WO2016125395A1 - ポリオレフィン系化粧シート用フィルム - Google Patents
ポリオレフィン系化粧シート用フィルム Download PDFInfo
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- WO2016125395A1 WO2016125395A1 PCT/JP2015/084901 JP2015084901W WO2016125395A1 WO 2016125395 A1 WO2016125395 A1 WO 2016125395A1 JP 2015084901 W JP2015084901 W JP 2015084901W WO 2016125395 A1 WO2016125395 A1 WO 2016125395A1
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- WIPO (PCT)
- Prior art keywords
- polyolefin
- decorative sheet
- film
- heat
- resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to a polyolefin-based decorative sheet film.
- the present invention relates to a base film for a polyolefin-based decorative sheet that enables stable printing and embossing when producing a polyolefin-based decorative sheet, a decorative sheet using the same, and a decorative material for building interiors. .
- Cosmetic materials such as decorative plywood used for furniture and architectural interior materials are well known in that printed decorative sheets are pasted on base materials such as wood and steel plates such as plywood.
- base materials such as wood and steel plates such as plywood.
- paper and plastic film are widely used as a material for the decorative sheet.
- Patent Document 1 Japanese Patent Laid-Open No. 10-36590
- Patent Document 2 Japanese Patent Laid-Open No. 11-172017. Techniques for decorative sheets that are less likely to occur are disclosed.
- the decorative sheet is often subjected to a wood grain conduit groove, a float pattern (uneven pattern of annual rings), a hairline, a grain of grain, a satin texture, etc. are known.
- the above-described conventional technique using a polypropylene resin has a problem that the process of embossing a decorative sheet does not have sufficient performance. Specifically, when processed at a temperature until the embossing is sufficient, there is a problem that the film cannot withstand the processing temperature and breaks during processing, while the film does not break during processing. When processed, there is a problem that the embossing becomes insufficient, and the processability of the decorative sheet using the olefin resin film is still insufficient.
- JP 10-36590 A Japanese Patent Laid-Open No. 11-172017
- An object of the present invention is to provide a polyolefin decorative sheet film having good embossability.
- the present inventors have intensively studied in view of such problems, and found that a polyolefin-based decorative sheet excellent in embossability can be obtained by adjusting the balance of the heat of crystal fusion in the high temperature region and the low temperature region. Thus, the present invention has been completed.
- polyolefin film for decorative sheet according to [3], wherein the polypropylene resin contains a random copolymer of propylene and ⁇ -olefin.
- a polyolefin decorative sheet comprising the polyolefin decorative sheet film described in any one of [1] to [4] as a base film.
- a decorative material for architectural interiors wherein the base film side surface of the polyolefin-based decorative sheet described in [5] is attached to an adherend. Is provided.
- a polyolefin-based decorative sheet film excellent in embossability can be provided.
- One aspect of the present invention is characterized in that the heat of crystal fusion (A) at 115 to 150 ° C. is 7 to 60 J / g, and the heat of crystal fusion (B) at 150 to 180 ° C. is 10 to 90 J / g. It is the film for polyolefin type decorative sheets.
- the heat of crystal fusion (A) at 115 to 150 ° C. of the polyolefin-based decorative sheet film is 7 to 60 J / g, preferably 7 to 50 J / g, and preferably 8 to 40 J. / G is more preferable, and 10 to 30 J / g is still more preferable.
- the heat of crystal fusion (B) at 150 to 180 ° C. of the film for polyolefin-based decorative sheet is 10 to 90 J / g, preferably 20 to 80 J / g, It is more preferably ⁇ 70 J / g, and further preferably 25 to 60 J / g.
- the value obtained by dividing the heat of crystal fusion (A) by the heat of crystal fusion (B), that is, the ratio of the heat of crystal fusion (A) to the heat of crystal fusion (B) is 0.1. As described above, it is preferably 1 or less, more preferably 0.1 or more and 0.9 or less, and further preferably 0.2 or more and 0.8 or less.
- embossing can be more stably performed in the process of embossing the decorative sheet film and embossing.
- the decorative sheet film can be further prevented from being damaged, and more stable embossability can be imparted.
