WO2017164410A1 - 化粧シート及び化粧シートの製造方法 - Google Patents
化粧シート及び化粧シートの製造方法 Download PDFInfo
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- WO2017164410A1 WO2017164410A1 PCT/JP2017/012188 JP2017012188W WO2017164410A1 WO 2017164410 A1 WO2017164410 A1 WO 2017164410A1 JP 2017012188 W JP2017012188 W JP 2017012188W WO 2017164410 A1 WO2017164410 A1 WO 2017164410A1
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- Prior art keywords
- decorative sheet
- nucleating agent
- crystalline polypropylene
- polypropylene resin
- layer
- Prior art date
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the present invention relates to a decorative sheet used as a building interior material, a surface material for joinery, a surface material for home appliances, and a method for manufacturing the decorative sheet.
- the decorative sheet is used as a decorative plate by being bonded to a substrate such as a wooden board, an inorganic board, or a metal plate.
- Patent Documents 1 and 2 many decorative sheets using an olefin-based resin have been proposed as decorative sheets that replace polyvinyl chloride decorative sheets. Since these decorative sheets do not use a vinyl chloride resin, generation of toxic gas or the like during incineration is suppressed.
- the conventional olefin-based resin decorative sheet uses a general polypropylene sheet and thus has poor surface scratch resistance, which is inferior to conventional polyvinyl chloride decorative sheets. It was a thing.
- the present inventors proposed a decorative sheet having excellent surface scratch resistance as described in Patent Document 3 in order to eliminate these drawbacks.
- the quality of the decorative sheet other than the scratch resistance is improved. Improvement of post-processing resistance such as V-groove bending is required.
- decorative sheets having improved post-processing properties decorative sheets described in Patent Documents 4 to 6 have been proposed. These decorative sheets are decorative sheets having a transparent resin layer obtained by adding a soft component to a random polymerization type polypropylene resin.
- this decorative sheet has a problem that the scratch resistance deteriorates because the sheet becomes flexible as the post-processability is improved.
- the present invention has been made paying attention to the above points, and a decorative sheet having a transparent resin layer excellent in V-groove bending workability (post-workability) while maintaining high scratch resistance and transparency, and It aims at providing the manufacturing method of a decorative sheet.
- the present inventors have intensively studied and applied a low crystalline polypropylene resin having a tensile modulus of 25 to 500 MPa to a transparent resin layer mainly composed of a high crystalline polypropylene resin. It has been found that the addition of 1 to 20 parts by mass results in a transparent resin layer having excellent post-processability while maintaining high scratch resistance and transparency.
- a decorative sheet is a decorative sheet comprising at least a transparent resin layer mainly composed of a highly crystalline polypropylene resin,
- a transparent resin layer mainly composed of a highly crystalline polypropylene resin
- a low crystalline polypropylene resin having a tensile elastic modulus of 25 MPa or more and 500 MPa or less is added in an amount of 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the high crystalline polypropylene resin.
- the transparent resin layer is formed by adding a nano-sized nucleating agent to the highly crystalline polypropylene resin.
- the surface strength (scratch resistance) of the decorative sheet is increased by using a highly crystalline polypropylene resin as the main component of the transparent resin layer.
- the low crystalline polypropylene resin is highly compatible with the high crystalline polypropylene resin, high transparency with respect to the transparent resin layer can be obtained by adding the low crystalline polypropylene resin whose tensile modulus is in the above range. It is possible to improve post-workability while imparting.
- a decorative sheet excellent in scratch resistance and post-processability can be obtained.
- the crystallinity of the highly crystalline polypropylene resin is improved, and extremely high transparency is achieved.
- a decorative sheet having the same can be obtained.
- the scratch resistance and post-processability of the decorative sheet can be further improved.
- the decorative sheet 1 of the present embodiment a plurality of resin layers are laminated on the surface side of the base material layer 6, and the transparent resin layer 3 is disposed as a resin layer on the surface side of the plurality of resin layers.
- the decorative sheet 1 of the present embodiment has a pattern layer 5 and a transparent resin layer on one surface (surface) of the base material layer 6 constituting the raw fabric layer. 3 and the surface protective layer 2 are laminated in this order.
- Reference numeral 4 denotes an adhesive layer.
- the concealing layer 7 and the primer layer 8 are formed in this order on the other surface (back surface) of the base material layer 6.
- the concealing layer 7 may be formed between the base layer 6 and the pattern layer 5 or may be omitted.
- the layer thickness of the decorative sheet 1 having the above configuration is 3 to 20 ⁇ m for the surface protective layer 2, 20 to 200 ⁇ m for the transparent resin layer 3, and 1 to 1 for the adhesive layer 4 in consideration of printing workability and cost.
- the pattern layer 5 is 3 to 20 ⁇ m
- the base layer 6 is 20 to 150 ⁇ m
- the masking layer 7 is 2 to 20 ⁇ m
- the primer layer 8 is 0.1 to 20 ⁇ m
- the total thickness of the decorative sheet 1 is 49 Within the range of 450 ⁇ m.
- FIG. 1 the case where the decorative sheet 1 of this embodiment is affixed on the base material B and the decorative board is comprised is illustrated.
- the base material layer 6 is comprised from paper, a resin sheet, foil, etc.
- paper include thin paper, titanium paper, resin-impregnated paper, organic or inorganic nonwoven fabric, and synthetic paper.
- the resin for the resin sheet include polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic and other synthetic resins, foams of these synthetic resins, and ethylene-propylene copolymers.
- Examples of the rubber include polymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane.
- Examples of the foil include metal foils such as aluminum, iron, gold, and silver.
