WO2013015185A1 - ポリオキシアルキレン変性ビニルアルコール系重合体およびその用途 - Google Patents
ポリオキシアルキレン変性ビニルアルコール系重合体およびその用途 Download PDFInfo
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- WO2013015185A1 WO2013015185A1 PCT/JP2012/068291 JP2012068291W WO2013015185A1 WO 2013015185 A1 WO2013015185 A1 WO 2013015185A1 JP 2012068291 W JP2012068291 W JP 2012068291W WO 2013015185 A1 WO2013015185 A1 WO 2013015185A1
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- poa
- coating
- polyoxyalkylene
- pva
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- B41M5/52—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
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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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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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
- D21H27/001—Release paper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/26—All layers being made of paper or paperboard
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/12—Coating on the layer surface on paper layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2554/00—Paper of special types, e.g. banknotes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/32—Thermal receivers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/14—Layer or component removable to expose adhesive
- Y10T428/1476—Release layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
Definitions
- the present invention relates to a polyoxyalkylene-modified vinyl alcohol polymer having a polyoxyalkylene group in the side chain and a method for producing the same.
- the present invention also provides an aqueous solution and a coating agent containing the polyoxyalkylene-modified vinyl alcohol polymer, a coated product obtained by coating the coating agent on the surface of the substrate, and the coating agent on the surface of the substrate.
- the present invention relates to an ink jet recording material coated on the surface and a method for producing the same.
- this invention relates to the film containing the said polyoxyalkylene modified vinyl alcohol-type polymer, release paper base paper, oil-resistant paper, and methods for manufacturing them.
- a vinyl alcohol polymer represented by polyvinyl alcohol (hereinafter, the vinyl alcohol polymer may be abbreviated as “PVA”) is a few crystalline water-soluble polymers.
- PVA is used as a raw material for synthetic fiber vinylon by utilizing its strength characteristics.
- PVA is also used for paper processing agents, fiber pastes, dispersants, adhesives, films, and the like by utilizing its excellent film forming ability, surface active ability, hydrogen bond forming ability, and the like. Furthermore, since PVA has excellent interface characteristics and strength characteristics, it is also used as a stabilizer for emulsions and various binders.
- PVA having a polyoxyalkylene (hereinafter sometimes abbreviated as “POA”) group various developments have been made on PVA having a polyoxyalkylene (hereinafter sometimes abbreviated as “POA”) group.
- POA having an allyl group at the terminal a methacrylic acid ester having a POA group, or a methacrylic acid group-containing compound in which a POA group is bonded to a nitrogen atom, and a POA that saponifies a copolymer of vinyl ester.
- a method for synthesizing PVA having a group is disclosed. After the development of such a synthesis method, PVA having a POA group has been used for various applications.
- PVA is used to improve the quality of printed matter in paper processing applications.
- PVA is used as a binder for fillers in inkjet recording materials, a surface sizing agent for general paper, an undersizing agent for art paper / coated paper, a dispersant for fluorescent dyes, and the like.
- inkjet printers have expanded, and inkjet recording materials are used for color proofing in commercial printing, design image output in the design field, and documents for overhead projectors.
- the properties required for the ink jet recording material in these applications are that the surface of the ink receiving layer is highly glossy, the transparency of the ink receiving layer is high, the image density is high, the color reproducibility is good, Examples thereof include high ink absorbability and good dot reproducibility.
- recording materials are known in which a void layer composed of inorganic fine particles and a hydrophilic binder is provided as an ink receiving layer (see Patent Documents 2 and 3).
- This recording material achieves both high ink absorbability and water resistance by an ink absorption mechanism utilizing capillary action.
- it is usually necessary to contain a large amount of fine particles with respect to the binder. In this case, the ratio of the binder to the fine particles is low, and the ink receiving layer is high in rigidity and hard.
- a method of preventing the cracking by increasing the viscosity of the coating film before drying the coating film is considered.
- a method has been proposed in which a coating liquid obtained by adding boric acid as a curing agent to polyvinyl alcohol having a high polymerization degree is used, and the coating film is cooled to 20 ° C. or less after coating (Patent Document). 4).
- Patent Document a coating liquid obtained by adding boric acid as a curing agent to polyvinyl alcohol having a high polymerization degree
- this method has a problem that energy loss is large because it is necessary to lower the temperature of the coating film once after coating. Moreover, since the temperature of the coating film is once lowered after coating, there is a problem that it takes time to form the coating film and the production speed cannot be increased. Furthermore, since this method uses polyvinyl alcohol having a high degree of polymerization, the viscosity of the coating solution at room temperature was high. Therefore, it was necessary to keep the concentration of the coating solution low in terms of its handleability. When the concentration of the coating solution was low, it took time to dry the coating film, and the production rate further decreased.
- Patent Document 5 describes a block copolymer and a graft copolymer composed of a polyvinyl alcohol component and a polyalkenyl ether component in which the aqueous solution exhibits a cloud point, as PVA in which the aqueous solution exhibits thermal sensitivity.
- Patent Document 7 PVA having a polyoxyalkylene group is described. By adjusting the content of the polyoxyalkylene group and the number of repeating units in the polyoxyalkylene group in the PVA, it is said that temperature-sensitive thickening is imparted to the PVA. It is described that an ink jet recording material with few cracks could be manufactured by applying the temperature-sensitive thickening of PVA.
- Patent Document 7 has a polyoxyalkylene group mainly composed of a polyoxypropylene group.
- a PVA having a polyoxyalkylene group composed of a single oxyalkylene unit has a temperature-sensitive thickening property, but its properties may not be exhibited when the PVA concentration in the solution is low. Therefore, although there is a slight improvement effect against cracks due to drying of the coating film, it is still insufficient.
- Patent Document 8 describes PVA having a polyoxybutylene group, but the PVA has a high viscosity even near room temperature and has a difficulty in handling.
- the release paper has release performance on the surface, and is used as a base material for obtaining an adhesive label, an adhesive tape, an industrial adhesive paper or the like, or as a release paper.
- the release paper is usually obtained by applying an oily varnish containing a silicone resin and a solvent (such as toluene) that can form a coating film having water and oil repellency to the paper to form a release layer.
- an oily varnish containing a silicone resin and a solvent (such as toluene) that can form a coating film having water and oil repellency to the paper to form a release layer.
- paper has many voids between pulp fibers and the like, it has high permeability and air permeability. For this reason, when the oil varnish is directly applied to the surface of the paper, the oil varnish penetrates into the paper, and a release paper having sufficient release performance cannot be obtained. Further, since the oily varnish penetrates into the paper, the coating amount increases, which is uneconomical.
- a method using the excellent film forming ability and oil resistance of PVA is generally employed. That is, this is a method in which an oily varnish is applied to a release paper base paper obtained by previously applying an aqueous PVA solution as a coating agent (sealing agent) to the paper surface.
- an aqueous PVA solution as a coating agent (sealing agent)
- ordinary PVA is excellent in oil resistance against the paint for the release layer and the organic solvent contained therein, it is inferior in water resistance, and there is a problem that PVA is eluted and blocked by humidification during processing of the adhesive layer. there were.
- Patent Document 9 For the purpose of improving the water resistance of PVA, a release paper base paper using a modified PVA containing an ⁇ -olefin unit having 4 or less carbon atoms has been proposed (see Patent Document 9). However, further performance improvement has been demanded.
- a release paper base paper using a modified PVA containing a polyoxyalkylene group in the side chain has been proposed for the purpose of improving such performance (see Patent Document 10).
- the aqueous solution of the modified PVA has a high viscosity even near room temperature, and has a difficulty in handling.
- Oil-resistant paper is a generic term for “1) oil-resistant paper in JIS P0001: 1998“ Paper, paperboard and pulp terminology. ”2) Paper or paperboard with extremely high resistance to penetration of grease or fat Is defined.
- Oil-resistant paper with oil resistance is widely used in packaging materials such as food.
- oil-resistant paper is used for foods containing a large amount of oil and fat components such as chocolate, pizza, and donut so that the oil does not penetrate into the packaging material.
- oil and fat components contained in the food penetrate into the packaging material, various problems occur.
- oil can penetrate to the surface that is not in contact with food, causing oil stains, deteriorating the appearance and reducing the value of the product, printing parts becoming black with oil stains, making characters unreadable, barcodes, The suitability of OCR such as QR code (registered trademark) decreases.
- oil-resistant paper is used in portions that come into contact with food because there is a problem that oil is transferred to the clothes and gets dirty.
- fluorine-based compounds particularly perfluorofluorine-based compounds
- perfluorofluorinated compounds generate perfluorooctanoic acid and perfluorosulfonic acid by heat treatment
- safety is a concern.
- various fluorine-based compounds with improved safety have been developed, but both oil resistance and safety are still insufficient.
- PVA can be used as a non-fluorinated oilproof agent.
- PVA is a hydrophilic resin and forms a strong film. Therefore, PVA prevents oil penetration and is excellent in oil resistance.
- a method for imparting oil resistance to a paper base material by PVA for example, a method of providing a coating layer containing PVA and shellac (shellac) on at least one surface of a base material sheet (see Patent Document 11), base material A method of providing a coating layer containing PVA cured with an isocyanate compound on at least one surface of a sheet is known (see Patent Document 12).
- the water resistance can be improved by the above method, but the oil resistance cannot be sufficiently improved. Further, in the above method, since PVA easily penetrates into paper, pinholes are easily generated. Therefore, it is necessary to increase the coating amount of the coating agent containing PVA, and there is a problem that the drying load becomes too large and the productivity is extremely lowered.
- Patent Document 13 proposes a melt-molding resin that can be used as a film raw material
- Patent Document 14 proposes an alkaline material packaging film
- Patent Document 15 proposes a water-resistant flexible film that has been devised for heat treatment of the film. ing.
- Patent Documents 1 and 13 to 15 PVA having a polyoxyethylene group or a polyoxypropylene group as a POA group is used in order to obtain a polymer or film having excellent water solubility at a low temperature.
- a film containing PVA has a problem that the strength of the film is lowered.
- An object of the present invention is to provide a PVA excellent in temperature-sensitive thickening and a simple production method thereof. More specifically, an object of the present invention is to provide a PVA suitable for use in the production of ink jet recording materials, thermal paper, release paper base paper, oil resistant paper and films. Another object of the present invention is to provide an aqueous solution or a coating agent containing the PVA, and a coated product obtained by applying the coating agent on the surface of a substrate.
- the present invention relates to an inkjet recording material having an ink-receiving layer with less surface cracking and excellent ink absorbability, and a method for producing the same; release paper base paper having excellent sealing properties, oil resistance and water resistance, and a method for producing the same And a release paper using the same and a laminate having peelability; an oil-resistant paper excellent in oil resistance and water resistance; and a production method thereof; and a film having high strength and high stretchability and a production method thereof Objective.
- the present inventors have intensively studied to develop PVA useful for producing inkjet recording materials, thermal paper, release paper base paper, oil-resistant paper, films and the like.
- PVA useful for producing inkjet recording materials
- thermal paper release paper base paper
- oil-resistant paper films and the like.
- an ink jet recording material having few cracks on the coating film surface and excellent ink absorbability; release paper base paper excellent in sealing property, oil resistance and water resistance; oil resistance and Oil-resistant paper excellent in water resistance; found that a film having high strength and high stretchability can be produced, and the present invention has been completed.
- the present invention comprises a polyoxypropylene block and a (poly) oxyethylene block, has a POA group represented by the following general formula (I) in the side chain, and has a viscosity average polymerization degree of 150 to 5,000.
- a POA-modified PVA having a saponification degree of 40 mol% or more and 99.99 mol% or less and a POA group modification rate of 0.05 mol% or more and 10 mol% or less.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- One of R 2 and R 3 is a methyl group and the other is a hydrogen atom. 10 ⁇ m ⁇ 40, and 1 ⁇ n ⁇ 50.
- the ratio ⁇ between the viscosity ⁇ 1 at 20 ° C. and the viscosity ⁇ 2 at 60 ° C. 2 / ⁇ 1 is preferably 2.0 or more.
- the present invention is an aqueous solution containing the POA-modified PVA.
- the present invention relates to the POA, wherein the unsaturated monomer represented by the following general formula (II) and a vinyl ester monomer are copolymerized to saponify the obtained POA-modified vinyl ester polymer. It is a manufacturing method of modified PVA.
- R 1 , R 2 , R 3 , m and n are the same as those in the general formula (I).
- R 4 represents a hydrogen atom or a —COOM group, where M is a hydrogen atom.
- R 5 represents a hydrogen atom, a methyl group or a —CH 2 —COOM group, wherein M is as defined above, X is —O—, —CH 2 —O—.
- R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and 1 ⁇ k ⁇ 15.
- a coating agent containing the POA-modified PVA is a preferred embodiment of the present invention.
- a coated product obtained by coating the surface of the substrate with the coating agent is also a preferred embodiment of the present invention.
- the manufacturing method of the said coated material which has the process to do is also a suitable embodiment of this invention.
- An ink jet recording material in which the coating agent is coated on the surface of the substrate is also a preferred embodiment of the present invention.
- Thermal paper containing the POA-modified PVA is also a preferred embodiment of the present invention.
- a release paper base containing the POA-modified PVA is also a preferred embodiment of the present invention.
- the release paper base paper has a paper base and a coating layer formed on the surface of the paper base, and the coating layer contains the POA-modified PVA.
- coating the said coating agent to a paper base material is also a suitable embodiment of this invention. At this time, it is more preferable that the viscosity of the coating agent is 10 mPa ⁇ s or more and 3000 mPa ⁇ s or less.
- a release paper having the release paper base paper and a release layer formed on the surface of the release paper base paper is also a preferred embodiment of the present invention, and the release paper base paper and the release paper formed on the surface of the release paper base paper.
- a laminate having a layer and an adhesive layer formed on the surface of the release layer is also a preferred embodiment of the present invention.
- Oil resistant paper containing the POA-modified PVA is also a preferred embodiment of the present invention.
- the oil-resistant paper has a paper base and a coating layer formed on the surface of the paper base, and the coating layer contains the POA-modified PVA.
- the weight per unit area of the coating layer is more preferably 0.2 g / m 2 or more and 20 g / m 2 or less.
- a method for producing oil-resistant paper having a step of coating the surface of the paper substrate with the coating agent is also a preferred embodiment of the present invention.
- a film containing the POA-modified PVA is also a preferred embodiment of the present invention.
- a method for producing the film formed using a solution containing POA-modified PVA is also a preferred embodiment of the present invention.
