WO2018225780A1 - 多層フィルムおよびその製造方法 - Google Patents
多層フィルムおよびその製造方法 Download PDFInfo
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- WO2018225780A1 WO2018225780A1 PCT/JP2018/021685 JP2018021685W WO2018225780A1 WO 2018225780 A1 WO2018225780 A1 WO 2018225780A1 JP 2018021685 W JP2018021685 W JP 2018021685W WO 2018225780 A1 WO2018225780 A1 WO 2018225780A1
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- WO
- WIPO (PCT)
- Prior art keywords
- multilayer film
- resin
- layer
- polymer composition
- thermoplastic
- Prior art date
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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
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
- B29C45/14811—Multilayered articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C48/885—External treatment, e.g. by using air rings for cooling tubular films
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
- B29C63/02—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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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
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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
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- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
Definitions
- the present invention relates to a multilayer film suitable for decorating an article having a three-dimensional solid surface and a method for producing the same.
- Ceramics, metals, and synthetic resins with excellent design, durability, heat resistance, and mechanical strength are widely used in various applications such as home appliances, electronic parts, machine parts, and automobile parts. These members may be used by adhering or combining different materials depending on applications, component configurations, and usage methods.
- exterior and wallpaper of home appliances, interior decoration of automobiles, etc. are decorated with patterns such as wood grain, design features such as metallic tone and piano black tone, and functionality such as scratch resistance and weather resistance
- a decorative resin film is used.
- the resin decorative film can be thermoformed and can be adhered to the surface of the article as described above, which often has a three-dimensional solid shape, and thus has been suitably used.
- a method of obtaining a decorative molded body by inserting a decorative film coated with an adhesive into an injection mold and injection molding is known.
- This is a method generally called a film insert injection molding method.
- the adhesive is poured by the injection-molded molten resin to reduce the adhesion between the decorative film and the molded body.
- Patent Document 1 a so-called backing film is used. After the base resin layer (backing layer) and the decorative film are bonded and intimately bonded via an adhesive, a molded body obtained by preforming the laminated film and the laminated film into a three-dimensional shape is injection molded. A method is described in which a decorative molded body is obtained by injection molding a molten resin of the same type as that of the base resin layer from the surface opposite to the decorative film, which is set in a mold.
- Patent Document 2 a decorative film with an adhesive layer obtained by forming a release layer on a base film and applying a clear coating layer, a design layer, and an adhesive layer in this order is compressed under vacuum conditions. And after covering and bonding to a three-dimensional solid shape, a method is described in which a decorative molded body is obtained by peeling the base film and the release layer.
- Patent Document 3 a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit, or a thermoplastic elastomer which is a hydrogenated product thereof and a polar group-containing polypropylene system
- a method of manufacturing an adhesive body in which a film made of a resin composition containing a resin is bonded to an insert member and then the resin member is subjected to insert injection molding is proposed, and the case where the insert member and the resin member are different materials is also shown. Yes.
- the decoration is required to be applicable to the above-mentioned adherends having various three-dimensional shapes.
- the material of the injection molding resin that is, the material of the adherend having a three-dimensional solid shape is limited by the material of the backing layer. Therefore, it is necessary to prepare a film in which the material of the adhesive applied to the backing layer and the backing layer is changed for each material of the adherend. In this case, since the number of brands increases, troubles such as switching and management are problematic.
- corresponds only to the film insert injection molding method as a decoration construction method, and a decoration construction method is limited.
- Patent Document 2 can be bonded to a wide variety of adherend shapes at a lower temperature than the injection molding temperature because the adhesive is applied, but the adhesive has a high tackiness. For this reason, there arises a problem that the yield decreases due to the occurrence of problems such as adhesion of foreign substances such as environmental dust and sticking of the adhesive surfaces.
- the film described in Patent Document 3 can hot-melt bond dissimilar materials with different polarities at a lower temperature (100 ° C. or higher) than the injection molding temperature, but it should be compatible with a wide variety of adherend shapes.
- a lower temperature 100 ° C. or higher
- the film when the film is set on the molding machine, the film may be bent and the handling property may be poor, or the decorative surface may be wrinkled.
- the preform molded body has low shape retention and poor setability to the mold, so that the preform molded body falls off, and the injection molding resin becomes behind. .
- the object of the present invention is excellent in handling properties and low-temperature adhesiveness to adherends of various materials, and is free to select materials and decoration methods applied to various decorative moldings to three-dimensional solid shapes. It is providing a multilayer film with high degree and its manufacturing method.
- the above object is achieved by providing the following [1] to [12].