- the pattern pattern layer 5 can be provided using a known printing method.
- printing for forming the pattern layer 5 can be performed with a roll-to-roll printing apparatus.
- the printing method is not particularly limited, but for example, a gravure printing method can be used in consideration of productivity and picture quality.
- the design pattern it is sufficient to adopt an arbitrary design pattern in consideration of the design properties according to the use place such as flooring or wall material, and various wood grain is often used if it is a wood type design, In addition to the grain, cork can be used as a pattern. For example, if it is an image of a stone floor such as marble, it may be used as a pattern such as a marble stone.
- an artificial pattern such as an artificial pattern or a geometric pattern using these as a motif can also be used.
- the ink corresponding to a printing system can be selected suitably.
- a colorant such as a pigment or a dye, an extender pigment, a solvent, and a binder, which are contained in a normal ink, are appropriately added.
- the pigment include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica.
- the binder may be water-based, solvent-based, or emulsion type, and the curing method is particularly limited, such as a one-component type, a two-component type consisting of a main agent and a curing agent, or a type that is cured by ultraviolet rays or electron beams. Not what you want. Among them, the most common method is a two-component type, which uses a urethane-based main agent and a curing agent made of isocyanate. In addition, the design may be applied by vapor deposition or sputtering of various metals.
- the adhesive layer 4 is provided for the purpose of strengthening the adhesion between the base material layer 6 and the pattern / pattern layer 5 and the transparent resin layer 3. When this adhesion is strong, it is possible to give the decorative sheet 1 bending workability that follows a curved surface or a right angle surface.
- the adhesive layer 4 is preferably transparent.
- the adhesive layer 4 can be selected from any material as an adhesion method, and includes a laminating method such as thermal lamination, extrusion lamination, and dry lamination.
- the adhesive may be acrylic, polyester, polyurethane, epoxy, or the like. It can be selected as appropriate.
- a urethane-based material obtained by a reaction with a polyol using an isocyanate as a two-component curing type because of its cohesive strength.
- the adhesive layer 4 may be omitted when the adhesive strength between the transparent resin layer 3 and the pattern layer 5 is sufficiently obtained.
- the transparent resin layer 3 is manufactured and laminated as a transparent resin sheet, for example.
- the transparent resin layer 3 contains a highly crystalline polypropylene resin as a main component.
- the main component refers to, for example, 80 to 100 parts by mass, preferably 90 to 100 parts by mass of the resin constituting the transparent resin layer 3.
- 0.1 to 20 parts by mass of a low crystalline polypropylene resin having a tensile modulus of 25 MPa or more and 500 MPa or less is added to 100 parts by mass of the high crystalline polypropylene resin.
- the tensile modulus is more preferably 50 to 120 MPa.
- the highly crystalline polypropylene resin that is the main component of the transparent resin layer 3 is designed by appropriately selecting, for example, isotactic polypropylene, syndiotactic polypropylene, random polypropylene, block polypropylene, and mixtures thereof having different pentad fractions. Can do.
- the highly crystalline polypropylene resin is a homopolymer of propylene having a pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more, that is, a highly crystalline homopolypropylene. It is preferable to use a resin.
- the pentad fraction (mmmm fraction) is a resin composition constituting the transparent resin layer 3 by a 13 C-NMR measurement method (nuclear magnetic resonance measurement method) using carbon C (nuclide) having a mass number of 13. It is calculated from a numerical value (electromagnetic wave absorption rate) obtained by resonating an object at a predetermined resonance frequency.
- the pentad fraction (mmmm fraction) defines the atomic arrangement, electronic structure, and molecular microstructure in the resin composition.
- the pentad fraction of the polypropylene resin is a ratio of five propylene units determined by 13 C-NMR, and is used as a measure of crystallinity or stereoregularity.
- a pentad fraction is one of the important factors that mainly determine the scratch resistance of the surface. Basically, the higher the pentad fraction, the higher the crystallinity of the sheet. Will improve. And the surface strength (scratch resistance) of a decorative sheet becomes high by making the main component of the transparent resin layer 3 into a highly crystalline polypropylene resin.
- the low crystalline polypropylene resin added to the transparent resin layer 3 is preferably a polypropylene resin satisfying at least one of the following characteristics.
- ⁇ Mesopentad fraction is 20-60% (More preferably, 40 to 55%)
- ⁇ MFR at 230 °C is 30-100 (More preferably, 30-60)
- Mass average molecular weight (Mw) is 10,000 to 500,000 (More preferably, 50,000 to 200,000)
- Mw / Mn is less than 4.
- a differential scanning calorimeter (DSC) is obtained by holding at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere and then increasing the temperature at 10 ° C./minute.
- the melting point defined as the peak top of the peak observed on the highest temperature side of the melting endotherm curve is 0 to 120 ° C (More preferably, 40 to 100 ° C.)
- Low crystalline polypropylene resins tend to have low crystallinity, softness, low melting point, and high solubility in solvents. By adopting such low crystalline polypropylene resins, they can be added to high crystalline polypropylene resins. In this case, while having the performance of high compatibility and slowing down the crystallization speed, the crystallinity of the highly crystalline polypropylene resin is not affected, or the influence on the crystallinity is greatly reduced.
- a nano-sized nucleating agent is added to the transparent resin layer 3.
- the nano-sized nucleating agent is preferably added in the form of a nucleating agent vesicle encapsulated in a vesicle having a single-layer outer membrane.
- the nucleating agent vesicle can be prepared by the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, the supercritical reverse phase evaporation method and the like. Among them, the supercritical reverse phase evaporation method is particularly preferable.
