (en) | 2020-09-09 |
US20200231844A1 (en) | 2020-07-23 |
JP6670981B2 (ja) | 2020-03-25 |
US11649380B2 (en) | 2023-05-16 |
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