- the POA-modified PVA of the present invention is excellent in temperature-sensitive thickening, which is a characteristic that when the aqueous solution temperature is higher than room temperature, the aqueous solution viscosity is higher than that at room temperature. That is, when an aqueous solution containing POA-modified PVA is heated, its viscosity increases greatly. Therefore, a coated product or an inkjet recording material obtained by coating the coating surface containing the POA-modified PVA of the present invention on the surface of the substrate has few cracks due to drying of the coating layer, and is excellent in ink absorbability. According to the method for producing a POA-modified PVA of the present invention, the POA-modified PVA can be easily produced.
- the ink jet recording material can be easily produced.
- the release paper base paper of the present invention is excellent in sealing properties, oil resistance and water resistance by containing the POA-modified PVA. Therefore, the release paper and laminate produced using the release paper base paper have excellent peelability.
- the said release paper base paper can be manufactured simply.
- the oil-resistant paper of the present invention is excellent in oil resistance and water resistance by containing the POA-modified PVA.
- the said oil resistant paper can be manufactured simply.
- the film of the present invention has high strength and high stretchability by containing the POA-modified PVA. According to the method for producing a film of the present invention, the film can be easily produced.
- polyoxyalkylene-modified vinyl alcohol polymer of the present invention (hereinafter, polyoxyalkylene may be abbreviated as “POA”, and vinyl alcohol polymer may be abbreviated as “PVA”).
- the polyoxyalkylene group modification rate is 0.05 mol% or more and 10 mol% or less.
- R 1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- One of R 2 and R 3 is a methyl group, and the other is a hydrogen atom. 10 ⁇ m ⁇ 40 and 1 ⁇ n ⁇ 50.
- the POA-modified PVA is a monomer unit having a POA group represented by the above general formula (I) composed of a polyoxypropylene block and a (poly) oxyethylene block in the side chain, a vinyl alcohol unit (—CH 2 A copolymer containing —CHOH—) and vinyl ester units.
- the POA-modified PVA may further have other monomer units as long as the gist of the present invention is not impaired.
- the content of other monomers is preferably 10 mol% or less based on the number of moles of all monomer units in the POA-modified PVA.
- the POA group represented by the general formula (I) contained in the side chain of the POA-modified PVA of the present invention has a polyoxypropylene block in which the number of repeating units of oxypropylene units is m and the number of repeating units of oxyethylene units is n. It is composed of a certain (poly) oxyethylene block, and the (poly) oxyethylene block is arranged on the terminal side of the POA group.
- n 1, the POA group is composed of a polyoxypropylene block and an oxyethylene block.
- n is 2 or more, the POA group is a polyoxypropylene block and a polyoxypropylene block. It is comprised from an ethylene block.
- the repeating unit number m of the oxypropylene unit in the POA group represented by the general formula (I) needs to satisfy 10 ⁇ m ⁇ 40, preferably 15 ⁇ m ⁇ 38, and more preferably 20 ⁇ m ⁇ 35.
- m is less than 10
- the temperature-sensitive thickening due to the interaction between POA groups is not sufficiently exhibited.
- the sealing property of the release paper base paper and the water resistance and oil resistance of the oil resistant paper are not sufficiently exhibited. Furthermore, the strength of the film decreases.
- the number of repeating units n of the oxyethylene unit needs to be 1 ⁇ n ⁇ 50, preferably 3 ⁇ n ⁇ 40, more preferably 5 ⁇ n ⁇ 10.
- n is less than 1
- temperature-sensitive thickening due to the interaction between POA groups is not sufficiently exhibited.
- the oil resistance of the release paper base paper and the oil resistant paper is not sufficiently exhibited.
- the strength of the film decreases.
- n exceeds 50, the interaction between POA groups is not sufficiently exhibited. Further, the sealing property and oil resistance of the release paper base paper and the oil resistance of the oil resistant paper are not exhibited, and the strength of the film is lowered.
- R 1 in the POA group represented by the general formula (I) is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- R 1 is preferably a hydrogen atom, a methyl group, an ethyl group, or a butyl group, more preferably a hydrogen atom, a methyl group, or a butyl group, and even more preferably a hydrogen atom or a methyl group.
- R 2 and R 3 in the POA group represented by the general formula (I) is a methyl group, and the other is a hydrogen atom. At this time, it is preferable that R 2 is a methyl group and R 3 is a hydrogen atom because it is easy to produce POA-modified PVA.
- the method for producing the POA-modified PVA of the present invention is not particularly limited, but an unsaturated monomer having a POA group represented by the above general formula (I) composed of a polyoxypropylene block and a (poly) oxyethylene block; A method of saponifying the obtained POA-modified vinyl ester polymer by copolymerizing with a vinyl ester monomer is preferred.
- the unsaturated monomer is preferably an unsaturated monomer represented by the following general formula (II). Therefore, as a method for producing POA-modified PVA, a polyoxypropylene block and a (poly) oxyethylene block are used, and the POA group having a POA group represented by the general formula (I) is represented by the following general formula (II). A method of saponifying the resulting POA-modified vinyl ester polymer by copolymerizing a saturated monomer and a vinyl ester monomer is more preferable.
- R 1 , R 2 , R 3 , m, and n are the same as those in the general formula (I).
- R 4 represents a hydrogen atom or a —COOM group, where M represents a hydrogen atom, an alkali metal or an ammonium group.
- R 5 represents a hydrogen atom, a methyl group or a —CH 2 —COOM group, where M is as defined above. Note that M in R 4 and M in R 5 may be the same or different.
- X represents —O—, —CH 2 —O—, —CO—, — (CH 2 ) k —, —CO—O— or —CO—NR 6 —. When X is asymmetric, the direction is not limited.
- R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and 1 ⁇ k ⁇ 15.
- X is preferably —CO—NH— * or —CH 2 —O— *, more preferably —CO—NH— *.
- the POA base side is designated as “*”.
- R 1 , R 2 , R 3 , m, and n are the same as those described above in the description of the general formula (I).
- R 2 is a methyl group and R 3 is a hydrogen atom.
- R 1 is preferably a hydrogen atom or a methyl group
- R 4 is a hydrogen atom
- R 5 is preferably a hydrogen atom or a methyl group.
- the unsaturated monomer represented by the general formula (II) is a polyoxyalkylene mono (Meth) acrylamide, polyoxyalkylene mono (meth) allyl ether, polyoxyalkylene monovinyl ether, polyoxyalkylene mono (meth) acrylate, and the like, specifically, polyoxypropylene (poly) oxyethylene monoacrylamide, Polyoxypropylene (poly) oxyethylene monomethacrylamide, polyoxypropylene (poly) oxyethylene monoallyl ether, polyoxypropylene (poly) oxyethylene monomethallyl ether, polyoxypropylene (poly) oxyethylene monovinyl ether, polyoxypro Examples include pyrene (poly) oxyethylene monoacrylate and polyoxypropylene (poly) oxyethylene monomethacrylate.
- polyoxypropylene (poly) oxyethylene monoacrylamide polyoxypropylene (poly) oxyethylene monomethacrylamide
- polyoxypropylene (poly) oxyethylene monovinyl ether polyoxypropylene (poly) oxyethylene monoallyl ether are preferred. Used for.
- polyoxypropylene (poly) oxyethylene monoacrylamide, polyoxypropylene (poly) oxyethylene monomethacrylamide, polyoxypropylene (poly) oxyethylene Monovinyl ether is more preferably used, and polyoxypropylene (poly) oxyethylene monomethacrylamide and polyoxypropylene (poly) oxyethylene monovinyl ether are more preferably used.
- polyoxypropylene (poly) oxyethylene monoacrylamide, polyoxypropylene (poly) oxyethylene monomethacrylamide, polyoxypropylene (poly) oxyethylene Monoallyl ether is more preferably used, and polyoxypropylene (poly) oxyethylene monomethacrylamide and polyoxypropylene (poly) oxyethylene monoallyl ether are more preferably used.
- polyoxypropylene (poly) oxyethylene monomethacrylamide, polyoxypropylene (poly) oxyethylene monovinyl ether, polyoxypropylene (poly) oxyethylene monoallyl ether Preferably used.
- R 1 in the general formula (II) is an alkyl group having 1 to 8 carbon atoms
- the unsaturated monomer represented by the general formula (II) is specifically R 1 in the general formula (II) is hydrogen.
- R 1 in the general formula (II) is hydrogen.
- examples thereof include those in which the hydroxyl group at the terminal of the above unsaturated monomer exemplified in the case of atoms is substituted with an alkoxy group having 1 to 8 carbon atoms.
- a monomer is preferably used.
- the hydroxyl group at the end of polyoxypropylene (poly) oxyethylene monomethacrylamide or polyoxypropylene (poly) oxyethylene monovinyl ether is replaced with a methoxy group.
- the unsaturated monomer is more preferably used.
- the hydroxyl group at the end of polyoxypropylene (poly) oxyethylene monomethacrylamide or polyoxypropylene (poly) oxyethylene monoallyl ether is a methoxy group
- An unsaturated monomer substituted with is more preferably used.
- An unsaturated monomer in which the terminal hydroxyl group of polyoxypropylene (poly) oxyethylene monomethacrylamide is substituted with a methoxy group is particularly preferably used.
- the temperature when copolymerizing the unsaturated monomer represented by the general formula (II) and the vinyl ester monomer is not particularly limited, but is preferably 0 ° C. or higher and 200 ° C. or lower, and 30 ° C. or higher and 140 ° C. The following is more preferable.
- the copolymerization temperature is lower than 0 ° C., it is difficult to obtain a sufficient polymerization rate.
- polymerizes is higher than 200 degreeC, it is difficult to obtain POA modified PVA which has the POA group modification rate prescribed
- the heat generated by the polymerization is balanced with the heat released from the surface of the reactor.
- Examples thereof include a method and a method of controlling by an external jacket using an appropriate heat medium, but the latter method is preferable from the viewpoint of safety.
- the polymerization method employed for the copolymerization of the unsaturated monomer represented by the general formula (II) and the vinyl ester monomer is batch polymerization, semi-batch polymerization, continuous polymerization, or semi-continuous polymerization. Either of these may be used.
- a polymerization method an arbitrary method can be adopted from known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
- a bulk polymerization method or a solution polymerization method in which polymerization is performed in the absence of a solvent or in the presence of an alcohol solvent is preferably employed.
- an emulsion polymerization method is employed.
- the alcohol solvent used in the bulk polymerization method or the solution polymerization method methanol, ethanol, n-propanol or the like can be used, but is not limited thereto. Two or more of these solvents can be used in combination.
- azo initiators As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like may be appropriately selected according to the polymerization method.
- the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile) and the like
- peroxide initiators include perisopropyl compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl Perester compounds such as peroxyneodecanate, ⁇ -cumylperoxyneodecanate, and t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-tri
- the initiator can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator.
- the redox initiator include a combination of the above-described peroxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, Rongalite and the like.
- the POA-modified PVA caused by the decomposition of the vinyl ester monomer Coloring may be seen.
- an antioxidant such as tartaric acid may be added to the polymerization system in an amount of 1 ppm to 100 ppm (with respect to the mass of the vinyl ester monomer) for the purpose of preventing coloring.
- Vinyl ester monomers used for copolymerization include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, and lauric acid. Examples thereof include vinyl, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate and the like. Of these, vinyl acetate is most preferred.
- another monomer may be copolymerized within a range that does not impair the gist of the present invention.
- monomers that can be used include ⁇ -olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and salts thereof; acrylic acid esters; methacrylic acid and salts thereof; methacrylic acid esters; acrylamide; -Methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt, acrylamidopropyldimethylamine and its salt or quaternary salt thereof, N-methylolacrylamide and its derivatives, etc.
- Copolymerization may be carried out in the presence of a chain transfer agent as long as the gist of the present invention is not impaired.
- Chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; halogenated hydrocarbons such as trichloroethylene and perchloroethylene; sodium phosphinate 1 Examples thereof include phosphinic acid salts such as hydrates, among which aldehydes and ketones are preferably used.
- the addition amount of the chain transfer agent can be determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target POA-modified vinyl ester polymer. 0.1 mass% or more and 10 mass% or less are desirable.
- the saponification reaction of the POA-modified vinyl ester polymer may be an alcoholysis reaction using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as p-toluenesulfonic acid. Hydrolysis reactions can be applied.
- the solvent that can be used in this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene; These can be used alone or in combination of two or more. Among them, it is convenient and preferable to perform the saponification reaction using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.
- the POA-modified PVA of the present invention needs to have a POA group modification rate of 0.05 mol% or more and 10 mol% or less, preferably 0.05 mol% or more and 5 mol% or less, preferably 0.1 mol% or more and 2 mol%. The following is more preferable, and 0.15 mol% or more and 1.5 mol% or less is more preferable.
- the POA group modification rate exceeds 10 mol%, the water solubility of the POA-modified PVA decreases due to an increase in the proportion of POA groups contained in one molecule of the POA-modified PVA.
- the temperature-sensitive thickening in the high-concentration aqueous solution is not sufficiently exhibited, and the strength and stretchability of the resulting film are lowered.
- the ratio of the POA group is increased, when the release paper base or oil-resistant paper is produced using the coating agent containing the POA-modified PVA, the viscosity of the coating agent at a high temperature becomes too high. Sometimes unevenness tends to occur. When such unevenness occurs, the water resistance of the resulting release paper base and oil-resistant paper is not sufficiently developed.
- the POA group modification rate is less than 0.05 mol%, the ratio of POA groups contained in one molecule of POA-modified PVA is low, and therefore, temperature-sensitive thickening due to interaction between POA groups, and POA The oil resistance and water resistance of the oil resistant paper due to the interaction between groups are not sufficiently developed. Moreover, since the ratio of the POA group is low, the sealing property, oil resistance and water resistance of the release paper base paper are not sufficiently exhibited, and the strength of the film is lowered.
- the POA group modification rate is the ratio of the number of moles of the POA group represented by the general formula (I) in the side chain of the POA-modified PVA to the number of moles of all monomer units constituting the POA-modified PVA (moles). %).
- the POA group modification rate may be determined from POA-modified PVA or may be determined from the precursor POA-modified vinyl ester polymer, both of which can be determined by proton NMR.
- the POA group modification rate can be calculated by this method. That is, for example, when obtaining from a precursor POA-modified vinyl ester polymer (POA-modified polyvinyl acetate), specifically, first, a POA-modified vinyl ester polymer using a mixed solvent of n-hexane / acetone. After the reprecipitation purification is sufficiently performed three times or more, drying is performed under reduced pressure at 50 ° C.
- the POA group modification rate can be easily obtained by appropriately changing the peak to be calculated and the calculation formula.