- Supercritical reversed-phase evaporation method is a method of producing nano-sized vesicles (capsules) encapsulating target substances using carbon dioxide under supercritical conditions, temperature conditions above the critical point or pressure conditions above the critical point. It is. Carbon dioxide in the supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ⁇ 0.0030 MPa) or higher, under temperature conditions above the critical point or Carbon dioxide under pressure conditions above the critical point means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical condition.
- an emulsion of supercritical carbon dioxide and an aqueous phase is generated by injecting and stirring the aqueous phase into a mixed fluid of supercritical carbon dioxide, phospholipid, and nucleating agent as an inclusion substance. Thereafter, when the pressure is reduced, carbon dioxide expands and evaporates to cause phase inversion, and nanovesicles in which the surface of the nucleating agent nanoparticles are covered with a monolayer film are generated. According to this supercritical reverse phase evaporation method, since a vesicle of a single layer film can be generated, a very small size vesicle can be obtained.
- the average particle diameter of the nucleating agent vesicle encapsulating the nano-sized nucleating agent is preferably 1 ⁇ 2 or less of the visible light wavelength (400 to 750 nm), more specifically 200 nm to 375 nm or less.
- the nucleating agent is not particularly limited as long as it is a substance that becomes a starting point of crystallization when the resin is crystallized.
- the nucleating agent include phosphoric acid ester metal salts, benzoic acid metal salts, pimelic acid metal salts, rosin metal salts, benzylidene sorbitol, quinacridone, cyanine blue and talc.
- phosphoric acid ester metal salts phosphoric acid ester metal salts
- benzoic acid metal salts pimelic acid metal salts
- rosin metal salts benzylidene sorbitol
- quinacridone quinacridone
- cyanine blue and talc cyanine blue and talc.
- a molten benzylidene sorbitol may be appropriately mixed and used with a non-melting nucleating agent.
- the transparent resin layer contains a nucleating agent contained in a vesicle”. Then, by adding the nucleating agent to the resin composition in a state where the nucleating agent is encapsulated in the vesicle, there is an effect that the dispersibility of the nucleating agent in the resin material, that is, in the transparent resin layer is drastically improved. It can be said that it is impractical to specify the characteristics directly by the structure and characteristics of the object in the state of the finished decorative sheet, because it may be difficult depending on the situation. The reason is as follows.
- the nucleating agent added in the state of vesicle is in a dispersed state having high dispersibility, and the nucleating agent is highly dispersed in the transparent resin layer even in the state of the produced decorative sheet.
- the decorative sheet is usually produced by a compression treatment or curing to the laminate.
- Various treatments such as treatment are performed, but by such treatment, the outer membrane of the vesicle encapsulating the nucleating agent is crushed or chemically reacted, and the nucleating agent is not included (encapsulated) in the outer membrane.
- the present invention is different from the conventional one in that the nucleating agent is blended in a highly dispersed state, whether or not it is because it is added in the state of a vesicle encapsulating the nucleating agent is a cosmetic. In the state of the sheet, it may be impractical to specify the structure and characteristics within the numerical range analyzed based on the measurement.
- a surface protective layer 2 On the outermost surface of the decorative sheet 1, there is provided a surface protective layer 2 that serves as surface protection and gloss adjustment.
- the material for the surface protective layer 2 can be appropriately selected from polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, and the like.
- the form of the material is not particularly limited, such as aqueous, emulsion, solvent type.
- the curing method can be appropriately selected from a one-component type, a two-component type, an ultraviolet curing method, and the like.
- Isocyanates include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), methylhexane diisocyanate (HTDI), although it can be appropriately selected from methylcyclohexanone diisocyanate (HXDI), trimethylhexamethylene diisocyanate (TMDI), etc., in view of weather resistance, hexamethylene diisocyanate (HMDI) having a linear molecular structure is preferred.
- a resin curable with active energy rays such as ultraviolet rays and electron beams.
- active energy rays such as ultraviolet rays and electron beams.
- These resins can be used in combination with each other.
- a hybrid type of a thermosetting type and a photocurable type it is possible to improve surface hardness, suppress curing shrinkage, and improve adhesion. Can be planned.
- the concealing layer 7 is formed by printing, for example, in the same manner as the picture pattern layer 5 for the purpose of maintaining concealment.
- the pigment to be included in the ink it is preferable to use an opaque pigment, titanium oxide, iron oxide or the like. It is also possible to add metals such as gold, silver, copper, and aluminum in order to improve the concealing property. In general, flaky aluminum is often added.
- the masking layer 7 can be omitted when the base material layer 6 is opaque and has masking properties.
- the primer layer 8 is formed in order to improve the adhesion with the base material B.
- the primer layer 8 is, for example, an ester resin, a urethane resin, an acrylic resin, a polycarbonate resin, a vinyl chloride-vinyl acetate copolymer, a polyvinyl butyral resin.
- a nitrocellulose-based resin can be used, and these resins can be used alone or mixed to form an adhesive composition, which can be formed using an appropriate coating means such as a roll coating method or a gravure printing method.
- the resin constituting the primer layer 8 is preferably a urethane-acrylate resin, that is, it is particularly preferably formed of a resin composed of a copolymer of an acrylic resin and a urethane resin and an isocyanate.
- a low crystalline polypropylene resin having a tensile elastic modulus in the range of the present embodiment is added to the transparent resin layer 3 mainly composed of a high crystalline polypropylene resin within the range of the present embodiment. Since the low crystalline polypropylene resin is highly compatible with the high crystalline polypropylene resin, high transparency can be imparted to the transparent resin layer 3. Furthermore, by making the addition amount of the low crystalline polypropylene resin within the range of this embodiment, a decorative sheet having excellent scratch resistance and post-processability can be obtained.