- the heat of crystal fusion in the present invention means that when the temperature was increased from 25 ° C. to 230 ° C. at a temperature increase rate of 2 ° C./min using a differential scanning calorimeter (DSC) measured according to JIS K7122. It is a value calculated from the crystal peak area on the DSC chart.
- DSC differential scanning calorimeter
- the polyolefin resin used in the present invention is a polyolefin resin having a heat of crystal melting (A) of 7 to 60 J / g at 115 to 150 ° C. and a heat of crystal melting (B) of 10 to 90 J / g at 150 to 180 ° C. If it is resin, it will not specifically limit, A polypropylene resin, a polyethylene-type resin, these mixtures, etc. are mention
- the polyolefin film for decorative sheet of the present invention preferably contains at least a polypropylene resin.
- polypropylene resin examples include a homopolymer of propylene, a copolymer, or a mixture (polymer blend) of the homopolymer and / or the copolymer with another polymer.
- copolymer examples include a random copolymer or block copolymer of propylene and ethylene or other ⁇ -olefin, or a graft copolymer of propylene using a polyolefin-based copolymer as a backbone polymer.
- the ⁇ -olefin copolymerizable with propylene preferably has 4 to 12 carbon atoms.
- the mixing ratio of ⁇ -olefin is preferably 1 to 10% by weight, particularly 2 to 6% by weight, based on propylene.
- polystyrene-butene rubber examples include ethylene-propylene rubber, ethylene-butene rubber, and ethylene-propylene-diene rubber.
- Polymers that can be mixed with propylene homopolymers and / or copolymers to give polymer blends include, for example, isoprene rubber, butadiene rubber, butyl rubber, propylene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-isoprene.
- Diene rubber such as rubber, polyolefin-based thermoplastic elastomers such as ethylene-propylene copolymer rubber, ethylene-propylene non-conjugated diene rubber, ethylene-butadiene copolymer rubber, and styrene-butadiene and styrene-isoprene Styrenic thermoplastic elastomer is mentioned.
- polyolefin-based thermoplastic elastomers such as ethylene-propylene copolymer rubber, ethylene-propylene non-conjugated diene rubber, ethylene-butadiene copolymer rubber, and styrene-butadiene and styrene-isoprene Styrenic thermoplastic elastomer is mentioned.
- the polyolefin resin used in the present invention it is preferable to use a random copolymer of propylene and ⁇ -olefin.
- the polyolefin film for decorative sheet of the present invention contains a random copolymer of propylene and ⁇ -olefin, preferably 70% by mass or less, more preferably 68% by mass or less, relative to 100% by mass of the olefin resin.
- the heat of crystal fusion (A) at 115 to 150 ° C. can be easily set in the range of 7 to 60 J / g, and the polyolefin decorative sheet of the present invention can be used.
- Melting component elution can be suppressed during storage of the film, printability during secondary processing can be improved, and even when a polyolefin-based decorative sheet film is used for a long time, the melting component It is possible to suppress elution and deterioration of the resin and to improve stability.
- the polyolefin film for decorative sheet of the present invention it is particularly preferable to use a mixture of a propylene homopolymer and a random copolymer of propylene and ⁇ -olefin as the polyolefin resin.
- the weight ratio of the propylene homopolymer and the mixture of the random copolymer of propylene and ⁇ -olefin is preferably 10:90 to 60:40, more preferably 20:80 to 55:45, and 22:78. More preferably, it is ⁇ 50: 50.
- the heat of crystal fusion (A) at 115 to 150 ° C. is 7 to 60 J / g and 150 to 180
- the heat of crystal fusion (B) at 0 ° C. can be easily set in the range of 10 to 90 J / g. By doing so, it becomes possible to make a combination of materials having good compatibility as a whole polyolefin resin and more stable. The performance of the resin can be retained for a long time.
- the melt flow rate of the polypropylene resin used for the polyolefin decorative sheet film of the present invention is preferably 0.1 to 30 (g / 10 min) under the conditions of 230 ° C. and 2.16 kgf. If the melt flow rate is 0.1 or more, it is easy to mold and a smooth film is easily obtained. Moreover, if the melt flow rate is 30 or less, the melt viscosity will not be too low, and molding into a film will not be difficult.