- the viscosity average polymerization degree of the POA-modified PVA (hereinafter, the viscosity average polymerization degree may be simply referred to as the polymerization degree) needs to be 150 or more and 5000 or less.
- the degree of polymerization is preferably 200 or more, more preferably 500 or more, still more preferably 1000 or more, particularly preferably 1500 or more, and most preferably 2000 or more.
- the degree of polymerization is preferably 4000 or less, more preferably 3500 or less, and still more preferably 3000 or less.
- the saponification degree of the POA-modified PVA needs to be 40 mol% or more and 99.99 mol% or less, preferably 50 mol% or more and 99.9 mol% or less, and more preferably 60 mol% or more and 99 mol% or less.
- the saponification degree is less than 40 mol%, the water solubility of the POA-modified PVA is lowered and the temperature-sensitive thickening is not sufficiently exhibited.
- the solubility of the POA-modified PVA is lowered, making it difficult to produce a film.
- the oil resistance of the resulting release paper base or oil-resistant paper is not sufficiently developed.
- the degree of saponification exceeds 99.99 mol%, production of POA-modified PVA becomes difficult, which is not practical.
- the saponification degree is preferably 60 mol% or more and 99.99 mol% or less, more preferably 70 mol% or more and 99.5 mol% or less, and 80 mol% or more. 99 mol% or less is more preferable.
- the saponification degree of the POA-modified PVA is a value that can be measured according to JIS-K6726.
- the viscosity ratio ⁇ 2 / ⁇ 1 is more preferably 5.0 or more, further preferably 10 or more, and particularly preferably 100 or more.
- the viscosity ratio ⁇ 2 / ⁇ 1 is less than 2.0, when the POA-modified PVA is used as an ink jet recording material, the interaction between the POA groups is small, and the physical properties accompanying the POA modification are not sufficiently exhibited, There are cases where warm thickening cannot be utilized. But not limited viscosity ratio ⁇ 2 / ⁇ 1 of the upper limit particularly, it is preferred that the viscosity ratio ⁇ 2 / ⁇ 1 is 2000 or less, more preferably 1000 or less.
- ⁇ Aqueous solution containing POA-modified PVA> By utilizing the viscosity behavior of the aqueous solution containing the POA-modified PVA of the present invention with respect to the above temperature change, the aqueous solution can be suitably used in a wide range of fields.
- content of POA modified PVA in the said aqueous solution is not specifically limited, It is preferable that they are 1 mass% or more and 20 mass% or less.
- the content of the POA-modified PVA is less than 1% by mass, the temperature-sensitive thickening may not be sufficiently exhibited.
- the content of the POA-modified PVA is more preferably 2% by mass or more.
- the POA-modified PVA of the present invention is suitably used as a coating agent by utilizing the viscosity behavior with respect to temperature change of an aqueous solution containing it.
- the coating agent of the present invention is not particularly limited as long as it contains POA-modified PVA, but is preferably a solution in which POA-modified PVA is dissolved in a liquid medium.
- the coating agent can be prepared by dissolving POA-modified PVA in the liquid medium. It is preferable to use water or a mixture of water and an organic solvent as the liquid medium. More preferably, the liquid medium is water, that is, the coating agent is an aqueous solution containing POA-modified PVA.
- organic solvent used for the liquid solvent examples include alcohol solvents such as methanol and ethanol; ester solvents such as methyl acetate and ethyl acetate; diethyl ether, 1,4-dioxane, cellosolve, MTBE (methyl-t- Ether solvents such as butyl ether); ketone solvents such as acetone and diethyl ketone; glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol; diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, Glycol ether solvents such as 3-methoxy-3-methyl-1-butanol; ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomer) Ether acetate), diethylene glycol monobutyl ether acetate, and the like glycol ester solvents such as diethylene glycol monoethyl ether acetate.
- the content of POA-modified PVA in the coating agent is not particularly limited, and the coating amount (the increase in the dry mass of the substrate caused by coating) , Arbitrarily selected according to the apparatus used for coating, operating conditions, etc., preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and more preferably 2% by mass to 10% by mass. % Or less is more preferable.
- the coating agent of the present invention may be a dispersion, and the content of the dispersoid in this case is preferably 5% by mass or more and 50% by mass or less.
- the dispersion medium at this time a solution in which the above-described POA-modified PVA is dissolved in a liquid medium is preferable.
- the content of the POA-modified PVA in the dispersion medium is preferably the amount described above as the content of the POA-modified PVA in the solution containing the POA-modified PVA.
- the coating agent of the present invention may further contain other components other than the above-described POA-modified PVA, water, and an organic solvent as long as the gist of the present invention is not impaired.
- the other components include various polymers (water-soluble polymers, polymer dispersions, etc.), fillers, water resistance agents, surfactants (nonionic, anionic, etc.), lubricants, antifoaming agents, dispersants. , Wetting agents, pH adjusting agents, ultraviolet absorbers and the like.
- a coated product obtained by coating the surface of the substrate with the coating agent containing the POA-modified PVA is also a preferred embodiment of the present invention.
- the type of the coated material is not particularly limited, and includes an inkjet recording material, a paper base material, and a coating layer formed on the surface of the paper base material, which will be described later.
- the method for producing the coated product is not particularly limited, but a method having a step of coating the coating agent on the surface of a substrate that has been previously adjusted to 50 ° C. or more and 100 ° C. or less is suitable.
- the coating agent containing POA-modified PVA is preferably used for the production of an ink jet recording material, and an ink jet recording material obtained by coating the coating agent on the surface of a substrate is also a preferred embodiment of the present invention.
- the POA modified PVA is an ink receiving layer of the ink jet recording material. It can function as a binder for the filler.
- the coating agent can be suitably used for the production of a high gloss inkjet recording material.
- the POA-modified PVA may be used alone or in combination with other water-soluble polymers or water-dispersible polymers.
- water-soluble polymers that can be used in combination with POA-modified PVA include cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose (CMC), albumin, gelatin, casein, starch, cationized starch, gum arabic,
- CMC carboxymethylcellulose
- albumin cellulose derivatives
- gelatin casein
- starch cationized starch
- gum arabic examples include poly (meth) acrylamide, polyvinylpyrrolidone, sodium poly (meth) acrylate, non-modified PVA, anion-modified PVA, sodium alginate, water-soluble polyester resin, water-soluble polyamide resin, and water-soluble melamine resin.
- water-dispersible polymers that can be used in combination with POA-modified PVA include styrene-butadiene copolymers, nitrile-butadiene copolymers, vinyl acetate polymers, ethylene-vinyl acetate copolymers, (meth) acrylic esters.
- vinyl polymers and vinyl chloride polymers examples include vinyl polymers and vinyl chloride polymers.
- the coating agent used for producing the inkjet recording material further contains a filler.
- the filler is contained in the ink receiving layer.
- the average particle size of the filler is not particularly limited, but is preferably 30 nm or more and 400 nm or less, and more preferably 80 nm or more and 400 nm or less.
- the average particle size is smaller than 30 nm, it is difficult to form capillaries in the ink receiving layer, so that the ink absorbability of the ink jet recording material may be lowered.
- the average particle diameter exceeds 400 nm, the glossiness of the ink receiving layer surface may be lowered.
- the average particle diameter of the filler can be measured using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd .; LA-910).
- Both inorganic fine particles and organic fine particles are used as the filler.
- examples of such inorganic fine particles include precipitated silica, gel silica, colloidal silica, gas phase method silica, colloidal alumina, alumina sol, aluminum oxide fine particles, fine particle titanium oxide, fine particle zinc oxide, aluminum hydroxide, pseudoboehmite, clay, Examples include talc, diatomaceous earth, zeolite, calcium carbonate, and satin white.
- colloidal silica, gas phase method silica, alumina sol, and aluminum oxide fine particles are preferably used.
- examples of the organic fine particles include fine particles such as organic pigment, polystyrene resin, polyacrylic resin, and styrene / acrylic copolymer resin.
- Colloidal silica refers to amorphous silica particles dispersed in water to form a colloidal shape.
- colloidal silica for the filler those having a negatively charged surface charge can generally be used.
- those imparted with a positive charge by surface treatment such as a silane coupling agent or those aggregates thereof are also suitably used as the filler.
- Vapor phase method silica is silicon dioxide obtained from volatile silane compounds.
- Vapor phase process silica usually consists of spherical primary particles having an average particle diameter of several tens of nanometers, and these primary particles aggregate to form secondary aggregates. Fine particles having an average particle diameter of 30 nm or more and 400 nm or less obtained by pulverizing this secondary aggregate with a pulverizing means such as a bead mill, a homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer are preferably used as the filler.
- a vapor phase method silica those having a negatively charged surface charge can generally be used. Further, those imparted with a positive charge by surface treatment are also preferably used.
- ⁇ -type crystal form aluminum oxide fine particles are used as the aluminum oxide fine particles for the filler.
- the aluminum oxide in the ⁇ -type crystal form can reduce the average particle diameter of primary particles to about 10 nm.
- primary particles generally form secondary aggregates in a powder state.
- the particle size of the secondary aggregate is usually on the order of several ⁇ m. Fine particles having an average particle diameter of 30 nm or more and 400 nm or less obtained by pulverizing this secondary aggregate with a pulverizing means such as a bead mill, a homogenizer, an ultrasonic homogenizer, or a high-pressure homogenizer are preferably used as the filler.
- the mass ratio of POA-modified PVA / filler is not particularly limited, but the mass ratio of POA-modified PVA / filler is 3/97 or more and 50/50 or less. It is preferably 5/95 or more and 40/60 or less, and more preferably 8/92 or more and 30/70 or less.
- the mass ratio of POA-modified PVA / filler is less than 3/97, an ink receiving layer having sufficient strength may not be obtained.
- the mass ratio of POA-modified PVA / filler is larger than 50/50, it is difficult to form capillaries necessary for ink absorption, and ink absorbability may be inferior.
- the coating agent used in the production of the ink jet recording material can also contain a cationic monomer, oligomer or polymer as an ink fixing agent.
- a cationic monomer, oligomer or polymer as an ink fixing agent.
- Those that can be used for this purpose are preferably monomers, oligomers or polymers having primary to tertiary amines or quaternary ammonium salts that dissociate when dissolved in water and exhibit cationic properties.
- oligomers or polymers are preferred. preferable.
- the fixing agent include dimethylamine / epichlorohydrin polycondensate, acrylamide / diallylamine copolymer, polyvinylamine copolymer, polyallylamine copolymer, diallyldimethylammonium chloride copolymer, polyethyleneimine, and the like. However, it is not limited to these.
- any conventionally known transparent or opaque support substrate can be used as the base material used in the production of the above-described ink jet recording material.
- the transparent support substrate include polyester, polystyrene, polyvinyl chloride, polymethyl methacrylate, cellulose acetate, polycarbonate, polyimide, cellophane, celluloid films, sheets, and highly transparent paper.
- the POA-modified PVA in the ink receiving layer formed using the coating agent of the present invention has high transparency. Therefore, an inkjet recording material with high transparency can be obtained by using the coating agent of the present invention.
- the opaque support substrate include general paper, pigment-coated paper (art paper, coated paper, cast-coated paper), cloth, wood, metal plate, synthetic paper, synthetic resin film or sheet subjected to opacification treatment, and the like. It is done.
- a coating agent is prepared by dissolving or dispersing in a medium, and the resulting coating agent is applied to the surface of the substrate using a conventionally known size press, air knife coater, roll coater, bar coater, blade coater, curtain coater, cast coater, etc. The method of coating is mentioned.
- coating temperature temperature of a coating agent
- 10 to 60 degreeC More preferably, it is 15 to 50 degreeC, More preferably, it is 20 to 40 degreeC. It is as follows. Further, when the substrate is paper, a method of internally adding the above aqueous solution or aqueous dispersion during paper making can also be employed.
- the coating agent When an inkjet recording material is produced by applying the coating agent containing the POA-modified PVA of the present invention to the substrate surface, the coating agent is applied to the substrate surface that has been conditioned to 60 ° C. or more and 100 ° C. or less in advance. It is preferable.
- the temperature of the substrate surface is more preferably 60 ° C. or higher and 90 ° C. or lower, and further preferably 60 ° C. or higher and 80 ° C. or lower.
- the coating temperature (coating) is not cooled after the coating has been cooled.
- the coating can be prevented from cracking only by drying at a temperature higher than the temperature of the agent.
- the production speed, that is, productivity is remarkably improved, and utility costs such as power consumption can be greatly saved.
- the coating agent containing POA-modified PVA is increased in viscosity by being applied to a heated substrate surface, and further gelled by increasing the concentration by evaporation of water during the drying process.
- the coating film obtained in this way has a strong three-dimensional structure and is considered to be a film that does not easily crack.
- the structure having a polyoxyethylene block at the terminal portion of the POA group is considered to promote the hydrophobic interaction.
- the POA-modified PVA of the present invention is considered to exhibit a very excellent temperature-sensitive thickening.
- the POA-modified PVA of the present invention has a greater temperature sensitivity than POA-modified PVA having a POA group consisting only of polyoxypropylene blocks and POA-modified PVA in which oxypropylene units and oxyethylene units are randomly arranged. It has been confirmed to show thickening.
- the release paper base paper of the present invention contains the POA-modified PVA.
- the layer structure of the release paper base paper is not limited, it has a paper base material and a coating layer formed on the surface of the paper base material, and the coating layer contains the POA-modified PVA. It is preferable. According to such a release paper base paper, the sealing property, oil resistance and water resistance can be improved more effectively.
- paper bases obtained by papermaking chemical pulp such as hardwood kraft pulp, softwood kraft pulp, mechanical pulp such as GP (crushed wood pulp), RGP (refiner ground pulp), TMP (thermomechanical pulp), etc. Paper or synthetic paper can be used. Further, as the paper substrate, fine paper, medium paper, alkaline paper, glassine paper, semi-glassine paper, and the like can be used, and semi-glassine paper is preferable.
- the paper base material may contain organic and inorganic pigments and papermaking auxiliary chemicals such as a paper strength enhancer, a sizing agent, and a yield improver.
- the basis weight of the paper base material is not particularly limited, but is preferably 10 g / m 2 or more and 120 g / m 2 or less, and preferably 40 g / m 2 or more in consideration of the sealing property and handleability of the obtained release paper base paper. 100 g / m 2 or less is more preferable.
- the release paper base paper of the present invention can be produced by applying the coating agent to the paper substrate.
- the coating agent may be applied to one side of the paper substrate or may be applied to both sides.