- the mesopentad fraction of the low crystalline polypropylene resin is 20 to 60%. By setting the mesopentad fraction to 20 to 60%, solidification does not slow during melt extrusion, and sticking of the transparent resin layer 3 after film formation can be suppressed.
- the MFR of the low crystalline polypropylene resin at 230 ° C. is 30-100. By setting the MFR of the low crystalline polypropylene resin within this range, the flowability of the low crystalline polypropylene resin becomes appropriate, and the film can be formed without any problem in a melt extruder.
- the mass average molecular weight (Mw) of the low crystalline polypropylene resin is 10,000 to 500,000. By setting the mass average molecular weight of the low crystalline polypropylene resin within this range, the viscosity of the low crystalline polypropylene resin becomes moderate, and a film can be formed without any problem during melt extrusion.
- the molecular weight distribution (Mw / Mn) of the low crystalline polypropylene resin is less than 4. By making molecular weight distribution into this range, the fall of the film forming property of the transparent resin layer 3 is suppressed.
- a nano-processed nucleating agent is added to the transparent resin layer 3.
- the dispersibility of the nucleating agent in the transparent resin layer 3 can be remarkably improved.
- scratch resistance can be improved while maintaining transparency and post-processability.
- the transparent resin layer 3 is formed by adding a nano-structured nucleating agent to a highly crystalline polypropylene resin.
- the nucleating agent By subjecting the nucleating agent to nano-treatment, the dispersibility of the nucleating agent in the transparent resin layer 3 can be remarkably improved. As a result, scratch resistance can be improved while maintaining transparency and post-processability.
- the nucleating agent is a nucleating agent vesicle in which a nucleating agent is included in a vesicle having an outer layer of a single layer film.
- the nucleating agent is encapsulated in the vesicle by the supercritical reverse phase evaporation method.
- the nucleating agent can be surely included in the vesicle.
- the basic manufacturing method of each decorative sheet is as follows.
- a highly crystalline polypropylene resin a highly crystalline homopolypropylene resin having a pentad fraction of 97.8%, an MFR (melt flow rate) of 15 g / 10 min (230 ° C.), and a molecular weight distribution MWD (Mw / Mn) of 2.3 is used. used.
- Hindered phenolic antioxidant (Irganox 1010: manufactured by BASF) 500PPM, benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by BASF) 2000PPM, hindered amine light High crystallinity with a thickness of 80 ⁇ m is used as a transparent resin layer 3 by extruding a resin (Kimasorb 944: manufactured by BASF) with 2000 PPM and a low crystalline polypropylene resin using a melt extruder. A transparent resin sheet made of polypropylene resin was formed.
- the corona treatment was applied to both surfaces of the obtained transparent resin sheet, and the wet tension of the transparent resin sheet surface was set to 40 dyn / cm or more.
- a two-component urethane ink (V180; manufactured by Toyo Ink Manufacturing Co., Ltd.) is hindered with respect to the binder resin content of the ink.
- the pattern layer 5 was provided by performing pattern printing by a gravure printing method using an ink to which 0.5% by mass of a light stabilizer (Kimasorb 944; manufactured by BASF) was added.
- a primer layer 8 was provided on the other surface of the base material layer 6.
- the transparent resin sheet 3 is passed through an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc .; application amount 2 g / m 2 ) as the adhesive layer 4. Were bonded together by a dry laminating method.
- embossed pattern 3a is applied to the surface of transparent resin sheet 3
- a two-component curable urethane topcoat (W184; manufactured by DIC Graphics) is applied at a coating thickness of 6 g / m 2 to form surface protective layer 2.
- the decorative sheet of the present invention shown in FIG. 2 having a total thickness of 170 ⁇ m was obtained.
- the low crystalline polypropylene resin to be added is as shown in Table 1.
- the nano-ized nucleating agent was added.
- a nucleating agent vesicle vesicled by a supercritical reverse phase evaporation method was used as the nano-structured nucleating agent. That is, a resin composition for forming the transparent resin layer 3 was prepared using a supercritical reverse phase evaporation method as follows.
- a nucleating method for a nucleating agent using a supercritical reverse phase evaporation method is as follows: 100 parts by mass of methanol, phosphate metal salt nucleating agent as a nucleating agent (ADK STAB NA-11, manufactured by ADEKA) 82 parts by mass, 5 parts by mass of phosphatidylcholine as a substance constituting the outer membrane of the vesicle are placed in a high-pressure stainless steel container kept at 60 ° C. and sealed, and carbon dioxide is injected so that the pressure becomes 20 MPa. Then, 100 parts by mass of ion-exchanged water is injected with vigorous stirring and mixing.
- a nucleating agent comprising an outer membrane composed of a phospholipid encapsulating a nucleating agent by stirring for 15 minutes while maintaining the temperature and pressure in a supercritical state and then discharging carbon dioxide to return to atmospheric pressure. Liposomes are obtained.
- the pentad fraction is 97.8%
- the MFR melting flow rate
- MWD molecular weight distribution MWD
- vesicles whose outer membrane is composed of biological lipids such as phospholipids are referred to as liposomes.
- liposomes vesicles whose outer membrane is composed of biological lipids such as phospholipids.
- ⁇ Comparative Examples 1 to 7> The presence / absence of low crystalline polypropylene resin, its constitution and the presence / absence of a nucleating agent were set as shown in Table 2 to produce a decorative sheet of a comparative example. Others were produced in the same manner as in the examples.
- I997 is a peak intensity value of the wave number 997cm -1
- I938 is a peak intensity value of the wave number 938cm -1
- I973 represents the peak intensity value of the wave number 973 cm -1.