- Polyethylene resins include ethylene homopolymers and / or copolymers of ethylene and other monomers copolymerizable with ethylene (low density polyethylene (LDPE), linear low Density polyethylene (LLDPE), high density polyethylene (HDPE), polyethylene obtained by polymerization using a metallocene catalyst, etc.) or a mixture of the homopolymer and / or copolymer with other copolymer ( Polymer blend) and the like.
- LDPE low density polyethylene
- LLDPE linear low Density polyethylene
- HDPE high density polyethylene
- Polymer blend Polymer blend
- Polymers that can be mixed with the homopolymer and / or copolymer to give a polymer blend include, for example, isoprene rubber, butadiene rubber, butyl rubber, propylene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-isoprene rubber, and the like.
- polyolefin-based thermoplastic elastomers such as diene rubber, ethylene-propylene non-conjugated diene rubber, and ethylene-butadiene copolymer rubber, and styrene-based thermoplastic elastomers such as styrene-butadiene and styrene-isoprene.
- the melt flow rate of the polyethylene resin used for the polyolefin decorative sheet film of the present invention is preferably 0.1 to 30 (g / 10 min) under the conditions of 190 ° C. and 2.16 kgf. If the melt flow rate is 0.1 or more, it is easy to mold and a smooth film is easily obtained. Moreover, if the melt flow rate is 30 or less, the melt viscosity will not be too low, and molding into a film will not be difficult.
- the film for polyolefin-based decorative sheet of the present invention has 115 to 150 ° C. if the heat of crystal fusion (A) at 115 to 150 ° C. and the heat of crystal fusion (B) at 150 to 180 ° C. are within the ranges specified in the present invention.
- a polyolefin-based resin that does not have the characteristics that the heat of crystal fusion (A) at 150 ° C. is 7 to 60 J / g and the heat of crystal fusion (B) at 150 to 180 ° C. is 10 to 90 J / g may be included.
- the polyolefin film for decorative sheet has a heat of crystal melting (A) of 7 to 60 J / g at 115 to 150 ° C. and a heat of crystal melting (B) of 150 to 180 ° C. of 10 to 90 J. / G of polyolefin resin alone.
- the polyolefin decorative sheet film has a heat of crystal fusion (A) at 115 to 150 ° C. of 7 to 60 J / g and a heat of crystal fusion (B) at 150 to 180 ° C. of 10 Including a mixture of polyolefin-based resin that is ⁇ 90 J / g. Any of the polyolefin-based resins in the mixture may have the characteristics of the heat of crystal fusion as long as the mixture as a whole has the characteristics of the heat of crystal fusion.
- the polyolefin decorative sheet film of the present invention has a temperature of 115 to 150 ° C., for example, by mixing a polyolefin resin having a heat of crystal fusion in a temperature range of 115 to 150 ° C. alone or by mixing a plurality of resins. Mixing so that the heat of crystal fusion (A) in the range is 7 to 60 J / g, and mixing polyolefin resin having crystal heat of heat in the temperature range of 150 to 180 ° C. alone or in combination with a plurality of resins. Thus, the amount of heat of crystal fusion (B) in the temperature range of 150 to 180 ° C. is blended so as to be 10 to 90 J / g, and these polyolefin resins can be further mixed.
- the polyolefin decorative sheet film of the present invention may be a single layer or a multilayer.
- a multi-layer it may be a two-layer that will be a surface layer and a base material layer, may be a three-layer configuration comprising at least a surface layer, an intermediate layer, and a back layer, A layer made of a polyolefin resin may be further provided between the back layer and the intermediate layer.
- An adhesive layer may be provided between the surface layer and the intermediate layer and between the back layer and the intermediate layer.
- the ratio of the thickness of the intermediate layer to the total thickness is preferably 70% to 99.9%, and preferably 75% to 95%. % Is more preferable.
- the content of the pigment in the intermediate layer is larger than the content of the pigment in the front layer or the back layer, or only in the intermediate layer. Pigments can be included. In this way, even if the amount of the pigment is increased, the intermediate layer of the film contains a large amount of pigment, and the addition amount of the surface layer and the back layer is reduced or not added as much as possible. It is possible to preferentially prevent the occurrence of scum.
- any of organic pigments and inorganic pigments can be used.