- the content of the POA-modified PVA in the coating agent used for the production of the release paper base paper is not particularly limited, the coating amount (increase in the dry mass of the paper generated by coating), the apparatus used for coating, Although arbitrarily selected according to operation conditions etc., 1 to 15 mass% is preferable and 2 to 10 mass% is more preferable.
- the viscosity of the coating agent is not particularly limited, but the viscosity at the time of coating is preferably 10 mPa ⁇ s to 3000 mPa ⁇ s, more preferably 12 mPa ⁇ s to 2000 mPa ⁇ s. 15 mPa ⁇ s or more and 1000 mPa ⁇ s or less is more preferable.
- the viscosity of the coating agent is within the above range, it is difficult for the coating agent to penetrate into the paper substrate, and a coating layer with sufficient thickness and less unevenness can be easily formed on the surface of the paper substrate. As a result, the sealing property and oil resistance are further improved.
- the water-soluble polymer and polymer dispersion that can be contained in the coating agent in the production of the release paper base include starch and derivatives thereof, cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose.
- the filler that the coating agent can contain include kaolin, clay, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, silica, colloidal silica, aluminum oxide, aluminum hydroxide, Examples thereof include synthetic aluminum silicate, synthetic magnesium silicate, polystyrene fine particles, polyvinyl acetate fine particles, urea-formalin resin fine particles, and wheat flour.
- water-proofing agent examples include glyoxal, urea resin, melamine resin, polyvalent metal salt, and water-soluble polyamide resin.
- the method for producing the release paper base paper by applying the coating agent to a paper substrate is not particularly limited, and can be performed by a known method.
- a 2-roll size press, a gate roll size press, a metering size press, an air knife coater, a bar coater, a roll coater, a blade coater and the like can be used.
- the coating amount of the coating agent is not particularly limited, usually, 0.05 g / m 2 or more 3 g / m 2 or less are preferred per side of the paper substrate in terms of solid content, 0.1 g / m 2 or more 2g / M 2 or less is more preferable.
- the coating amount is in the above range, the sealing property, oil resistance and water resistance are further improved.
- coating temperature temperature of a coating agent
- it is 10 to 60 degreeC, More preferably, it is 15 to 55 degreeC, More preferably, it is 20 to 40 degreeC. .
- a release paper base paper by applying the coating agent to a paper base material, it is preferable to apply the coating agent to a paper base material that has been conditioned at 50 ° C. to 100 ° C. in advance.
- the temperature of the paper substrate after temperature adjustment is more preferably 50 ° C. or higher and 90 ° C. or lower, and further preferably 50 ° C. or higher and 80 ° C. or lower.
- the drying treatment can be performed by hot air, infrared rays, a heating cylinder, or a method combining these.
- the dried release paper base can be further improved in oil resistance by subjecting it to humidity control and calendering.
- the humidity conditioning condition is preferably a condition in which the moisture content in the paper is 5 to 20% by mass.
- the roll temperature is preferably from room temperature to 200 ° C., and the roll linear pressure from 20 to 350 kg / cm.
- the release paper base paper may contain the POA-modified PVA in a paper base material. Even in such a case, the release paper base paper can exhibit high sealing properties and water resistance.
- the release paper of the present invention has the release paper base paper and a release layer formed on the surface of the release paper base paper.
- the release paper base paper include those having a paper base and a coating layer formed on the surface of the paper base as described above, but the release layer is a coating layer in the release paper base paper. When formed on the surface, the excellent performance of the release paper base paper of the present invention is more effectively exhibited.
- Such a release paper can be obtained by coating the release paper base paper with a release agent for forming a release layer as the varnish.
- the release agent include solvent-based silicone, non-solvent-based (emulsion-based, oligomer-based) silicone, and the like.
- the solvent contained in the release agent include organic solvents such as toluene.
- the laminate of the present invention has at least the release paper base paper, a release layer formed on the surface of the release paper base paper, and an adhesive layer formed on the surface of the release layer.
- a base material layer such as a paper layer or a plastic layer is further disposed on the surface of the pressure-sensitive adhesive layer opposite to the side on which the release layer contacts.
- Such a laminate is excellent in peelability between the release layer and the adhesive layer.
- Such a laminate can be obtained by applying a pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer on the release layer of the release paper.
- the pressure-sensitive adhesive include solvent-based pressure-sensitive adhesives and emulsion-based pressure-sensitive adhesives.
- the oil-resistant paper of the present invention contains the POA-modified PVA.
- the layer structure of the oil-resistant paper is not limited, but has a paper base and a coating layer formed on the surface of the paper base, and the coating layer contains the specific POA-modified PVA. Preferably there is. According to such oil resistant paper, production efficiency, oil resistance and water resistance can be improved more effectively.
- the paper base material chemical pulp such as hardwood kraft pulp and softwood kraft pulp, and mechanical pulp such as GP (crushed wood pulp), RGP (refiner ground pulp), TMP (thermomechanical pulp) and the like are known. Paper or synthetic paper can be used.
- high-quality paper, medium-quality paper, alkaline paper, glassine paper, semi-glassine paper, or paperboard used for corrugated cardboard, building material, whiteball, chipball, and the like are also used. be able to.
- the paper base material may contain organic and inorganic pigments and papermaking auxiliary chemicals such as a paper strength enhancer, a sizing agent, and a yield improver. Further, the paper base material may be subjected to various surface treatments.
- the basis weight of the paper base is not particularly limited, but considering the oil resistance of the resulting oil-resistant paper, it is preferably 20 g / m 2 or more and 150 g / m 2 or less for wrapping paper, and for a molded container such as a box. Is preferably 150 g / m 2 or more and 500 g / m 2 or less.
- the oil-resistant paper of the present invention can be produced, for example, by applying a coating agent containing the POA-modified PVA to the surface of the paper substrate.
- the oil-resistant paper of the present invention thus obtained usually has a paper base and a coating layer formed on the surface of the paper base, and the coating layer contains the POA-modified PVA.
- the surface of the paper base means at least one side of the paper base and may be both sides.
- the content of the POA-modified PVA in the coating agent used for the production of oil-resistant paper is not particularly limited, and the coating amount (the increase in the dry mass of the paper generated by coating), the equipment used for coating, and the operation Although arbitrarily selected according to conditions etc., 1 to 15 mass% is preferable and 2 to 10 mass% is more preferable.
- the coating agent of the present invention may further contain an oil-resistant agent other than the POA-modified PVA.
- the oil-resistant paper of the present invention is excellent in oil resistance because it contains the POA-modified PVA, but the oil resistance can be further improved by containing other oil-resistant agents.
- oil-proofing agents include PVA other than the above POA-modified PVA, acrylic resins, polyester resins, polyurethane resins, styrene-butadiene resins, polyolefin resins, carboxymethyl cellulose resins, polyamide resins, starches, Examples thereof include vinyl chloride resins, vinylidene chloride resins, silicone resins, mixtures of acrylic resins and waxes, and mixtures of styrene-acrylic resins and waxes.
- the coating agent when used in the production of oil-resistant paper, the coating agent further contains an inorganic or organic filler from the viewpoint of imparting various physical properties to the oil-resistant paper, such as suppressing blocking between oil-resistant papers. You may do it.
- inorganic fillers include kaolin, synthetic mica, calcium carbonate, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, alumina, aluminum hydroxide, magnesium carbonate, magnesium oxide, silica, magnesium aluminosilicate, and silicic acid.
- examples include calcium, white carbon, bentonite, zeolite, sericite, and smectite. Of these, kaolin is preferred.
- Organic fillers include polydienes such as polyisoprene, polychloroprene, and polybutadiene; polyolefins such as polybutene, polyisobutylene, and polypropylene; vinyl acetate, styrene, (meth) acrylic acid, and (meth) acrylic acid alkyl esters.
- Polymers of vinyl monomers such as (meth) acrylamide and methyl vinyl ether; polyurethane resins; polyester resins; polyamide resins; particles of amino resins such as urea resins, melamine resins and benzoguanamine resins .
- the content of the filler is not particularly limited, but is preferably 75% by mass or less based on the total solid content in the coating agent.
- the coating agent of the present invention when used for the production of oil-resistant paper, the coating agent further contains an auxiliary agent such as a dispersant such as polycarboxylic acid, a surfactant, and a water retention agent, if necessary. Also good.
- an auxiliary agent such as a dispersant such as polycarboxylic acid, a surfactant, and a water retention agent, if necessary. Also good.
- the coating amount of the coating agent applied to the surface of the paper substrate is preferably 0.2 g / m 2 or more and 20 g / m 2 or less in terms of solid content, and 0.5 g / m 2 or more and 10 g / m 2 or less. More preferred.
- the coating amount of the coating agent in terms of solid content usually corresponds to the weight per unit area of the coating layer formed on the surface of the paper substrate.
- the coating amount of the coating agent is in the above range, an oil-resistant paper having more excellent oil resistance can be efficiently obtained.
- a coating agent is applied to both surfaces of a paper base material, it is preferable that the total coating amount of both surfaces exists in the said range.
- An oil-resistant coating layer is formed by coating the surface of the paper substrate with the coating agent containing the POA-modified PVA.
- the layer structure of the oil-resistant paper of the present invention is not particularly limited, and for example, at least one coating layer may be provided on at least one side of the paper substrate.
- a multilayer structure is preferable because oil resistance is improved as compared to a single layer structure.
- each layer may have the same composition or may be different.
- coating apparatuses such as blade coaters, air knife coaters, roll coaters, reverse roll coaters, bar coaters, curtain coaters, slot die coaters, gravure coaters, Champlex coaters, brushes
- a coating method using a coater, a slide bead coater, a two-roll or metering blade type size press coater, a bill blade coater, a short dwell coater, a gate roll coater, a nip coater using a calendar, or the like is appropriately employed.
- ⁇ On-machine coating method is preferable in terms of cost. Particularly, in the nip coating at the calender part located in the latter half of the papermaking part, it is possible to perform multi-stage coating according to the number of stages of the smoothing roll, so that high oil resistance is easily obtained with a small coating amount, and a preferred embodiment It is.
- the coating temperature (the temperature of the coating agent at the time of coating) is not particularly limited, but is preferably 10 ° C or higher and 60 ° C or lower, more preferably 15 ° C or higher and 55 ° C or lower, and further preferably 20 ° C or higher and 50 ° C or lower.
- the coating agent when manufacturing the oil-resistant paper by applying the coating agent on the surface of the paper base material, it is preferable to apply the coating agent on the surface of the paper base material that has been conditioned to 60 ° C. or higher and 100 ° C. or lower in advance.
- the temperature of the paper substrate after temperature adjustment is more preferably 60 ° C. or higher and 90 ° C. or lower, and further preferably 60 ° C. or higher and 80 ° C. or lower.
- a drying process is performed.
- hot air, infrared rays, a heating cylinder or a combination of these can be employed.
- the oil resistance can be further improved by subjecting the oil-resistant paper after drying to humidity conditioning and / or smoothing treatment.
- As the humidity control condition a condition in which the moisture content in the oil-resistant paper is 5% by mass or more and 20% by mass or less is preferable.
- the smoothing process can be performed using a smoothing apparatus such as a super calendar, a gloss calendar, or a soft calendar.
- the processing conditions are a roll temperature of room temperature to 200 ° C., and a roll linear pressure of 20 kg / cm or more. It is preferably 350 kg / cm or less.
- the smoothing process may be appropriately performed on-machine or off-machine.
- the oil-resistant paper of the present invention may further have layers other than the above-described paper base layer and coating layer.
- the oil-resistant paper may contain the POA-modified PVA in a paper base material. Even in such a case, the oil-resistant paper can exhibit high oil resistance and water resistance.
- the film of the present invention contains the POA-modified PVA.
- the method for producing the film of the present invention is not particularly limited, for example, a method of forming a film using a solution containing the POA-modified PVA can be suitably used.
- the solvent in the solution is not particularly limited, and for example, water, an organic solvent, or a mixed solution of water and an organic solvent can be used.
- the solution can be obtained by dissolving the POA-modified PVA in such a solvent.
- the solution may contain a plasticizer, a surfactant, a dichroic dye, inorganic salts, and the like, if necessary.
- a method of forming the solution by casting or die casting can be employed.
- a method of forming the solution on the resin film, the drying drum, or the drying belt by the film forming method can be used. It is preferable to dry the film after forming the solution. Here, after drying, heat treatment may be performed as necessary.
- the content of the POA-modified PVA in the obtained film is preferably 50% by mass or more, and more preferably 80% by mass or more.
- the thickness of the obtained film is not particularly limited, but is preferably 1 to 150 ⁇ m, more preferably 1 to 100 ⁇ m.
- the film of the present invention thus obtained has sufficient strength and stretchability even if it is a single layer. Therefore, the film of the present invention can be suitably used as a single layer film.
- the film of the present invention can be suitably used for production of a multilayer structure formed by laminating a film and a substrate.
- the manufacturing method of the said multilayered structure is not specifically limited, For example, the method of forming the film of this invention on a base material is employable.
- the film formation method the same method as the film production method described above can be adopted.
- the support base material generally used can be used conveniently.
- the support substrate may be transparent or opaque.
- the transparent support substrate include polyester, polystyrene, polyvinyl chloride, polymethyl methacrylate, cellulose acetate, polycarbonate, polyimide, cellophane, celluloid and other films or sheets, or highly transparent paper.
- the opaque support substrate include general paper, pigment-coated paper (art paper, coated paper, cast-coated paper), cloth, wood, metal plate, synthetic paper, synthetic resin film or sheet subjected to opacification treatment, and the like. It is done.
- the mechanism by which the film of the present invention exhibits high strength and high stretchability is not clear, but is estimated as follows.
- the POA group has a polyoxypropylene block on the main chain side of the POA-modified PVA and a (poly) oxyethylene block on the terminal side.
- the POA group has such a structure, it is considered that hydrophobic interaction due to aggregation between polyoxypropylene blocks is easily developed.
- a film having high strength and high stretchability can be obtained by promoting the physical cross-linking action between the POA groups.
- the film of the present invention is a film containing a POA-modified PVA having a POA group consisting only of polyoxypropylene units, a (poly) oxyethylene block on the PVA main chain side, and a poly on the terminal side.
- a film containing POA-modified PVA having a POA group having an oxypropylene block and a film containing POA-modified PVA in which oxypropylene units and oxyethylene units are randomly arranged it has high strength and high stretchability. Has been confirmed.
- the POA-modified PVA of the present invention is excellent in temperature-sensitive thickening as described above. Taking advantage of such characteristics, it is suitably used not only for the above-described ink jet recording material, thermal paper, release paper base paper, oil-resistant paper and film, but also as materials for various functional special papers such as pressure sensitive paper.