- each decorative sheet 1 produced by the above method is attached to one surface of a medium fiber board (MDF) constituting the base material B using a urethane-based adhesive, and the other side of the base material B A V-shaped groove is inserted up to the boundary where the base material B and the decorative sheet 1 are bonded together so that the decorative sheet 1 on the opposite side is not scratched.
- MDF medium fiber board
- the base material B is bent up to 90 degrees along the V-shaped groove so that the surface of the decorative sheet 1 is mountain-folded, and no whitening or cracking occurs in the bent portion of the surface of the decorative sheet 1.
- the decorative sheet of Comparative Example 1 is whitened during V-groove processing.
- neck-in occurs during melt extrusion, resulting in poor film formation.
- the decorative sheet of Comparative Example 3 neck-in occurs during melt extrusion, resulting in poor film formation.
- the decorative sheet of the comparative example 4 it whitened at the time of V-groove processing.
- the decorative sheet of Comparative Example 5 was whitened during V-groove processing.
- the amount of the low crystalline polypropylene resin added was too small and the post-processability was not improved, that is, whitened. Further, in the decorative sheet of Comparative Example 7, since the amount of the low crystalline polypropylene resin added was too large, neck-in occurred at the time of melt extrusion, and the scratch resistance was deteriorated due to the resin being too soft.
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Abstract
Description
しかし、従来のオレフィン系樹脂製の化粧シートは、一般的なポリプロピレンシートを使用しているために表面の耐傷性が悪く、従来のポリ塩化ビニル製の化粧シートに比べて耐傷性に劣っているものであった。
ここで、後加工性を向上させた化粧シートとして、特許文献4~6に記載の化粧シートが提案されている。これらの化粧シートは、ランダム重合タイプのポリプロピレン樹脂に軟質成分を添加した透明樹脂層をもつ化粧シートである。しかしながら、この化粧シートは、後加工性の向上に伴いシートが柔軟になっていることから、耐傷性が悪化するという問題点がある。
課題を解決するために、本発明の一態様である化粧シートは、高結晶性ポリプロピレン樹脂を主成分とする透明樹脂層を少なくとも具備してなる化粧シートであって、
上記透明樹脂層は、高結晶性ポリプロピレン樹脂100質量部に対し、引張り弾性率が25MPa以上500MPa以下の低結晶性ポリプロピレン樹脂が0.1質量部以上20質量部以下で添加されている。
また、本発明の一態様である化粧シートの製造方法は、上記透明樹脂層を、上記高結晶性ポリプロピレン樹脂に、ナノサイズの造核剤を添加して形成する。
また、低結晶性ポリプロピレン樹脂は高結晶性ポリプロピレン樹脂と高い相溶性を示すため、引張り弾性率が上記の範囲である低結晶性ポリプロピレン樹脂を添加することで、透明樹脂層に対して高い透明性を付与しつつ後加工性を向上させることができる。さらに、低結晶性ポリプロピレン樹脂の添加量を上記の範囲とすることによって、耐傷性と後加工性に優れた化粧シートを得ることができる。
また、上記の高結晶性ポリプロピレン樹脂にナノサイズの造核剤を添加して、上記の透明樹脂層を形成することで、高結晶性ポリプロピレン樹脂の結晶化度が向上し、極めて高い透明性を有する化粧シートを得ることができる。また、化粧シートの耐傷性と後加工性とをさらに向上させることができる。
ここで、図面は模式的なものであり、厚さと平面寸法との関係、各層の厚さの比率等は現実のものとは異なる。また、以下に示す実施形態は、本発明の技術的思想を具体化するための構成を例示するものであって、本発明の技術的思想は、構成部品の材質、形状、構造等が下記のものに特定するものでない。本発明の技術的思想は、特許請求の範囲に記載された請求項が規定する技術的範囲内において、種々の変更を加えることができる。