- examples thereof include titanium oxide, carbon black, iron oxide, azo compounds, phthalocyanine compounds, titanium oxide / antimony oxide / nickel oxide solid solution, and the like.
- the pigment content is preferably in the range of 1 to 60 parts by weight with respect to 100 parts by weight of the polyolefin resin, although it depends on the concealability required for the decorative sheet.
- the polyolefin decorative sheet film of the present invention preferably contains an ultraviolet absorber and / or a hindered amine light stabilizer.
- the blending amount of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight per 100 parts by weight of the polyolefin resin in each layer. If the blending amount is 0.01 parts by weight or more, the effect of preventing browning and deterioration can be easily obtained.
- the ultraviolet absorber used for the polyolefin-based decorative sheet film of the present invention is 2- [2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methyl.
- Phenyl] benzotriazole (molecular weight 388), 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole (molecular weight 448), 2,2-methylenebis [4- ( Benzotriazole ultraviolet absorbers such as 1,1,3,3-tetramethylbutyl-6- (2H-benzotriazol-2-yl) phenol] (molecular weight 659), and 2,4-dihydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy- Examples thereof include benzophenone ultraviolet absorbers such as 4-dimethoxybenzophenone and bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane.
- a benzotriazole-based ultraviolet absorber is suitable for reducing the coloring of the product, and the molecular weight thereof is in the range of 380 to 1000, preferably in the range of 400 to 800. Those within are more preferred. By setting the molecular weight within the above range, the bloom preventing effect is further increased.
- the blending amount of the hindered amine light stabilizer is preferably 0.01 to 10 parts by weight per 100 parts by weight of the polyolefin resin in each layer. If the blending amount is 0.01 parts by weight or more, a stabilizing effect is easily obtained, and if it is 10 parts by weight or less, an effect commensurate with the blending amount is obtained and there is no possibility of causing bloom.
- hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n- Bis (1,2,2,6,6-pentamethyl-4-piperidyl) butylmalonate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate Polycondensates and poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl Examples thereof include hindered amine light stabilizers such as -4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ].
- polyolefin-based decorative sheet film of the present invention other synthetic resins and, if necessary, additives such as antioxidants, slip agents, colorants, fillers, nucleating agents, etc., do not impair the purpose of the present invention. You may add in. Moreover, about these additives, it is common to use what was previously mix
- a method for producing a polyolefin-based decorative sheet film is not particularly limited as long as a general polyolefin-based resin film molding method such as a T-die extrusion molding method, an inflation molding method, or a calendar molding method is used.
- the thickness of the polyolefin decorative sheet film of the present invention is preferably less than 200 ⁇ m, more preferably 150 ⁇ m or less. In the present invention, even when the thickness of the film is set in this way, it can be a decorative sheet film excellent in embossing and printing processability.
- the thickness of the polyolefin-based decorative sheet film is an average value obtained by measuring the thickness of the film using a dial gauge having a scale of 0.001 mm according to JIS B 7503, and is generally used for measuring the thickness of the film. It is the arithmetic average value measured by the place to consider and the number of samples.
- Another embodiment of the present invention is a decorative sheet comprising the above polyolefin film for decorative sheet as a base film.
- a decorative sheet include those in which a print layer is formed on the film surface layer side of the polyolefin-based decorative sheet and a transparent surface layer is laminated thereon.
- one or both surfaces of the polyolefin-based decorative sheet film of the present invention are subjected to corona treatment, a primer mainly composed of a chlorinated polyolefin resin or the like is applied, and the grain of the grain is obtained by gravure printing on the treated sheet.
- the decorative sheet according to the present invention can be manufactured by performing tone printing and further applying an embossing process by laminating a transparent sheet.
- the surface of the decorative sheet is often provided with a surface layer in order to improve the weather resistance, abrasion resistance, scratch resistance, etc. of the decorative material.
- This layer is a polyolefin resin, polyester resin, acrylic resin, It can be formed by laminating or coating urethane resin or the like. You may emboss this surface layer.
- the printing layer can be formed by a transfer method in addition to a method of performing printing such as gravure printing, offset printing, offset gravure printing, and silk screen printing using an ink in which a pigment or the like is dispersed. .