- the PVA obtained by the following production examples was evaluated according to the following method.
- Viscosity average degree of polymerization and degree of saponification The viscosity average polymerization degree and saponification degree of PVA were determined by the method described in JIS-K6726.
- POA group modification rate The POA group modification rate of PVA was determined according to the method using proton NMR described above. For proton NMR, JEOL GX-500 (500 MHz) was used.
- Viscosity of PVA aqueous solution A PVA aqueous solution having a concentration of 4% was prepared, and the viscosity at a temperature of 20 ° C., 30 ° C. or 60 ° C. was measured at a rotor rotation speed of 6 rpm using a BL type viscometer.
- Production Example 1-1 (Manufacture of PVA1-1) A 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer dropping port and an initiator addition port was added to 900 g of vinyl acetate, 100 g of methanol, and a single monomer that is an unsaturated monomer having a POA group.
- Monomer A (monomer A is represented by the general formula (II), R 1 to R 5 , X, m and n are as shown in Table 2.
- Arrangement of oxypropylene units and oxyethylene units is in a block form
- the block of the oxypropylene unit is located on the X side with respect to the block of the oxyethylene unit.)
- 3.7 g was charged, and the inside of the system was purged with nitrogen for 30 minutes while carrying out nitrogen bubbling.
- dissolving the monomer A in methanol as a delay solution was prepared, and nitrogen substitution was carried out by bubbling of nitrogen gas.
- the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization.
- AIBN 2,2′-azobisisobutyronitrile
- alkaline solution (10% methanol solution of sodium hydroxide) was added to 386 g of POA-modified PVAc methanol solution prepared by adding methanol to this solution (100.0 g of POA-modified PVAc in the solution).
- POA modified PVAc concentration in saponified solution 25%, molar ratio of sodium hydroxide to vinyl acetate units in POA modified PVAc 0.03 After adding the alkaline solution, a gel-like material was formed in about 1 minute. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to allow saponification to proceed, and then 500 g of methyl acetate was added to remain. The alkali was neutralized.
- a white solid was obtained by filtration, and a washing operation was performed by adding 2000 g of methanol thereto and allowing to stand at room temperature for 3 hours. After repeating this washing operation three times, the white solid obtained by centrifugation and draining was left to dry in a dryer at 65 ° C. for 2 days to obtain POA-modified PVA (PVA1-1).
- Table 3 shows the measurement results of the viscosity average degree of polymerization, degree of saponification, POA group modification rate, and viscosity of the PVA aqueous solution of PVA1-1.
- Example 1-1 Preparation of vapor phase silica fine particle dispersion 600 g of Aerosil A300 (manufactured by Nippon Aerosil Co., Ltd.), a gas phase method silica powder having an average primary particle size of about 12 nm, is added to 2400 g of ion-exchanged water in which 12 g of acetic acid is dissolved, and dispersed by stirring with a three-one motor. And a dispersion having a solid content of 20% was prepared.
- Aerosil A300 manufactured by Nippon Aerosil Co., Ltd.
- a gas phase method silica powder having an average primary particle size of about 12 nm is added to 2400 g of ion-exchanged water in which 12 g of acetic acid is dissolved, and dispersed by stirring with a three-one motor.
- a dispersion having a solid content of 20% was prepared.
- This dispersion was pulverized with a homogenizer (manufactured by IKA; ULTRA-TURRAX T25 type) at 9500 rpm for 5 minutes to obtain a milky white slurry-like viscous dispersion (solid content concentration 20%).
- the average particle size of the inorganic fine particles dispersed in this dispersion was measured with a laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd .; LA-910) and found to be 230 nm.
- the ink receiving layer was evaluated for cracks by the method described below. Further, the ink absorbability when printing on the recording material using an ink jet printer was evaluated.
- (1) Cracks The surface of the ink receiving layer was observed with an optical microscope (magnification 100 times) and evaluated according to the following criteria. 5: No cracks are observed on the surface. 4: Almost no cracks are observed on the surface. 3: Partial cracks were observed on the surface. 2: Many cracks were observed on the surface. 1: Cracks were observed on the entire surface.
- Production Examples 1-2 to 1-13, 1-16 to 1-22, 1-24, 1-25 (Production of PVA 1-2 to 1-13, 1-16 to 1-22, 1-24, 1-25) Charge amount of vinyl acetate and methanol (before the start of polymerization), type of unsaturated monomer having POA group used during polymerization (Table 2), use amount and polymerization rate, concentration of POA-modified PVAc during saponification, acetic acid Except that the molar ratio of sodium hydroxide to vinyl units was changed as shown in Table 1, various POA-modified PVAs (PVA1-2 to 1-13, 1-16 to 1-6) were prepared in the same manner as in Production Example 1-1. 1-22, 1-24, 1-25) were obtained.
- Table 3 shows the evaluation results of PVA 1-2 to 1-13, 1-16 to 1-22, 1-24, 1-25 and ink jet recording materials produced using them.
- Production Example 1-14 (Manufacture of PVA14) Monomer I which is an unsaturated monomer having 850 g of vinyl acetate, 150 g of methanol and POA group was added to a 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and an initiator addition port.
- Form I is represented by the general formula (II), and R 1 to R 5 , X, m and n are as shown in Table 2.
- the arrangement of the oxypropylene unit and the oxyethylene unit is a block, and the oxypropylene unit Was placed on the X side with respect to the block of the oxyethylene unit.) 42 g was charged, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen.
- the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to start polymerization, and polymerization was performed at 60 ° C. for 3 hours. Then, the polymerization was stopped by cooling. The solid content concentration when the polymerization was stopped was 25.5%. Subsequently, unreacted vinyl acetate was removed while occasionally adding methanol at 30 ° C. under reduced pressure to obtain a methanol solution (concentration 30%) of POA-modified vinyl ester polymer (POA-modified PVAc).
- AIBN 2,2′-azobisisobutyronitrile
- Example 1-14 Using the obtained POA-modified PVA, a coating agent was prepared in the same manner as in Example 1-1 to produce an ink jet recording material.
- Table 3 shows the evaluation results of PVA1-14 and an inkjet recording material produced using the PVA1-14.
- Production Examples 1-15 and 1-23 (Production of PVA1-15, 1-23) Various POA modifications were carried out in the same manner as in Production Example 1-14 except that the type of unsaturated monomer having POA group used during polymerization (Table 2) and the amount used were changed as shown in Table 1. PVA (PVA1-15, 1-23) was obtained.
- Example 1-15 Comparative Example 1-8 Using the obtained POA-modified PVA, a coating agent was prepared in the same manner as in Example 1-1 to produce an ink jet recording material.
- Table 3 shows the evaluation results of PVA 1-15 and 1-23 and ink jet recording materials produced using them.
- Production Examples 1-26, 1-27 (Production of PVA1-26, 1-27) Unsaturated monomers having the following structures (Production Example 1-26: Compound III, Production Example 1-27: Compound IV) were used as unsaturated monomers having a POA group to be used at the time of polymerization.
- the various POA-modified PVA (1-26, 1-27) were prepared in the same manner as in Production Example 1-1 except that the amounts and amounts of vinyl acetate and methanol (before the start of polymerization) were changed as shown in Table 1. )
- Table 3 shows the measurement results of the viscosity average polymerization degree, saponification degree, POA group modification rate, and viscosity of the PVA aqueous solution of these POA-modified PVA.
- Example 1-16 A coating agent was prepared in the same manner as in Example 1-3, except that the temperature of the corona-treated PET film (base material) was changed to 20 ° C. when producing the inkjet recording material, and inkjet recording was performed. A material was prepared. Table 3 shows the evaluation results of PVA1-3 and an inkjet recording material produced using the PVA1-3.
- Production Example 2-1 Manufacture of PVA2-1
- PVA2-1 POA-modified PVA (PVA2-1) was obtained in the same manner as in Production Example 1-1.
- Table 4 shows the measurement results of the viscosity average degree of polymerization, the degree of saponification, and the POA group modification rate of PVA2-1.
- Production Examples 2-2 to 2-15, 2-18 to 2-24, 2-26, 2-27 (Production of PVA 2-2 to 2-15, 2-18 to 2-24, 2-26, 2-27) Charge amount of vinyl acetate and methanol (before the start of polymerization), kind of unsaturated monomer having POA group used during polymerization (Table 2) and its use amount, polymerization rate, concentration of POA-modified PVAc during saponification, acetic acid
- Various POA-modified PVA (PVA 2-2 to 2-15, 2-18 to 2) were prepared in the same manner as in Production Example 1-1 except that the molar ratio of sodium hydroxide to vinyl units was changed as shown in Table 4. 2-24, 2-26, 2-27).
- Table 5 shows the measurement results of the viscosity average polymerization degree, saponification degree, and POA group modification rate of these POA-modified PVA.
- Production Example 2-16 Manufacture of PVA2-16) POA-modified PVA (PVA2-16) was obtained in the same manner as in Production Example 1-14.
- Table 5 shows the measurement results of the viscosity average degree of polymerization, degree of saponification, and POA group modification rate of PVA2-16.
- Production Examples 2-17 and 2-25 (Production of PVA2-17 and 2-25) Various POA modifications were carried out in the same manner as in Production Example 1-14 except that the type of unsaturated monomer having POA group used during polymerization (Table 2) and the amount used were changed as shown in Table 4. PVA (PVA2-17 and 2-25) was obtained. Table 5 shows the measurement results of the viscosity average polymerization degree, saponification degree, and POA group modification rate of these POA-modified PVA.
- Production Examples 2-28 and 2-29 (Production of PVA2-28 and 2-29) PVA 2-28 and 2-29 were obtained in the same manner as in Production Examples 1-26 and 1-27.
- Table 5 shows the measurement results of the viscosity average polymerization degree, saponification degree, and POA group modification rate of these POA-modified PVA.
- Production Example 2-30 Manufacture of PVA2-30
- a 3 L pressure-resistant reactor equipped with a stirrer, nitrogen inlet, ethylene inlet and initiator addition port was charged with 750 g of vinyl acetate and 250 g of methanol, heated to 60 ° C., and then bubbled with nitrogen for 30 minutes. Replaced with nitrogen. Next, ethylene was introduced so that the pressure in the reactor was 1.4 kg / cm 2 . The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization.
- AIBN 2,2′-azobisisobutyronitrile
- Et-modified PVAc methanol solution 100.0 g of Et-modified PVAc in the solution
- Et-modified PVAc concentration of saponification solution 29%, molar ratio of sodium hydroxide to vinyl acetate unit in Et-modified PVAc 0.03
- a gel-like material was formed in about 1 minute. This was pulverized with a pulverizer and allowed to stand at 60 ° C. for 1 hour to allow saponification to proceed, and then 500 g of methyl acetate was added to remain.
- Production Example 2-31 Manufacture of PVA2-31
- 700 g of vinyl acetate and 300 g of methanol were charged into a 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and an initiator addition port, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen.
- the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to start polymerization, and polymerization was performed at 60 ° C. for 3 hours. Then, the polymerization was stopped by cooling.
- the solid content concentration when the polymerization was stopped was 17.0%.
- Example 2-1 Manufacture of release paper base paper
- Semi-glassine paper (paper base material) having a basis weight of 80 g / m 2 and an air permeability of 140 seconds is heated to 60 ° C., and the concentration is applied to one surface as a coating agent (temperature 30 ° C., viscosity ⁇ 3 95 mPa ⁇ s).
- a 4% aqueous solution of PVA2-1 was applied by hand using a Mayer bar so that the coating amount was 1.1 g / m 2 per side of the paper substrate in terms of solid content.
- it was dried using a hot air dryer at 110 ° C. for 1 minute, conditioned at 20 ° C.
- a silicone solution having the following composition was prepared. Addition reaction type silicone (SD7220 manufactured by Toray Dow Coating Co., Ltd.) 4.5 parts platinum catalyst (manufactured by Toray Dow Coating Co., Ltd .: SRX212) 0.5 parts toluene 95 parts
- the prepared silicone solution is coated on the release paper base paper on one side of the paper base in terms of solid content. Using a Mayer bar, it was coated by hand so as to give a release paper of 2.0 g / m 2 .
- Examples 2-2 to 2-17, 19 and Comparative Examples 2-1 to 2-13 A release paper base paper, a release paper and a laminate were produced in the same manner as in Example 2-1, except that PVA shown in Table 5 was used instead of PVA2-1 used in Example 2-1.
- the release paper base paper was evaluated for sealing properties, oil resistance and water resistance in the same manner as in Example 2-1. The evaluation results are shown in Table 5.
- Example 2-18 Example 2 except that PVA2-3 was used instead of PVA2-1 used in Example 2-1, and that the temperature of the semi-glassine paper (paper substrate) at the time of coating the coating agent was changed to 20 ° C.
- Release paper base paper, release paper and laminate were produced in the same manner as in Example No. 1, and the sealing property, oil resistance and water resistance of the release paper base paper were evaluated in the same manner as in Example 2-1. The evaluation results are shown in Table 5.
- the release paper base paper of the present invention contains a specific POA-modified PVA and thus has excellent sealing properties, oil resistance, and water resistance. Therefore, the peeling layer becomes a problem when the release agent penetrates into the base paper generated when the release agent for forming the release layer is applied, or when the water-dispersible silicone resin and the water-dispersible adhesive are used. It is effective in improving problems such as peeling failure caused by elution of water into water.
- Production Example 3-1 Manufacture of PVA3-1) POA-modified PVA (PVA3-1) was obtained in the same manner as in Production Example 1-1.
- Table 6 shows the measurement results of the viscosity average degree of polymerization, degree of saponification, and POA group modification rate of PVA3-1.
- Production Examples 3-2 to 3-15, 3-18 to 3-25, 3-27 (Production of PVA 3-2 to 3-15, 3-18 to 3-25, 3-27) Charge amount of vinyl acetate and methanol (before the start of polymerization), kind of unsaturated monomer having POA group used during polymerization (Table 2) and its use amount, polymerization rate, concentration of POA-modified PVAc during saponification, acetic acid Various POA-modified PVA (3-2 to 3-15, 3-18 to 3) were prepared in the same manner as in Production Example 1-1 except that the molar ratio of sodium hydroxide to vinyl units was changed as shown in Table 6. 3-25, 3-27). Table 7 shows the measurement results of the viscosity-average polymerization degree, saponification degree, and POA group modification rate of these POA-modified PVA.
- Production Example 3-16 Manufacture of PVA3-16
- POA-modified PVA PVA3-16
- Table 7 shows the measurement results of the viscosity average degree of polymerization, degree of saponification, and POA group modification rate of PVA3-16.