また、基材層6の他方の面(裏面)に、隠蔽層7、プライマー層8がこの順に形成されている。なお、隠蔽層7は、基材層6と絵柄模様層5との間に形成しても良いし、省略しても構わない。
なお、図1においては、本実施形態の化粧シート1を基材Bに貼り付けて化粧板を構成する場合を例示している。
基材層6は、紙、樹脂シート、箔などから構成される。紙としては、薄葉紙、チタン紙、樹脂含浸紙、有機もしくは無機系の不織布、合成紙等が例示出来る。樹脂シートの樹脂としては、ポリエチレン、ポリプロピレン、ポリブチレン、ポリスチレン、ポリカーボネート、ポリエステル、ポリアミド、エチレン-酢酸ビニル共重合体、ポリビニルアルコール、アクリル等の合成樹脂、あるいはこれら合成樹脂の発泡体、エチレン-プロピレン共重合ゴム、エチレン-プロピレン-ジエン共重合ゴム、スチレン-ブタジエン共重合ゴム、スチレン-イソプレン-スチレンブロック共重合ゴム、スチレン-ブタジエン-スチレンブロック共重合ゴム、ポリウレタン等のゴムが例示出来る。箔としては、アルミニウム、鉄、金、銀等の金属箔等が例示出来る。
絵柄模様層5は、既知の印刷手法を用いて設けることが出来る。基材層6が巻取りの状態で用意できる場合には、ロールツーロールの印刷装置で絵柄模様層5の形成のための印刷を行うことができる。印刷手法は特に限定するものではないが、生産性や絵柄の品位を考慮すれば、例えばグラビア印刷法を用いることができる。
絵柄模様は、床材や壁材などの使用箇所に応じた意匠性を考慮して任意の絵柄模様を採用すればよく、木質系の絵柄であれば各種木目が好んで用いられることが多く、木目以外にもコルクを絵柄模様とすることもできる。例えば大理石などの石材の床をイメージしたものであれば大理石の石目などの絵柄模様として用いられることもある。また天然材料の絵柄模様以外にそれらをモチーフとした人工的絵柄模様や幾何学模様などの人工的絵柄模様も用いることができる。
印刷インキには、適宜、通常のインキに含まれている顔料、染料等の着色剤、体質顔料、溶剤、バインダーを添加する。顔料としては、縮合アゾ、不溶性アゾ、キナクリドン、イソインドリン、アンスラキノン、イミダゾロン、コバルト、フタロシアニン、カーボン、酸化チタン、酸化鉄、雲母等のパール顔料等が挙げられる。なお、バインダーは、水性、溶剤系、エマルジョンタイプのいずれでもよく、硬化方法についても1液タイプ、主剤と硬化剤とからなる2液タイプ、もしくは、紫外線や電子線などによって硬化するタイプなど特に限定するものではない。中でも最も一般的な方法は、2液タイプのもので、ウレタン系の主剤と、イソシアネートからなる硬化剤を用いる方法である。この他にも、各種金属の蒸着やスパッタリングで意匠を施すようにしてもよい。
接着剤層4は、基材層6および絵柄模様層5と透明樹脂層3の接着を強固にする目的で設けられる。この接着が強固であることによって、化粧シート1に対し、曲面や直角面に追随する曲げ加工性を付与することができる。接着剤層4は透明であることが好ましい。
接着剤層4は、その接着方法としては任意の材料選定が可能で、熱ラミネート、押出ラミネート、ドライラミネート等による積層方法があり、接着剤はアクリル系、ポリエステル系、ポリウレタン系、エポキシ系などから適宜選択できる。通常はその凝集力から2液硬化タイプのものとして、特にイソシアネートを用いたポリオールとの反応で得られるウレタン系の材料を用いることが望ましい。なお、接着剤層4は、透明樹脂層3と絵柄模様層5との接着強度が十分に得られる場合には、省略してもよい。
透明樹脂層3は、例えば透明樹脂シートとして製造して積層する。
透明樹脂層3は、高結晶性ポリプロピレン樹脂を主成分とする。主成分とは、例えば、透明樹脂層3を構成する樹脂のうちの80~100質量部、好ましくは90~100質量部であることを指す。
本実施形態の透明樹脂層3には、高結晶性ポリプロピレン樹脂100質量部に対し、引張り弾性率が25MPa以上500MPa以下の低結晶性ポリプロピレン樹脂が0.1~20質量部添加されている。引張り弾性率は、より好ましくは50~120MPaである。
透明樹脂層3の主成分となる高結晶性ポリプロピレン樹脂は、例えば、ペンタッド分率の異なるアイソタクチックポリプロピレンとシンジオタクチックポリプロピレン、ランダムポリプロピレン、ブロックポリプロピレンおよびこれらの混合物から適宜選択して設計することができる。本実施形態においては、当該高結晶性ポリプロピレン樹脂が、ペンタッド分率(mmmm分率)が95%以上、より好ましくは96%以上のプロピレンの単独重合体、すなわちホモポリマーである高結晶性ホモポリプロピレン樹脂とされることが好ましい。
そして、透明樹脂層3の主成分を高結晶性ポリプロピレン樹脂とすることで、化粧シートの表面強度(耐傷性)が高くなる。
透明樹脂層3に添加する低結晶性ポリプロピレン樹脂としては、下記に示す特徴のうちの少なくとも1つを満たすポリプロピレン樹脂であることが好ましい。
・メソペンタッド分率が20~60%
(より好ましくは、40~55%)
・230℃におけるMFRが30~100
(より好ましくは、30~60)
・質量平均分子量(Mw)が10,000~500,000
(より好ましくは、50,000~200,000)
・分子量分布(Mw/Mn)が4未満
・示差走査型熱量計(DSC)を用いて、窒素雰囲気下で、-10℃で5分間保持した後10℃/分で昇温させることによって得られた融解吸熱カーブの最も高温側に観測されるピークのピークトップとして定義される融点が0~120℃
(より好ましくは、40~100℃)
透明樹脂層3に、ナノサイズの造核剤が添加されていることが好ましい。特に、ナノサイズの造核剤が、単層膜の外膜を具備するベシクルに内包された、造核剤ベシクルの形で添加されていることが好ましい。