- a transfer method in addition to a method of performing printing such as gravure printing, offset printing, offset gravure printing, and silk screen printing using an ink in which a pigment or the like is dispersed.
- it is preferable to provide a primer layer between the substrate sheet and the printing layer because the adhesion between the two is further improved.
- a solution containing a chlorinated polyolefin resin, a polyester resin, an ethylene-vinyl alcohol copolymer or the like as a main component and a filler added thereto as necessary is a base material for a polyolefin-based decorative sheet film.
- a base material for a polyolefin-based decorative sheet film examples thereof include a layer formed by coating on a film.
- Another aspect of the present invention is a decorative material for architectural interiors, wherein the back surface of the base film of the polyolefin-based decorative sheet is adhered to an adherend.
- -Polypropylene resin A-1 “F327BV” (Random PP) manufactured by Prime Polymer Co., Ltd.
- Polypropylene resin A-2 “FLX80E4” (Homo PP) manufactured by Sumitomo Chemical Co., Ltd.
- Polypropylene resin A-3 “Novatec BC3HF” (Block PP) manufactured by Nippon Polypro Co., Ltd.
- -Polyethylene resin B-1 "LC500” manufactured by Nippon Polyethylene
- Polyethylene resin B-2 “SP0540” manufactured by Prime Polymer Co., Ltd.
- Olefin elastomer C-1 “F3900” manufactured by Prime Polymer Co., Ltd.
- the polyolefin-based decorative sheet films of Examples 1 to 4 have the heat of crystal fusion specified in the present invention and are excellent in embossability.
- Example 1 was very excellent in embossability and the result that it was easy to process was obtained.
- the polyolefin-based decorative sheet films of Comparative Examples 2 to 6 have a small amount of heat of crystal melting at 115 ° C. to 150 ° C., so that it is difficult to stably provide the embossing and the embossing processability is poor.
- Comparative Example 1 since the heat of crystal melting from 150 ° C. to 180 ° C. is small, the strength of the polyolefin-based decorative sheet film becomes unstable depending on the embossing temperature, and the performance to stably process is inferior. Is recognized.
- the polyolefin film for decorative sheet of the present invention is a film for decorative sheet having very excellent embossability.