- Production Examples 3-17 and 3-26 (Production of PVA 3-17 and 3-26) Various POA modifications were carried out in the same manner as in Production Example 1-14 except that the type of unsaturated monomer having POA group used during polymerization (Table 2) and the amount used were changed as shown in Table 6. PVA (PVA3-17 and 3-26) was obtained. Table 7 shows the measurement results of the viscosity-average polymerization degree, saponification degree, and POA group modification rate of these POA-modified PVA.
- Production Examples 3-28 and 3-29 (Production of PVA3-28 and 3-29) PVA3-28 and 3-29 were obtained in the same manner as in Production Examples 1-26 and 1-27.
- Table 7 shows the measurement results of the viscosity-average polymerization degree, saponification degree, and POA group modification rate of these POA-modified PVA.
- Production Example 3-30 (Manufacture of PVA3-30) Et-modified PVA (PVA3-30) was obtained in the same manner as in Production Example 2-30.
- Table 7 shows the measurement results of the viscosity average degree of polymerization, degree of saponification, and ethylene modification rate of PVA3-30.
- Production Example 3-31 Manufacture of PVA3-31) Unmodified PVA (PVA3-31) was obtained in the same manner as in Production Example 2-31.
- Table 7 shows the measurement results of the viscosity average polymerization degree and the saponification degree of PVA3-31.
- Example 3-1 Manufacture of oil-resistant paper
- a non-coated paperboard (paper substrate) having a basis weight of 350 g / m 2 is heated to 60 ° C., and an aqueous solution of the above PVA3-1 having a concentration of 4% as a coating agent (temperature 30 ° C.) is applied to one surface thereof.
- the coating was performed by hand coating using a Mayer bar so that the coating amount was 1.0 g / m 2 per one side of the paper substrate in terms of solid content. Next, it is dried at 100 ° C. for 30 seconds using a hot air drier, conditioned at 20 ° C.
- Examples 3-2 to 3-18 and Comparative Examples 3-1 to 3-13 An oil-resistant paper was obtained in the same manner as in Example 3-1, except that various PVAs shown in Table 7 were used instead of PVA3-1. The obtained oil resistant paper was evaluated for oil resistance, practical oil resistance and water resistance in the same manner as in Example 3-1. Table 7 shows the evaluation results.
- Example 3-19 An oil-resistant paper was obtained in the same manner as in Example 3-3, except that the temperature of the paper substrate when applying the coating agent containing POA-modified PVA (PVA3-3) was changed to 20 ° C. The obtained oil resistant paper was evaluated for oil resistance, practical oil resistance and water resistance in the same manner as in Example 3-1. Table 7 shows the evaluation results.
- Examples 3-20 to 3-22 An oil-resistant paper was obtained in the same manner as in Example 3-2 except that the coating amount (solid content converted value) of the coating agent containing POA-modified PVA (PVA3-2) was changed as shown in Table 7. .
- the obtained oil resistant paper was evaluated for oil resistance, practical oil resistance and water resistance in the same manner as in Example 3-1. Table 7 shows the evaluation results.
- Example 4-1 Production of (PVA4-1) POA-modified PVA (PVA4-1) was produced in the same manner as in Production Example 1-1 except that the amount of unsaturated monomer having a POA group was as shown in Table 8. Got. Table 9 shows the measurement results of the viscosity average polymerization degree, saponification degree, POA group modification rate, and viscosity of the PVA aqueous solution of the obtained POA-modified PVA.
- PVA4-1 was dissolved in water to prepare a 4% concentration aqueous solution, which was cast on a polyethylene terephthalate film, dried at 20 ° C. for 1 week, and then peeled off from the polyethylene terephthalate to give a 100 ⁇ m thick PVA film Got.
- the strength and stretchability of the film were evaluated by the following methods. The results are shown in Table 9.
- Production Examples 4-2 to 4-13, 4-16 to 4-22, 4-24, 4-25 (Production of PVA4-2 to 4-13, 4-16 to 4-22, 4-24, 4-25) Charge amount of vinyl acetate and methanol (before the start of polymerization), kind of unsaturated monomer having POA group used during polymerization (Table 2) and its use amount, polymerization rate, concentration of POA-modified PVAc during saponification, acetic acid Except that the molar ratio of sodium hydroxide to vinyl units was changed as shown in Table 8, various POA-modified PVA (PVA4-2 to 4-13, 4-16 to 4-6) were prepared in the same manner as in Production Example 1-1. 4-22, 4-24, 4-25). Table 9 shows the measurement results of the viscosity average polymerization degree, saponification degree, POA group modification rate, and viscosity of the PVA aqueous solution of these POA-modified PVA.
- Examples 4-2 to 4-13, 4-16, Comparative Examples 4-1 to 4-7, 4-9 The viscosity of each aqueous solution of PVA 4-2 to 4-13, 4-16 to 4-22, 4-24, and 4-25 was measured by the method described above. Using each PVA, a PVA film was produced in the same manner as in Example 4-1. For each of the obtained films, the strength and stretchability of the film were evaluated in the same manner as in Example 4-1. Table 9 shows the evaluation results of each PVA and the film produced using them.
- Production Example 4-14 (Manufacture of PVA4-14) POA-modified PVA (PVA4-14) was obtained in the same manner as in Production Example 1-14.
- Table 9 shows the measurement results of the viscosity average polymerization degree, saponification degree, and POA group modification rate of PVA4-14.
- Example 4-14 The viscosity of the aqueous solution of PVA4-14 was measured by the method described above. A PVA film was produced using PVA4-14 in the same manner as in Example 4-1. With respect to the obtained film, the strength and stretchability of the film were evaluated in the same manner as in Example 4-1. Table 9 shows the evaluation results of PVA4-14 and films produced using the PVA4-14.
- Production Examples 4-15, 4-23 (Production of PVA4-15, 4-23) Except that the type of unsaturated monomer having a POA group used at the time of polymerization (Table 2) and the amount thereof used, and the molar ratio of sodium hydroxide to vinyl acetate units at the time of saponification were changed as shown in Table 8, Various POA-modified PVA (PVA4-15, 4-23) were obtained in the same manner as in Production Example 1-14. Table 9 shows the measurement results of the viscosity average polymerization degree, saponification degree, and POA group modification rate of these POA-modified PVA.
- Example 4-15 Comparative Example 4-8
- the viscosity of each aqueous solution of PVA 4-15 and 4-23 was measured by the method described above. Using each PVA, a PVA film was produced in the same manner as in Example 4-1. With respect to the obtained film, the strength and stretchability of the film were evaluated in the same manner as in Example 4-1. Table 9 shows the evaluation results of PVA 4-15 and 4-23, and films produced using them.
- Production Examples 4-26, 4-27 (Production of PVA4-26, 4-27)
- the above compound III or IV is used as an unsaturated monomer having a POA group to be used at the time of polymerization, the amount used, the amount of vinyl acetate and methanol (before the start of polymerization), the sodium hydroxide relative to the vinyl acetate unit at the time of saponification
- Various modified PVA (PVA4-26, 4-27) were obtained in the same manner as in Production Example 1-1 except that the molar ratio was changed as shown in Table 8.
- Table 9 shows the measurement results of the viscosity average polymerization degree, saponification degree, and POA group modification rate of these POA-modified PVA.
- the film containing the POA-modified PVA of the present invention has high strength and high stretchability (Examples 4-1 to 4-16).
- the polymerization degree, POA group modification rate, or saponification degree of the POA-modified PVA does not satisfy the prescribed range (Comparative Examples 4-1, 4-2, 4-4, and 4-5)
- the POA group has the prescribed structure.
- Comparative Example 4-3 is not satisfied (Comparative Examples 4-3 and 4-6 to 4-11), it can be seen that the strength and stretchability of the film containing the PVA were lowered.