高結晶性ポリプロピレン樹脂に対して造核剤ベシクルを添加することにより、高結晶性ポリプロピレン樹脂の結晶化度を向上させて、極めて高い透明性を有する透明樹脂シートを得ることができる。即ち、ナノサイズの造核剤を添加することで、耐傷性をさらに向上させることが出来る。
造核剤ベシクルは、Bangham法、エクストルージョン法、水和法、界面活性剤透析法、逆相蒸発法、凍結融解法、超臨界逆相蒸発法などによって調製することができる。その中でも特に超臨界逆相蒸発法がより好ましい。
化粧シート1の最表面には、表面の保護や艶の調整としての役割を果たす表面保護層2が設けられている。
表面保護層2の材料としては、ポリウレタン系、アクリルシリコン系、フッ素系、エポキシ系、ビニル系、ポリエステル系、メラミン系、アミノアルキッド系、尿素系などから適宜選択して用いることができる。材料の形態は、水性、エマルジョン、溶剤系など特に限定されるものではない。硬化法についても一液タイプ、二液タイプ、紫外線硬化法など適宜選択して行うことができる。
隠蔽層7は、隠蔽性を保たせることを目的として、例えば、絵柄模様層5と同様に印刷によって形成される。インキに含ませる顔料としては不透明な顔料、酸化チタン、酸化鉄等を使用することが好ましい。また隠蔽性を上げるために金、銀、銅、アルミ等の金属を添加することも可能である。一般的にはフレーク状のアルミを添加することが多い。なお、隠蔽層7は、基材層6が不透明で隠蔽性を有している場合には、省略することができる。
プライマー層8は、基材Bとの密着性を向上させるために形成する。
プライマー層8は、基材Bが木質系基材Bの場合には、例えば、エステル系樹脂、ウレタン系樹脂、アクリル系樹脂、ポリカーボネート系樹脂、塩化ビニル-酢酸ビニル共重合体、ポリビニルブチラール系樹脂、ニトロセルロース系樹脂等を挙げることができ、これらの樹脂は単独ないし混合して接着組成物とし、ロールコート法やグラビア印刷法等の適宜の塗布手段を用いて形成することができる。この場合、プライマー層8を構成する樹脂としては、ウレタン-アクリレート系樹脂が好ましい、すなわち、アクリル系樹脂とウレタン系樹脂との共重合体とイソシアネートとからなる樹脂で形成するのが特に好ましい。
(1)高結晶性ポリプロピレン樹脂を主成分とする透明樹脂層3に、引張り弾性率を本実施形態の範囲とする低結晶性ポリプロピレン樹脂を本実施形態の範囲内で添加する。
低結晶性ポリプロピレン樹脂は、高結晶性ポリプロピレン樹脂と高い相溶性を示すため、透明樹脂層3に対して高い透明性を付与することができる。
さらに、低結晶性ポリプロピレン樹脂の添加量を本実施形態の範囲とすることによって、耐傷性と後加工性に優れた化粧シートを得ることができる。
メソペンタッド分率を20~60%とすることで、溶融押出時に固化が遅くならず、製膜後の透明樹脂層3がべたつくのを抑制することができる。
(3)低結晶性ポリプロピレン樹脂の230℃におけるMFRが30~100である。
低結晶性ポリプロピレン樹脂のMFRを該範囲とすることにより、低結晶性ポリプロピレン樹脂の流動性が適度となり、溶融押出機にて問題なく製膜することができる。
低結晶性ポリプロピレン樹脂の質量平均分子量を該範囲とすることにより、低結晶性ポリプロピレン樹脂の粘度が適度となり、溶融押出時に問題なく製膜することができる。
(5)低結晶性ポリプロピレン樹脂の分子量分布(Mw/Mn)が4未満である。
分子量分布を該範囲とすることにより、透明樹脂層3の製膜性の低下が抑制される。
このような低結晶性ポリプロピレン樹脂を使用することで、透明樹脂層3に含まれる添加剤のブリードを抑制することができる。
造核剤にナノ化処理を施すことによって、透明樹脂層3に対する造核剤の分散性を著しく向上させることができる。これによって、透明性と後加工性を維持したまま、耐傷性を向上させることができる。
造核剤にナノ化処理を施すことによって、透明樹脂層3に対する造核剤の分散性を著しく向上させることができる。これによって、透明性と後加工性を維持したまま、耐傷性を向上させることができる。
造核剤をベシクルに内包させることによって、透明樹脂層3に対する造核剤の分散性をさらに向上させることができる。これによって、透明性と後加工性を維持したまま、耐傷性をさらに向上させることができる。
超臨界逆相蒸発法を用いることによって、造核剤をベシクルに確実に内包させることができる。
<実施例1~22>
各実施例として、透明樹脂層3の主成分である高結晶性ポリプロピレン樹脂100質量部に対して、表1に示すように、低結晶性ポリプロピレン樹脂を添加した透明樹脂層3を有する化粧シート1とした。
各化粧シートの基本的な製造方法については以下のとおりである。
高結晶性ポリプロピレン樹脂としてペンタッド分率が97.8%、MFR(メルトフローレート)が15g/10min(230℃)、分子量分布MWD(Mw/Mn)が2.3の高結晶性ホモポリプロピレン樹脂を使用した。
各実施例において、添加する低結晶性ポリプロピレン樹脂は、表1に記載の通りである。
また、実施例17と実施例21については、ナノ化した造核剤を添加した。ナノ化した造核剤は、後述の通り、超臨界逆相蒸発法によりベシクル化された造核剤ベシクルを使用した。
すなわち、次のようにして、超臨界逆相蒸発法を用いて透明樹脂層3を形成する樹脂組成物の調製を行った。
ここで、外膜がリン脂質のような生体脂質から構成されるベシクルをリポソームと称する。
<比較例1~7>
低結晶性ポリプロピレン樹脂の有無及びその構成、造核剤の有無を、表2のように設定して、比較例の化粧シートを製造した。その他は実施例と同じようにして製造した。
各実施例の化粧シート、及び各比較例の化粧シートについて、製膜性、結晶性の低下(結晶化度)、透明性、耐傷性、後加工性にて評価を行った。
その結果を、表3,表4に示す。
溶融押出時の透明樹脂シートの状態を目視にて観察した。
評価は下記の2段階にて行った。
○:良好(ネックインやフィルムの破断が確認できなかった)