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- Polymers & Plastics (AREA)
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Abstract
Description
[1]115~150℃における結晶融解熱量(A)が7~60J/g、かつ150~180℃における結晶融解熱量(B)が10~90J/gであることを特徴とするポリオレフィン系化粧シート用フィルム。
[2]前記結晶融解熱量(A)の前記結晶融解熱量(B)に対する比率は、0.1以上、1以下であることを特徴とする[1]に記載のポリオレフィン系化粧シート用フィルム。
[3]前記ポリオレフィン系化粧シート用フィルムが、少なくともポリプロピレン系樹脂を含んでいることを特徴とする[1]または[2]に記載のポリオレフィン系化粧シート用フィルム。
[4]前記ポリプロピレン系樹脂は、プロピレンとα-オレフィンとのランダム共重合体を含有していることを特徴とする[3]に記載のポリオレフィン系化粧シート用フィルム。
[5][1]~[4]のいずれか1項に記載のポリオレフィン系化粧シート用フィルムを基材フィルムとして含むポリオレフィン系化粧シート。
[6][5]に記載するポリオレフィン系化粧シートの基材フィルム側の面を被着材に貼着してなる建築内装用化粧材。
を、提供するものである。
なお、本発明における結晶融解熱量とは、JIS K7122に準拠して測定した示差走査熱量計(DSC)を用いて、昇温速度2℃/分で25℃から230℃まで昇温した時における、DSCチャート上の結晶ピーク面積より計算した値のことである。
本発明に使用するポリオレフィン系樹脂は、115~150℃における結晶融解熱量(A)が7~60J/g、かつ150~180℃における結晶融解熱量(B)が10~90J/gであるポリオレフィン系樹脂であれば特に限定されることはなく、ポリプロピレン系樹脂やポリエチレン系樹脂およびこれらの混合物等があげられる。
本発明のポリオレフィン系化粧シート用フィルムは、少なくともポリプロピレン系樹脂を含んでいることが好ましい。
ポリプロピレン系樹脂としては、プロピレンの単独重合体、共重合体、あるいは前記単独重合体及び/または共重合体と他の重合体との混合物(ポリマーブレンド)等が例示できる。該共重合体としてはプロピレンとエチレンまたは他のα-オレフィンとのランダム共重合体またはブロック共重合体、あるいはポリオレフィン系の共重合体を幹ポリマーとしたプロピレンのグラフト共重合体等が例示できる。
プロピレンの単独重合体及び/または共重合体と混合してポリマーブレンドを与えることのできる重合体としては、例えば、イソプレンゴム、ブタジエンゴム、ブチルゴム、プロピレン-ブタジエンゴム、アクリロニトリル-ブタジエンゴム、アクリロニトリル-イソプレンゴム等のジエン系ゴムや、エチレン-プロピレン共重合体ゴム、エチレン-プロピレン非共役ジエンゴム、エチレン-ブタジエン共重合体ゴム等のポリオレフィン系熱可塑性エラストマー、及びスチレン-ブタジエン系やスチレン-イソプレン系等のスチレン系熱可塑性エラストマーが挙げられる。
ポリエチレン系樹脂としては、エチレンの単独重合体および/またはエチレンを主成分とする、エチレンとこれと共重合可能な他の単量体との共重合体(低密度ポリエチレン(LDPE)、線状低密度ポリエチレン(LLDPE)、高密度ポリエチレン(HDPE)、メタロセン系触媒を用いて重合して得られたポリエチレン等)、あるいは前記単独重合体および/または共重合体と他の共重合体との混合物(ポリマーブレンド)等が例示できる。この単独重合体および/または共重合体と混合してポリマーブレンドを与えることのできる重合体としては、例えばイソプレンゴム、ブタジエンゴム、ブチルゴム、プロピレン-ブタジエンゴム、アクリロニトリル-ブタジエンゴム、アクリロニトリル-イソプレンゴム等のジエン系ゴム、エチレン-プロピレン非共役ジエンゴム、エチレン-ブタジエン共重合体ゴム等のポリオレフィン系熱可塑性エラストマー、およびスチレン-ブタジエン系やスチレン-イソプレン系等のスチレン系熱可塑性エラストマーがあげられる。
また、本発明の1つの側面において、ポリオレフィン系化粧シート用フィルムは、115~150℃における結晶融解熱量(A)が7~60J/g、かつ150~180℃における結晶融解熱量(B)が10~90J/gであるポリオレフィン系樹脂の混合物を含む。当該混合物中のポリオレフィン系樹脂の何れもが上記結晶融解熱量の特性を有していてもよいが、当該混合物全体として上記結晶融解熱量の特性を有していればよい。
紫外線吸収剤の配合量は、それぞれの層におけるポリオレフィン系樹脂100重量部当たり、0.01~10重量部が好ましく、特に0.05~5重量が好ましい。配合量が0.01重量部以上であれば、褐色・劣化の防止効果を得られやすく、10重量部以下であれば、配合量に見合った効果が得られ、またブリードを起こす恐れもない。
なお、ポリオレフィン系化粧シート用フィルムの厚みは、JIS B 7503による目盛0.001mmのダイヤルゲージを使用しフィルムの厚さを測定した平均値のことであり、フィルムの厚さを測定する場合に一般的に考慮する箇所、サンプル数にて測定した算術平均値のことである。