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Abstract
Description
本発明のポリオキシアルキレン変性ビニルアルコール系重合体(以下、ポリオキシアルキレンを「POA」と略記し、ビニルアルコール系重合体を「PVA」と略記することがある)は、ポリオキシプロピレンブロックと(ポリ)オキシエチレンブロックとから構成され、下記一般式(I)で示されるポリオキシアルキレン基を側鎖に有し、粘度平均重合度が150以上5000以下であり、けん化度が40モル%以上99.99モル%以下であり、かつポリオキシアルキレン基変性率が0.05モル%以上10モル%以下である。
POA基変性率(モル%)=[(ピークβの面積/3m)/{ピークαの面積+(ピークβの面積/3m)}]×100
粘度平均重合度=([η]×103/8.29)(1/0.62)
本発明のPOA変性PVAを含有する水溶液の上記の温度変化に対する粘度挙動を利用して、当該水溶液は幅広い分野に好適に用いることができる。当該水溶液中のPOA変性PVAの含有量は特に限定されないが、1質量%以上20質量%以下であることが好ましい。POA変性PVAの含有量が1質量%未満の場合には、感温増粘性が十分に発現しないおそれがある。また、当該水溶液の水分を蒸発させる場合に、水分を蒸発させるのに長時間を要し、作業性が低下する場合がある。POA変性PVAの含有量は、2質量%以上であることがより好ましい。
本発明のPOA変性PVAは、それを含有する水溶液の温度変化に対する粘度挙動等を利用して、コーティング剤に好適に使用される。本発明のコーティング剤は、POA変性PVAを含有するものであれば特に限定されないが、POA変性PVAが液体媒体に溶解した溶液であることが好ましい。当該コーティング剤は、POA変性PVAを前記液体媒体に溶解させることにより調製することができる。前記液体媒体としては水、または、水と有機溶媒との混合物を用いることが好ましい。前記液体媒体が水であること、すなわち、前記コーティング剤がPOA変性PVAを含有する水溶液であることがより好ましい。
前記POA変性PVAを含有するコーティング剤が基材表面に塗工されてなる塗工物も本発明の好適な実施態様である。
本発明の剥離紙原紙は、上記POA変性PVAを含有するものである。当該剥離紙原紙の層構成は限定されないが、紙基材と、この紙基材の表面に形成される塗工層とを有し、該塗工層が上記POA変性PVAを含有するものであることが好ましい。このような剥離紙原紙によれば、より効果的に目止め性、耐油性および耐水性を高めることができる。
本発明の剥離紙は、上記剥離紙原紙と、この剥離紙原紙の表面に形成される剥離層とを有する。上記剥離紙原紙の例としては、上述のように紙基材と、この紙基材の表面に形成される塗工層とを有するものが挙げられるが、剥離層が剥離紙原紙における塗工層の表面に形成される場合には、本発明の剥離紙原紙の優れた性能がより効果的に発揮される。このような剥離紙は、上記剥離紙原紙に、上記ワニスとして、剥離層を形成するための剥離剤を塗工することにより得ることができる。当該剥離剤としては、溶媒系のシリコーン、非溶媒系(エマルジョン系、オリゴマー系)のシリコーンなどを挙げることができる。剥離剤が含む溶媒としては、トルエン等の有機溶媒が挙げられる。
また、本発明の積層体は、上記剥離紙原紙、当該剥離紙原紙の表面に形成される剥離層、および当該剥離層の表面に形成される粘着層を少なくとも有する。当該積層体において、粘着層の、剥離層が接触する側とは反対の側の面には、紙層、プラスチック層等の基材層がさらに配置されるのが好ましい。このような積層体は、剥離層と粘着層との間での剥離性に優れる。このような積層体は剥離紙における剥離層に、粘着層を形成するための粘着剤を塗工することにより得ることができる。当該粘着剤としては、溶媒系の粘着剤やエマルジョン系の粘着剤を挙げることができる。
本発明の耐油紙は、上記POA変性PVAを含有するものである。当該耐油紙の層構成は限定されないが、紙基材と、該紙基材の表面に形成される塗工層とを有し、該塗工層が当該特定のPOA変性PVAを含有するものであることが好ましい。このような耐油紙によれば、より効果的に生産効率、耐油性および耐水性を高めることができる。
本発明のフィルムは、上記POA変性PVAを含有するものである。
PVAの粘度平均重合度およびけん化度は、JIS-K6726に記載の方法により求めた。
PVAのPOA基変性率は、上述したプロトンNMRを用いた方法に準じて求めた。なお、プロトンNMRは、JEOL GX-500(500MHz)を用いた。
濃度4%のPVA水溶液を調製し、BL型粘度計を用いてロータ回転数6rpmで温度が20℃、30℃または60℃における粘度を測定した。
(PVA1-1の製造)
撹拌機、還流冷却管、窒素導入管、単量体滴下口および開始剤の添加口を備えた3Lの反応器に、酢酸ビニル900g、メタノール100g、POA基を有する不飽和単量体である単量体A(単量体Aは一般式(II)で示され、R1~R5、X、mおよびnは表2に示すとおりである。オキシプロピレンユニットとオキシエチレンユニットの配置はブロック状であり、オキシプロピレンユニットのブロックがオキシエチレンユニットのブロックに対して上記X側に位置する。)3.7gを仕込み、窒素バブリングをしながら30分間系内を窒素置換した。また、ディレー溶液として単量体Aをメタノールに溶解して濃度20%とした溶液を調製し、窒素ガスのバブリングにより窒素置換した。反応器の昇温を開始し、内温が60℃となったところで、2,2’-アゾビスイソブチロニトリル(AIBN)0.25gを添加し重合を開始した。ディレー溶液を滴下して重合溶液中のモノマー組成(酢酸ビニルと単量体Aの比率)が一定となるようにしながら、60℃で3時間重合した後、冷却して重合を停止した。重合を停止するまでに使用した単量体の総量は17gであった。また重合停止時の固形分濃度は26.2%であった。続いて30℃、減圧下でメタノールを時々添加しながら未反応の酢酸ビニルの除去を行い、POA変性ビニルエステル系重合体(POA変性PVAc)のメタノール溶液(濃度35%)を得た。さらに、これにメタノールを加えて調製したPOA変性PVAcのメタノール溶液386g(溶液中のPOA変性PVAc100.0g)に、14.0gのアルカリ溶液(水酸化ナトリウムの10%メタノール溶液)を添加してけん化を行った(けん化溶液のPOA変性PVAc濃度25%、POA変性PVAc中の酢酸ビニル単位に対する水酸化ナトリウムのモル比0.03)。アルカリ溶液を添加後、約1分でゲル状物が生成したので、これを粉砕器にて粉砕し、40℃で1時間放置してけん化を進行させた後、酢酸メチル500gを加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール2000gを加えて室温で3時間放置する洗浄操作を行った。この洗浄操作を3回繰り返した後、遠心脱液して得られた白色固体を乾燥機中65℃で2日間放置して乾燥し、POA変性PVA(PVA1-1)を得た。PVA1-1の粘度平均重合度、けん化度、POA基変性率およびPVA水溶液の粘度の測定結果を表3に示す。
(気相法シリカ微粒子分散液の調製)
1次粒子の平均粒子径が約12nmの気相法シリカ粉末であるアエロジルA300(日本アエロジル株式会社製)600gを、酢酸12gを溶解したイオン交換水2400gに加え、スリーワンモーターにて撹拌して分散させ、固形分濃度20%の分散液を調製した。この分散液をホモジナイザー(IKA製;ULTRA-TURRAX T25型)にて、9500rpmで5分間粉砕し、乳白色スラリー状の粘稠分散液(固形分濃度20%)を得た。この分散液中に分散している無機微粒子の平均粒子径をレーザー回析/散乱式粒度分布測定装置(株式会社堀場製作所製;LA-910)にて測定したところ、230nmであった。
PVA1-1の濃度10%の水溶液200gを調製し、上記で得られた気相法シリカの固形分濃度20%の分散液1000gに加え、よく混合撹拌して分散液を得た。その後、蒸留水を添加してPVA1-1と気相法シリカの合計が15%のコーティング剤を調製した。次にコロナ処理を施したPETフィルム(基材)を70℃に加温し、その表面にメイヤーバーを用いて塗工量(乾燥時)が15g/m2となるように上記コーティング剤(温度30℃)を塗工し、熱風乾燥機にて100℃で5分間乾燥してインクジェット記録材を作製した。得られたインクジェット記録材を下記の方法により評価した。PVA1-1およびインクジェット記録材の評価結果を表3に示す。
後述の方法によりインク受理層のひび割れを評価した。さらにインクジェットプリンターを用いて該記録材に印刷を行ったときのインク吸収性を評価した。
(1)ひび割れ
インク受理層の表面を光学顕微鏡により観察し(拡大倍率100倍)、以下の基準にて評価した。
5:表面にひび割れが全く観察されない。
4:表面にひび割れがほとんど観察されない。
3:表面に部分的にひび割れが観察された。
2:表面に多数のひび割れが観察された。
1:表面全体にひび割れが観察された。
(2)インク吸収性
インクジェットプリンター(セイコーエプソン(株)製;PM2000C)を用いてインクジェット記録材に黒インクをベタ印字した後、一定時間ごとに印字面を指でこすり、かすれ具合を観察した。全くかすれなくなるまでの時間を測定し、以下の基準にて評価した。
5:5秒未満。
4:5秒以上10秒未満。
3:10秒以上30秒未満。
2:30秒以上60秒未満。
1:60秒以上。
(PVA1-2~1-13、1-16~1-22、1-24、1-25の製造)
酢酸ビニルおよびメタノール(重合開始前)の仕込み量、重合時に使用するPOA基を有する不飽和単量体の種類(表2)、その使用量および重合率、けん化時におけるPOA変性PVAcの濃度、酢酸ビニル単位に対する水酸化ナトリウムのモル比を表1に示すように変更したこと以外は、製造例1-1と同様の方法により各種のPOA変性PVA(PVA1-2~1-13、1-16~1-22、1-24、1-25)を得た。
得られたPOA変性PVAを用いて、実施例1-1と同様の方法によりコーティング剤を調製し、インクジェット記録材を作製した。PVA1-2~1-13、1-16~1-22、1-24、1-25およびそれらを用いて作製したインクジェット記録材の評価結果をそれぞれ表3に示す。
(PVA14の製造)
撹拌機、還流冷却管、窒素導入管および開始剤の添加口を備えた3Lの反応器に、酢酸ビニル850g、メタノール150g、POA基を有する不飽和単量体である単量体I(単量体Iは一般式(II)で示され、R1~R5、X、mおよびnは表2に示すとおりである。オキシプロピレンユニットとオキシエチレンユニットの配置はブロック状であり、オキシプロピレンユニットのブロックがオキシエチレンユニットのブロックに対して上記X側に位置する。)42gを仕込み、窒素バブリングをしながら30分間系内を窒素置換した。反応器の昇温を開始し、内温が60℃となったところで、2,2’-アゾビスイソブチロニトリル(AIBN)0.25gを添加し重合を開始し、60℃で3時間重合した後、冷却して重合を停止した。重合停止時の固形分濃度は25.5%であった。続いて30℃、減圧下でメタノールを時々添加しながら未反応の酢酸ビニルの除去を行い、POA変性ビニルエステル系重合体(POA変性PVAc)のメタノール溶液(濃度30%)を得た。さらに、これにメタノールを加えて調製したPOA変性PVAcのメタノール溶液463.2g(溶液中のPOA変性PVAc120.0g)に、16.7gのアルカリ溶液(水酸化ナトリウムの10%メタノール溶液)を添加してけん化を行った(けん化溶液のPOA変性PVAc濃度25%、POA変性PVAc中の酢酸ビニル単位に対する水酸化ナトリウムのモル比0.03)。アルカリ溶液を添加後、約1分でゲル状物が生成したので、これを粉砕器にて粉砕し、40℃で1時間放置してけん化を進行させた後、酢酸メチル500gを加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール2000gを加えて室温で3時間放置する洗浄操作を行った。この洗浄操作を3回繰り返した後、遠心脱液して得られた白色固体を乾燥機中65℃で2日間放置して乾燥し、POA変性PVA(PVA1-14)を得た。PVA1-14の粘度平均重合度、けん化度、POA基変性率およびPVA水溶液の粘度の測定結果を表3に示す。
得られたPOA変性PVAを用いて、実施例1-1と同様の方法によりコーティング剤を調製し、インクジェット記録材を作製した。PVA1-14およびそれを用いて作製したインクジェット記録材の評価結果を表3に示す。
(PVA1-15、1-23の製造)
重合時に使用するPOA基を有する不飽和単量体の種類(表2)およびその使用量を表1に示すように変更したこと以外は、製造例1-14と同様の方法により各種のPOA変性PVA(PVA1-15、1-23)を得た。
得られたPOA変性PVAを用いて、実施例1-1と同様の方法によりコーティング剤を調製し、インクジェット記録材を作製した。PVA1-15、1-23およびそれらを用いて作製したインクジェット記録材の評価結果をそれぞれ表3に示す。
(PVA1-26、1-27の製造)
重合時に使用するPOA基を有する不飽和単量体として下記の構造を有する不飽和単量体(製造例1-26:化合物III、製造例1-27:化合物IV)をそれぞれ使用し、その使用量、酢酸ビニルおよびメタノール(重合開始前)の仕込み量を表1に示すように変更したこと以外は、製造例1-1と同様の方法により各種のPOA変性PVA(1-26、1-27)を得た。これらのPOA変性PVAの粘度平均重合度、けん化度、POA基変性率およびPVA水溶液の粘度の測定結果を表3に示す。
得られたPOA変性PVA(PVA1-26、1-27)を用いて、実施例1-1と同様の方法によりコーティング剤を調製し、インクジェット記録材をそれぞれ作製した。PVA1-26および1-27、並びに、それらを用いて作製したインクジェット記録材の評価結果をそれぞれ表3に示す。
インクジェット記録材を作製する際に、コロナ処理を施したPETフィルム(基材)の温度を20℃に変更したこと以外は、実施例1-3と同様の方法によりコーティング剤を調製し、インクジェット記録材を作製した。PVA1-3およびそれを用いて作製したインクジェット記録材の評価結果を表3に示す。
(PVA2-1の製造)
製造例1-1と同様の方法によりPOA変性PVA(PVA2-1)を得た。PVA2-1の粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表4に示す。
(PVA2-2~2-15、2-18~2-24、2-26、2-27の製造)
酢酸ビニルおよびメタノール(重合開始前)の仕込み量、重合時に使用するPOA基を有する不飽和単量体の種類(表2)およびその使用量、重合率、けん化時におけるPOA変性PVAcの濃度、酢酸ビニル単位に対する水酸化ナトリウムのモル比を表4に示すように変更したこと以外は、製造例1-1と同様の手法により各種のPOA変性PVA(PVA2-2~2-15、2-18~2-24、2-26、2-27)を得た。これらのPOA変性PVAの粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表5に示す。
(PVA2-16の製造)
製造例1-14と同様の方法によりPOA変性PVA(PVA2-16)を得た。PVA2-16の粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表5に示す。
(PVA2-17および2-25の製造)
重合時に使用するPOA基を有する不飽和単量体の種類(表2)およびその使用量を表4に示すように変更したこと以外は、製造例1-14と同様の方法により各種のPOA変性PVA(PVA2-17および2-25)を得た。これらのPOA変性PVAの粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表5に示す。
(PVA2-28および2-29の製造)
製造例1-26および1-27と同様の方法によりPVA2-28および2-29を得た。これらのPOA変性PVAの粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表5に示す。
(PVA2-30の製造)
撹拌機、窒素導入口、エチレン導入口および開始剤の添加口を備えた3Lの耐圧反応器に、酢酸ビニル750g、メタノール250gを仕込み、60℃に昇温した後30分間窒素バブリングにより系中を窒素置換した。次いで反応器の圧力が1.4kg/cm2となるようにエチレンを導入した。反応器の昇温を開始し、内温が60℃となったところで、2,2’-アゾビスイソブチロニトリル(AIBN)0.25gを添加し重合を開始した。重合中はエチレンを導入して反応器圧力を5.9kg/cm2に、重合温度を60℃に維持した。4時間後に重合率が20%となったところで冷却して重合を停止した。反応器を開放して脱エチレンした後、窒素ガスをバブリングして脱エチレンを完全に行った。次いで、減圧下でメタノールを時々添加しながら未反応の酢酸ビニルの除去を行い、エチレン変性ビニルエステル系重合体(Et変性PVAc)のメタノール溶液を得た。さらに、これにメタノールを加えて調製したEt変性PVAcのメタノール溶液333g(溶液中のEt変性PVAc100.0g)に、14.1gのアルカリ溶液(水酸化ナトリウムの10%メタノール溶液)を添加してけん化を行った(けん化溶液のEt変性PVAc濃度29%、Et変性PVAc中の酢酸ビニル単位に対する水酸化ナトリウムのモル比0.03)。アルカリ溶液を添加後、約1分でゲル状物が生成したので、これを粉砕器にて粉砕し、60℃で1時間放置してけん化を進行させた後、酢酸メチル500gを加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール2000gを加えて室温で3時間放置する洗浄操作を行った。この洗浄操作を3回繰り返した後、遠心脱液して得られた白色固体を乾燥機中65℃で2日間放置して乾燥し、Et変性PVA(PVA2-30)を得た。PVA2-30の粘度平均重合度、けん化度、およびエチレン変性率の測定結果を表5に示す。
(PVA2-31の製造)