×:劣る(ネックインやフィルムの破断が認められた)
[結晶性の低下]
結晶性について、IRにて結晶化度を算出したのち、低結晶性ポリプロピレン樹脂を添加していない場合(比較例1)と数値を比較した。
結晶化度は、フーリエ型赤外分光測定において得られた吸光スペクトルから下記の数式1を用いて算出した。ここで、数式1において、I997は波数997cm-1のピーク強度値、I938は波数938cm-1のピーク強度値、I973は波数973cm-1のピーク強度値をあらわす。
○:良好(比較例1の結晶化度と同等以上)
×:劣る(比較例1の結晶化度より劣る)
[透明性]
製造した透明樹脂層3を目視で観察し、下層の絵柄模様の視認性によって評価した。
評価は下記の3段階にて行った。
○:良好(透明である)
△:意匠性は問題ないが、やや白濁している(実用上問題ないレベル)
×:劣る(白濁している)
[耐傷性]
鉛筆硬度試験にて評価した。
試験方法はJIS-K5600に準拠し、評価方法としては、透明樹脂層3の表面に凹みが付かない最高硬度がHB以上の場合「◎」、2B以上の場合「○」、3B以下の場合「×」とした。
V溝曲げ加工適性試験に評価した。
以下に、V溝曲げ加工適性試験の詳しい方法について述べる。
まず、基材Bを構成する中質繊維板(MDF)の一方の面に対して、上記の方法で作製した各化粧シート1をウレタン系の接着剤を用いて貼り付け、基材Bの他方の面に対して、反対側の化粧シート1にキズが付かないようにV型の溝を基材Bと化粧シート1とを貼り合わせている境界まで入れる。次に、化粧シート1の面が山折りとなるように基材Bを当該V型の溝に沿って90度まで曲げ、化粧シート1の表面の折れ曲がった部分に白化や亀裂などが生じていないかを光学顕微鏡を用いて観察し、耐後加工性の優劣の評価を行う。
評価は下記の3段階にて行った。
○:白化・亀裂などが認められなかった
△:軽微な白化・亀裂が認められるが、実用上問題ないレベルである
×:化粧シートとして容認できない白化・亀裂が認められた
また、比較例2の化粧シートでは、溶融押出時にネックインが発生し、製膜不良となっている。更に軟らかすぎて耐傷性が劣化した。
また、比較例3の化粧シートでは、溶融押出時にネックインが発生し、製膜不良となっている。更に軟らかすぎて耐傷性が劣化した。
また、比較例4の化粧シートでは、V溝加工時に白化した。
また、比較例5の化粧シートでは、V溝加工時に白化した。
また、比較例6の化粧シートでは、低結晶性ポリプロピレン樹脂の添加量が少なすぎて、後加工性が良化しなかった、すなわち、白化した。
また、比較例7の化粧シートでは、低結晶性ポリプロピレン樹脂の添加量が多すぎるため、溶融押出時にネックインが発生するとともに、樹脂が軟化しすぎてしまうことによって耐傷性が劣化した。
2 表面保護層
3 透明樹脂層
3a エンボス模様
4 接着剤層
5 絵柄模様層
6 基材層
7 隠蔽層
8 プライマー層
B 基材
Claims (13)
- 高結晶性ポリプロピレン樹脂を主成分とする透明樹脂層を有する化粧シートであって、
上記透明樹脂層は、高結晶性ポリプロピレン樹脂100質量部に対し、引張り弾性率が25MPa以上500MPa以下の低結晶性ポリプロピレン樹脂が0.1質量部以上20質量部以下で添加されていることを特徴とする化粧シート。 - 上記低結晶性ポリプロピレン樹脂は、メソペンタッド分率が20%以上60%以下であることを特徴とする請求項1に記載の化粧シート。
- 上記低結晶性ポリプロピレン樹脂は、230℃におけるMFR(melt flow rate)が30以上100以下であることを特徴とする請求項1又は請求項2に記載の化粧シート。
- 上記低結晶性ポリプロピレン樹脂は、質量平均分子量(Mw)が10,000以上500,000以下であることを特徴とする請求項1~請求項3のいずれか1項に記載の化粧シート。
- 上記低結晶性ポリプロピレン樹脂の分子量分布(Mw/Mn)が4未満であることを特徴とする請求項1~請求項4のいずれか1項に記載の化粧シート。
- 上記低結晶性ポリプロピレン樹脂は、示差走査型熱量計(DSC)を用いて、窒素雰囲気下、-10℃で5分間保持した後、10℃/分で昇温させることによって得られた融解吸熱カーブの最も高温側に観測されるピークのピークトップとして定義される融点が、0℃以上120℃以下であることを特徴とする請求項1~請求項5のいずれか1項に記載の化粧シート。
- 上記透明樹脂層に、ナノサイズの造核剤が添加されていることを特徴とする請求項1~請求項6のいずれか1項に記載の化粧シート。
- 上記透明樹脂層を、上記高結晶性ポリプロピレン樹脂に、ナノサイズの造核剤を添加して形成することを特徴とする請求項1~請求項6のいずれか1項に記載の化粧シート。
- 上記造核剤は、単層膜の外膜を具備するベシクルに造核剤が内包されている造核剤ベシクルであることを特徴とする請求項7又は請求項8に記載の化粧シート。
- 超臨界逆相蒸発法によって、上記造核剤をベシクルに内包させたことを特徴とする請求項9に記載の化粧シート。
- 請求項1~請求項10のいずれか1項に記載の化粧シートの製造方法であって、
上記透明樹脂層を、上記高結晶性ポリプロピレン樹脂に、ナノサイズの造核剤を添加して形成することを特徴とする化粧シートの製造方法。 - 上記造核剤は、単層膜の外膜を具備するベシクルに造核剤が内包されている造核剤ベシクルであることを特徴とする請求項11に記載の化粧シートの製造方法。
- 超臨界逆相蒸発法によって、上記造核剤をベシクルに内包させることを特徴とする請求項12に記載の化粧シートの製造方法。
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US20190016104A1 (en) | 2019-01-17 |
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