- thermoplastic resin layer having a flexural modulus of 60 to 30000 kPa ⁇ mm 3 is used as an intermediate layer (X), and an aromatic vinyl compound unit A block copolymer containing a polymer block (a1) comprising a polymer block (a2) comprising a conjugated diene compound unit or a thermoplastic elastomer (A) which is a hydrogenated product thereof, and a polypropylene resin.
- the conjugated diene compound constituting the polymer block (a2) in the thermoplastic elastomer (A) is butadiene, isoprene, or butadiene and isoprene, and 1,2-bond in the polymer block (a2)
- thermoplastic elastomer (A) in the thermoplastic polymer composition is 50% by mass or more.
- thermoplastic resin used in the intermediate layer (X) has a melt flow rate (MFR) of 0.1 to 20 g / measured under conditions of a temperature of 230 ° C. and a load of 2.16 kg (21.2 N). 10 minutes, MFR ratio (Y) / measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg (21.2 N) of the thermoplastic polymer composition layer (Y) with respect to the intermediate layer (X)
- MFR ratio (Y) measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg (21.2 N) of the thermoplastic polymer composition layer (Y) with respect to the intermediate layer (X)
- the multilayer film according to any one of [1] to [5], wherein (X) is 1 to 15.
- thermoplastic polymer composition layer (Y) on both surfaces of the intermediate layer (X) according to any one of [1] to [7], which is a surface layer
- thermoplastic resin layer (Y) is in a molten state and contacts a roll whose surface is a hydrophobic resin.
- thermoplastic polymer composition layer (Y) on both surfaces of the intermediate layer (X) according to any one of [1] to [7], A process for producing a multilayer film comprising the step of laminating X) and the thermoplastic resin layer (Y) by coextrusion.
- the multilayer film of the present invention is excellent in handling properties and low-temperature adhesiveness to adherends of various materials. Therefore, it can decorate by adhering firmly to both a decorating film and various adherends.
- the multilayer film of the present invention has shape retention and can be applied to various decorative moldings into a three-dimensional solid shape.
- the multilayer film of the present invention comprises a thermoplastic resin layer having a flexural modulus of 60 to 30000 kPa ⁇ mm 3 as an intermediate layer (X), and a polymer block (a1) composed of aromatic vinyl compound units and a conjugated diene compound unit.
- the MFR ratio (Y) / (X) under the temperature of 230 ° C. and the load of 2.16 kg (21.2 N) of the thermoplastic polymer composition layer (Y) with respect to the intermediate layer (X) is 1.
- each layer will be described in order.
- thermoplastic resin used in the intermediate layer (X) is not limited as long as it is used for a known film substrate.
- ZEONOR registered trademark
- Nippon Zeon ZEONEX registered trademark
- Arton registered trademark
- JSR Joint Photographic acid
- various polypropylene-based resins can be used, but those having a content of structural units derived from propylene (hereinafter sometimes referred to as propylene content) of 60 mol% or more are preferable.
- the content of the structural unit derived from propylene is preferably 80 mol% or more, more preferably 90 to 100 mol%, still more preferably 95 to 99 mol%.
- Examples of structural units derived from other than propylene include structural units derived from ethylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-nonene and 1-decene.
- structural units derived from modifiers described later are also included.
- Examples of the polypropylene resin used in the intermediate layer (X) include homopolypropylene, block polypropylene, propylene-ethylene random copolymer, propylene-butene random copolymer, propylene-ethylene-butene random copolymer, propylene- Examples include pentene random copolymers, propylene-hexene random copolymers, propylene-octene random copolymers, propylene-ethylene-pentene random copolymers, propylene-ethylene-hexene random copolymers, and modified products thereof. It is done.
- Examples of the modified product include those obtained by graft copolymerizing a modifier with a polypropylene resin, and those obtained by copolymerizing a modifier with the main chain of the polypropylene resin.
- Examples of the modifying agent include maleic acid, citraconic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo [2.2.1] -5-heptene.
- Unsaturated dicarboxylic acids such as -2,3-dicarboxylic acids; esters, amides or imides of unsaturated dicarboxylic acids; maleic anhydride, citraconic anhydride, halogenated maleic anhydride, itaconic anhydride, cis-4-cyclohexene anhydride
- Unsaturated dicarboxylic anhydrides such as 1,2-dicarboxylic acid, anhydrous endo-cis-bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid; acrylic acid, methacrylic acid, crotonic acid, etc.