撹拌機、還流冷却管、窒素導入管および開始剤の添加口を備えた3Lの反応器に、酢酸ビニル700g、メタノール300gを仕込み、窒素バブリングをしながら30分間系内を窒素置換した。反応器の昇温を開始し、内温が60℃となったところで、2,2’-アゾビスイソブチロニトリル(AIBN)0.25gを添加し重合を開始し、60℃で3時間重合した後、冷却して重合を停止した。重合停止時の固形分濃度は17.0%であった。続いて30℃、減圧下でメタノールを時々添加しながら未反応の酢酸ビニルの除去を行い、無変性ビニルエステル系重合体(無変性PVAc)のメタノール溶液(濃度30%)を得た。さらに、これにメタノールを加えて調製した無変性PVAcのメタノール溶液463.2g(溶液中の無変性PVAc120.0g)に、16.7gのアルカリ溶液(水酸化ナトリウムの10%メタノール溶液)を添加してけん化を行った(けん化溶液の無変性PVAc濃度25%、無変性PVAc中の酢酸ビニル単位に対する水酸化ナトリウムのモル比0.03)。アルカリ溶液を添加後、約1分でゲル状物が生成したので、これを粉砕器にて粉砕し、40℃で1時間放置してけん化を進行させた後、酢酸メチル500gを加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール2000gを加えて室温で3時間放置する洗浄操作を行った。この洗浄操作を3回繰り返した後、遠心脱液して得られた白色固体を、乾燥機中65℃で2日間放置して乾燥し、無変性PVA(PVA2-31)を得た。PVA2-31の粘度平均重合度、およびけん化度の測定結果を表5に示す。
(剥離紙原紙の製造)
坪量80g/m2、透気度140秒のセミグラシン紙(紙基材)を60℃に加温し、その一方の表面に、コーティング剤(温度30℃、粘度η3 95mPa・s)として濃度4%の上記PVA2-1の水溶液を、塗工量が固形分換算で紙基材の片面当たり1.1g/m2になるようメイヤーバーを用いて手塗り塗工した。次に、110℃で1分間熱風乾燥機を用いて乾燥させ、20℃、65%RHで72時間調湿し、150℃、250kg/cm、10m/分の条件でスーパーカレンダー処理を1回実施し、紙基材の表面に塗工層が形成された剥離紙原紙を得た。得られた剥離紙原紙について、下記に示す方法で、目止め性、耐油性および耐水性を評価した。評価結果を表5に示す。
下記組成のシリコーン溶液を調製した。
付加反応型シリコーン(東レ・ダウコーティング株式会社製SD7220)
4.5部
白金触媒(東レ・ダウコーティング株式会社製:SRX212)0.5部
トルエン 95部
調製したシリコーン溶液を、上記剥離紙原紙上に、塗工量が固形分換算で紙基材の片面当たり2.0g/m2になるようメイヤーバーを用いて手塗り塗工し、剥離紙を得た。
上記剥離紙のシリコーン塗工面に、アクリル系エマルジョン粘着剤(サイデン化学株式会社製:サイビノールAT560)を、塗工量25g/m2になるようメイヤーバーを用いて塗工した。次いで、この粘着剤上に、坪量72g/m2のロイコ染料系の感熱記録紙を重ねてプレスロールで貼り合わせ、積層体を得た。
JIS-P8117に準じ王研式滑度透気度試験機を用いて剥離紙原紙の透気度(目止め性)を測定し、下記の基準により目止め性を判定した。
5:50000秒以上
4:30000秒以上、50000未満
3:10000秒以上、30000未満
2:1000秒以上、10000未満
1:1000秒未満
剥離紙原紙の塗工層の表面に着色トルエン(赤)を5cm×5cmで塗布後、裏面(未塗布面)への裏抜け(小さな赤色の斑点ないし未塗布面の着色)の度合いを評価して、下記の基準によりトルエンバリア性(耐油性)を判定した。
5:裏面に斑点なし
4:斑点が数個(~3個)
3:斑点が多数(着色面積が塗布面積の20%未満)
2:着色面積が塗布面積の20%以上、50%未満
1:着色面積が塗布面積の50%以上
剥離紙原紙の塗工層の表面に20℃のイオン交換水を約1ml滴下した後に、その部分を指先でこすり、最初に指先にヌメリが感じられた時のこすった回数を測定(ウェットラブ試験)し、下記の基準により耐水性を判定した。
5:30回以上
4:20回以上、30回未満
3:10回以上、20回未満
2:5回以上、10回未満
1:5回未満
実施例2-1において用いたPVA2-1に代えて、表5に示したPVAを用いたこと以外は、実施例2-1と同様にして剥離紙原紙、剥離紙および積層体を製造し、その剥離紙原紙の目止め性、耐油性および耐水性を実施例2-1と同様にして評価した。その評価結果を表5に示す。
実施例2-1において用いたPVA2-1に代えてPVA2-3を用いたこと、およびコーティング剤塗工時のセミグラシン紙(紙基材)の温度を20℃に変更したこと以外は実施例2-1と同様にして剥離紙原紙、剥離紙および積層体を製造し、その剥離紙原紙の目止め性、耐油性および耐水性を実施例2-1と同様にして評価した。その評価結果を表5に示す。
(PVA3-1の製造)
製造例1-1と同様の方法によりPOA変性PVA(PVA3-1)を得た。PVA3-1の粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表6に示す。
(PVA3-2~3-15、3-18~3-25、3-27の製造)
酢酸ビニルおよびメタノール(重合開始前)の仕込み量、重合時に使用するPOA基を有する不飽和単量体の種類(表2)およびその使用量、重合率、けん化時におけるPOA変性PVAcの濃度、酢酸ビニル単位に対する水酸化ナトリウムのモル比を表6に示すように変更したこと以外は、製造例1-1と同様の手法により各種のPOA変性PVA(3-2~3-15、3-18~3-25、3-27)を得た。これらのPOA変性PVAの粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表7に示す。
(PVA3-16の製造)
製造例1-14と同様の方法によりPOA変性PVA(PVA3-16)を得た。PVA3-16の粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表7に示す。
(PVA3-17および3-26の製造)
重合時に使用するPOA基を有する不飽和単量体の種類(表2)およびその使用量を表6に示すように変更したこと以外は、製造例1-14と同様の方法により各種のPOA変性PVA(PVA3-17および3-26)を得た。これらのPOA変性PVAの粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表7に示す。
(PVA3-28および3-29の製造)
製造例1-26および1-27と同様の方法によりPVA3-28および3-29を得た。これらのPOA変性PVAの粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表7に示す。
(PVA3-30の製造)
製造例2-30と同様の方法によりEt変性PVA(PVA3-30)を得た。PVA3-30の粘度平均重合度、けん化度、およびエチレン変性率の測定結果を表7に示す。
(PVA3-31の製造)
製造例2-31と同様の方法により無変性PVA(PVA3-31)を得た。PVA3-31の粘度平均重合度、およびけん化度の測定結果を表7に示す。
(耐油紙の製造)
坪量350g/m2の非塗工板紙(紙基材)を60℃に加温し、その一方の表面に、コーティング剤(温度30℃)として濃度4%の上記PVA3-1の水溶液を、塗工量が固形分換算で紙基材の片面当たり1.0g/m2になるようメイヤーバーを用いて手塗り塗工した。次に、熱風乾燥機を用いて100℃で30秒間乾燥し、20℃、65%RHで72時間調湿し、150℃、250kg/cm、10m/分の条件でスーパーカレンダー処理を1回実施し、紙基材の表面に塗工層が形成された耐油紙を得た。得られた耐油紙について、下記に示す方法で、耐油性、実用耐油性および耐水性を評価した。評価結果を表7に示す。
TAPPI UM-557に準拠して以下のように耐油性の評価を行った。ひまし油、トルエン、n-ヘプタンの混合比が異なる試験液を実施例3-1で得られた耐油紙表面に1滴滴下し、15秒後にティッシュペーパーで滴下した試験液を拭き取った。このとき、試験液の浸透による汚れ、すなわち油分が滲み込んで濡れた部分が生じたか、はっきりとした黒い点が認められたら不合格とし、これらの汚れおよび黒い点が認められなかったら合格とした。5回測定を行い、各測定において合格した最大の液番号の平均値をキット指数として耐油性を評価した。なお、TAPPI UM-557では最高キット指数は12であり、このキット指数が高い程、耐油性が高いことを意味する。
2kgのゴム製ローラーを用いて、耐油紙に折り目をつけ、サラダ油0.1mlを耐油紙の折り目に滴下し、20℃で10秒間静置した。ガーゼでサラダ油を拭き取り、耐油紙裏面への浸透(裏抜け)を目視にて確認し、下記の基準により判定した。
○:全く裏抜けしていない
△:一部裏抜けしている
×:大部分が裏抜けしている
耐油紙の塗工層の表面に20℃のイオン交換水を約1ml滴下した後に、その部分を指先でこすり、最初に指先にヌメリが感じられた時のこすった回数を測定(ウェットラブ試験)し、下記の基準により耐水性を判定した。
5:30回以上
4:20回以上、30回未満
3:10回以上、20回未満
2:5回以上、10回未満
1:5回未満
PVA3-1に代えて、表7に示す各種PVAを用いたこと以外は、実施例3-1と同様にして耐油紙を得た。得られた耐油紙について、実施例3-1と同様にして耐油性、実用耐油性および耐水性を評価した。評価結果を表7に示す。
POA変性PVA(PVA3-3)を含有するコーティング剤を塗工する際の紙基材の温度を20℃に変更したこと以外は実施例3-3と同様にして耐油紙を得た。得られた耐油紙について、実施例3-1と同様にして耐油性、実用耐油性および耐水性を評価した。評価結果を表7に示す。
POA変性PVA(PVA3-2)を含有するコーティング剤の塗工量(固形分換算値)を表7に示すように変更したこと以外は、実施例3-2と同様にして耐油紙を得た。得られた耐油紙について、実施例3-1と同様にして耐油性、実用耐油性および耐水性を評価した。評価結果を表7に示す。
(PVA4-1)の製造
POA基を有する不飽和単量体の使用量が表8に示すとおりであったこと以外は、製造例1-1と同様の方法によりPOA変性PVA(PVA4-1)を得た。得られたPOA変性PVAの粘度平均重合度、けん化度、POA基変性率およびPVA水溶液の粘度の測定結果を表9に示す。
PVA4-1を水に溶解し、濃度4%水溶液を調整し、それをポリエチレンテレフタレートフィルム上に流延した後に20℃で1週間乾燥させた後に、ポリエチレンテレフタレートから剥がして、厚さ100μmのPVAフィルムを得た。このPVAフィルムを用いて、下記方法によりフィルムの強度および延伸性を評価した。結果を表9に示す。
厚さ100μmの単層のPVAフィルムを幅10mmにカットし、20℃、85%RHにて1週間調湿して得られたサンプルを強伸度測定に供した。株式会社島津製作所製オートグラフAG-ISを用いて、チャック間距離50mmおよび引張速度500mm/分の条件で強伸度測定を行った。引張弾性率によりフィルムの強度を評価し、伸度によりフィルムの延伸性を評価した。なお、1つのPVAフィルムにつき5サンプル測定した。5サンプルの平均値を求め、以下の評価基準で評価した。
(強度)
A:10kg/mm2以上。
B:5kg/mm2以上10kg/mm2未満。
C:3kg/mm2以上5kg/mm2未満。
D:3kg/mm2未満。
(延伸性)
A:400%以上。
B:300%以上400%未満。
C:200%以上300%未満。
D:200%未満。
(PVA4-2~4-13、4-16~4-22、4-24、4-25の製造)
酢酸ビニルおよびメタノール(重合開始前)の仕込み量、重合時に使用するPOA基を有する不飽和単量体の種類(表2)およびその使用量、重合率、けん化時におけるPOA変性PVAcの濃度、酢酸ビニル単位に対する水酸化ナトリウムのモル比を表8に示すように変更したこと以外は、製造例1-1と同様の手法により各種のPOA変性PVA(PVA4-2~4-13、4-16~4-22、4-24、4-25)を得た。これらのPOA変性PVAの粘度平均重合度、けん化度、POA基変性率およびPVA水溶液の粘度の測定結果を表9に示す。
PVA4-2~4-13、4-16~4-22、4-24、4-25の各水溶液の粘度を上述の方法により測定した。各PVAを用いて、実施例4-1と同様の方法により、PVAフィルムを作製した。得られた各フィルムについて、実施例4-1と同様の方法により、フィルムの強度および延伸性を評価した。各PVAおよびそれらを用いて作製したフィルムの評価結果をそれぞれ表9に示す。
(PVA4-14の製造)
製造例1-14と同様の方法によりPOA変性PVA(PVA4-14)を得た。PVA4-14の粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表9に示す。
PVA4-14の水溶液の粘度を上述の方法により測定した。PVA4-14を用いて、実施例4-1と同様の方法により、PVAフィルムを作製した。得られたフィルムについて、実施例4-1と同様の方法により、フィルムの強度および延伸性を評価した。PVA4-14およびそれを用いて作製したフィルムの評価結果をそれぞれ表9に示す。
(PVA4-15、4-23の製造)
重合時に使用するPOA基を有する不飽和単量体の種類(表2)およびその使用量、けん化時における酢酸ビニル単位に対する水酸化ナトリウムのモル比を表8に示すように変更したこと以外は、製造例1-14と同様の方法により各種のPOA変性PVA(PVA4-15、4-23)を得た。これらのPOA変性PVAの粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表9に示す。
PVA4-15、4-23の各水溶液の粘度を上述の方法により測定した。各PVAを用いて、実施例4-1と同様の方法により、PVAフィルムを作製した。得られたフィルムについて、実施例4-1と同様の方法により、フィルムの強度および延伸性を評価した。PVA4-15および4-23、並びに、それらを用いて作製したフィルムの評価結果をそれぞれ表9に示す。
(PVA4-26、4-27の製造)
重合時に使用するPOA基を有する不飽和単量体として上記化合物IIIまたはIVを使用し、その使用量、酢酸ビニルおよびメタノール(重合開始前)の仕込み量、けん化時における酢酸ビニル単位に対する水酸化ナトリウムのモル比を表8に示すように変更したこと以外は、製造例1-1と同様の方法により各種の変性PVA(PVA4-26、4-27)を得た。これらのPOA変性PVAの粘度平均重合度、けん化度、およびPOA基変性率の測定結果を表9に示す。
得られたPVA(PVA4-26、4-27)の水溶液の粘度を上述の方法により測定した。得られたPOA変性PVA(PVA4-26、4-27)を用いて、実施例4-1と同様の方法により、PVAフィルムをそれぞれ作製した。得られたフィルムについて、実施例4-1と同様の方法により、フィルムの強度および延伸性を評価した。PVA4-26および4-27、並びに、それらを用いて作製したフィルムの評価結果をそれぞれ表9に示す。
Claims (21)
- 前記ポリオキシアルキレン変性ビニルアルコール系重合体の4質量%水溶液の粘度を、ロータ回転数が6rpmの条件でBL型粘度計により測定したとき、20℃における粘度η1と60℃における粘度η2との比η2/η1が2.0以上である請求項1に記載のポリオキシアルキレン変性ビニルアルコール系重合体。
- 請求項1または2に記載のポリオキシアルキレン変性ビニルアルコール系重合体を含有する水溶液。
- 下記一般式(II)で示される不飽和単量体とビニルエステル系単量体との共重合を行い、得られたポリオキシアルキレン変性ビニルエステル系重合体をけん化することを特徴とする請求項1または2に記載のポリオキシアルキレン変性ビニルアルコール系重合体の製造方法。
- 請求項1または2に記載のポリオキシアルキレン変性ビニルアルコール系重合体を含有するコーティング剤。
- 請求項5に記載のコーティング剤が基材の表面に塗工されてなる塗工物。
- あらかじめ50℃以上100℃以下に調温した前記基材の表面に前記コーティング剤を塗工する工程を有する請求項6に記載の塗工物の製造方法。
- 請求項5に記載のコーティング剤が基材の表面に塗工されてなるインクジェット記録材。
- 請求項1または2に記載のポリオキシアルキレン変性ビニルアルコール系重合体を含有する感熱紙。
- 請求項1または2に記載のポリオキシアルキレン変性ビニルアルコール系重合体を含有する剥離紙原紙。
- 紙基材と、該紙基材の表面に形成される塗工層とを有し、該塗工層が前記ポリオキシアルキレン変性ビニルアルコール系重合体を含有する、請求項10に記載の剥離紙原紙。
- 請求項5に記載のコーティング剤を紙基材に塗工する工程を有する剥離紙原紙の製造方法。
- 前記コーティング剤の粘度が10mPa・s以上3000mPa・s以下である請求項12に記載の剥離紙原紙の製造方法。
- 請求項10または11に記載の剥離紙原紙と、該剥離紙原紙の表面に形成される剥離層とを有する剥離紙。
- 請求項10または11に記載の剥離紙原紙、該剥離紙原紙の表面に形成される剥離層、および該剥離層の表面に形成される粘着層を有する積層体。
- 請求項1または2に記載のポリオキシアルキレン変性ビニルアルコール系重合体を含有する耐油紙。
- 紙基材と、該紙基材の表面に形成される塗工層とを有し、該塗工層が前記ポリオキシアルキレン変性ビニルアルコール系重合体を含有する、請求項16に記載の耐油紙。
- 前記塗工層の単位面積当たりの重量が0.2g/m2以上20g/m2以下である請求項17に記載の耐油紙。
- 請求項5に記載のコーティング剤を紙基材の表面に塗工する工程を有する耐油紙の製造方法。
- 請求項1または2に記載のポリオキシアルキレン変性ビニルアルコール系重合体を含有するフィルム。
- 前記ポリオキシアルキレン変性ビニルアルコール系重合体を含有する溶液を用いて製膜する請求項20に記載のフィルムの製造方法。
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JPWO2013015185A1 (ja) | 2015-02-23 |
CN103827156B (zh) | 2016-01-06 |
US9181373B2 (en) | 2015-11-10 |
EP2735577B1 (en) | 2017-12-13 |
CN103827156A (zh) | 2014-05-28 |
EP2735577A4 (en) | 2015-11-11 |
TWI553026B (zh) | 2016-10-11 |
TW201311747A (zh) | 2013-03-16 |
US20140178609A1 (en) | 2014-06-26 |
JP5433817B2 (ja) | 2014-03-05 |
EP2735577A1 (en) | 2014-05-28 |
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