このような化粧シートとしては、例えば、上記のポリオレフィン系化粧シート用フィルム表層側に印刷層を形成し、その上に透明な表面層を積層したものが挙げられる。具体的には、本発明のポリオレフィン系化粧シート用フィルムの片面または両面にコロナ処理を施し、塩素化ポリオレフィン系樹脂などを主成分としたプライマーを塗布し、この処理済みシート上にグラビア印刷により木目調の印刷を行い、さらに透明シートを貼り合わせてエンボス処理を施すことにより、本発明にかかる化粧シートを製造することができる。
本発明の基材フィルムを層構成に有するポリオレフィン系化粧シートを使用することで、該内装用化粧材への貼付け性が良くなり、また長期に使用してもポリオレフィン系化粧シートが剥がれにくい長期性能に優れた建築内装用化粧材として優れたものを作製することができる。
・ポリプロピレン系樹脂A-1:プライムポリマー社製「F327BV」(ランダムPP)
・ポリプロピレン系樹脂A-2:住友化学社製「FLX80E4」(ホモPP)
・ポリプロピレン系樹脂A-3:日本ポリプロ社製「ノバテック BC3HF」(ブロックPP)
・ポリエチレン系樹脂B-1:日本ポリエチレン社製「LC500」
・ポリエチレン系樹脂B-2:プライムポリマー社製「SP0540」
・オレフィン系エラストマーC-1:プライムポリマー社製「F3900」
ポリオレフィン系化粧シート用フィルムの作製
表1に示す配合を用いて、50mmφの押出機1台と35mmφの押出機2台のTダイ押出機(Tダイ:650mm幅)を用い、ダイス温度230℃の条件で樹脂を押出し、冷却水を通した金属製成形ロールとゴム製成形ロールでニップ成形を行い、厚さ60μmの化粧シート用フィルムを作製した。
1)結晶融解熱量の測定
示差走査熱量測定装置(メトラー・トレド製 DSC823e)を用い、表1に示したポリオレフィン系樹脂(2種以上のポリオレフィン系樹脂の混合物の場合は混合物)から得られた化粧シート用フィルムの試料約5mgを、昇温速度2℃/分で25℃から230℃まで昇温した際に測定されたDSCチャート上の結晶ピーク面積より、表1に規定した各温度範囲の面積を計算した。
得られた化粧シート用フィルムを赤外線非接触方式のヒーターで加熱軟化させた後、凹凸を有するエンボス版で加圧し、賦形した。エンボスの加工性について下記の基準で評価した。
○:フィルムが破断する事無く、均一にエンボス加工が可能
×:フィルムが破断する、または均一にエンボス加工ができない
一方、比較例2~6のポリオレフィン系化粧シート用フィルムは、115℃~150℃における結晶融解熱量が小さいため、エンボス加工を安定的に付与することが難しく、エンボスの加工性が劣っている。また、比較例1は、150℃から180℃の結晶融解熱量が小さいため、エンボス加工する温度によってポリオレフィン系化粧シート用フィルムの強度が不安定になり、安定的に加工する性能が劣っていることが認められる。
Claims (6)
- 115~150℃における結晶融解熱量(A)が7~60J/g、かつ150~180℃における結晶融解熱量(B)が10~90J/gであることを特徴とするポリオレフィン系化粧シート用フィルム。
- 前記結晶融解熱量(A)の前記結晶融解熱量(B)に対する比率は、0.1以上、1以下であることを特徴とする請求項1に記載のポリオレフィン系化粧シート用フィルム。
- 前記ポリオレフィン系化粧シート用フィルムが、少なくともポリプロピレン系樹脂を含んでいることを特徴とする請求項1または2に記載のポリオレフィン系化粧シート用フィルム。
- 前記ポリプロピレン系樹脂は、プロピレンとα-オレフィンとのランダム共重合体を含有していることを特徴とする請求項3に記載のポリオレフィン系化粧シート用フィルム。
- 請求項1~4のいずれか1項に記載のポリオレフィン系化粧シート用フィルムを基材フィルムとして含むポリオレフィン系化粧シート。
- 請求項5に記載するポリオレフィン系化粧シートの基材フィルム側の面を被着材に貼着してなる建築内装用化粧材。
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JP2001288314A (ja) * | 2000-04-05 | 2001-10-16 | Mitsubishi Chem Mkv Co | 化粧シート用フィルム |
WO2006057361A1 (ja) * | 2004-11-25 | 2006-06-01 | Mitsui Chemicals, Inc. | プロピレン系樹脂組成物およびその用途 |
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JPH11152345A (ja) * | 1997-11-21 | 1999-06-08 | Mitsubishi Chem Mkv Co | 化粧シート用フィルム |
JPH11172017A (ja) * | 1997-12-15 | 1999-06-29 | Mitsubishi Chem Mkv Co | 化粧シート用フィルム |
JP2001288314A (ja) * | 2000-04-05 | 2001-10-16 | Mitsubishi Chem Mkv Co | 化粧シート用フィルム |
WO2006057361A1 (ja) * | 2004-11-25 | 2006-06-01 | Mitsui Chemicals, Inc. | プロピレン系樹脂組成物およびその用途 |
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