- the polypropylene resin used in the polypropylene resin layer (X) an unmodified one is preferable. Among these, homopolypropylene, propylene-ethylene random copolymer, and block polypropylene are preferable from the viewpoint of being relatively inexpensive and easily available. Furthermore, a propylene-ethylene random copolymer is particularly preferable from the viewpoint of adhesive strength with a polyolefin resin and reduction of warpage of the multilayer film.
- a polypropylene resin may be used individually by 1 type, and may use 2 or more types together.
- the intermediate layer (X) may contain other resins in addition to the polypropylene resin as long as the effects of the present invention are not impaired.
- the melt flow rate (MFR) measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg (21.2 N) N of the thermoplastic resin used in the intermediate layer (X) is a molding process of the resin composition (X). From the viewpoint of properties, it is preferably 0.1 to 20 g / 10 minutes, more preferably 0.3 to 15 g / 10 minutes, and further preferably 0.6 to 10 g / 10 minutes.
- the “melt flow rate” described in the present specification and claims is a value measured in accordance with JIS K 7210.
- the flow start temperature of the thermoplastic resin is not particularly limited, but is preferably 120 to 190 ° C, more preferably 120 to 180 ° C. Usually, the flow initiation temperature is defined in an amorphous resin, but in this specification, the flow initiation temperature of a crystalline resin is represented by a melting point.
- the bending rigidity rate of the thermoplastic resin layer used in the intermediate layer (X) is 60 to 30000 kPa ⁇ mm 3 from the viewpoint of handling property in molding a multilayer film and mold setting property in insert injection molding of a preform molded body. It is preferably 60 to 10,000 kPa ⁇ mm 3 , and more preferably 100 to 5000 kPa ⁇ mm 3 . If the flexural rigidity is lower than 60 kPa ⁇ mm 3 , the film and preform molded body are likely to be deformed, and if it is higher than 30000 kPa ⁇ mm 3 , the film formability may be lowered and the moldability may be inferior.
- thermoplastic polymer composition layer (Y) contains a polymer block (a1) composed of aromatic vinyl compound units and a polymer block (a2) composed of conjugated diene compound units.
- the thermoplastic elastomer (A) which is a block copolymer or its hydrogenated product is contained.
- the content of the thermoplastic elastomer (A) in the thermoplastic polymer composition is preferably 50% by mass or more, and more preferably 65% by mass or more.
- Thermoplastic elastomer (A) examples include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methyl. Styrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, etc. Can be mentioned.
- the polymer block containing the aromatic vinyl compound unit may be composed of a structural unit derived from only one of these aromatic vinyl compounds, or may be composed of a structural unit derived from two or more types. . Of these, styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferable.
- the polymer block (a1) comprising aromatic vinyl compound units is preferably 80% by mass or more of aromatic vinyl compound units, more preferably 90% by mass or more of aromatic vinyl compound units, and still more preferably 95% by mass of aromatic vinyl compound units.
- % Is a polymer block containing at least%.
- the polymer block (a1) may have only an aromatic vinyl compound unit, but has other copolymerizable monomer units together with the aromatic vinyl compound unit as long as the effects of the present invention are not impaired. You may do it. Examples of other copolymerizable monomers include 1-butene, pentene, hexene, butadiene, isoprene, methyl vinyl ether, and the like.
- the proportion thereof is preferably 20% by mass or less, more preferably 10%, based on the total amount of the aromatic vinyl compound unit and other copolymerizable monomer units. It is at most 5% by mass, more preferably at most 5% by mass.
- Examples of the conjugated diene compound constituting the polymer block (a2) composed of the conjugated diene compound unit contained in the thermoplastic elastomer (A) include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1 1,3-pentadiene, 1,3-hexadiene and the like. Of these, butadiene and isoprene are preferable.
- the polymer block (a2) containing a conjugated diene compound unit may be composed of a structural unit derived from only one of these conjugated diene compounds, or may be composed of a structural unit derived from two or more types. Good. In particular, it is preferably composed of a structural unit derived from butadiene or isoprene or a structural unit derived from butadiene and isoprene.
- the polymer block (a2) composed of conjugated diene compound units preferably contains 80% by mass or more of conjugated diene compound units, more preferably 90% by mass or more, more preferably 95% by mass or more of conjugated diene compound units. It is a polymer block.
- the polymer block (a2) may have only a conjugated diene compound unit, but has other copolymerizable monomer units together with the conjugated diene compound unit, as long as it does not interfere with the present invention. May be. Examples of other copolymerizable monomers include styrene, ⁇ -methylstyrene, 4-methylstyrene, and the like.
- the proportion thereof is preferably 20% by mass or less, more preferably 10% by mass with respect to the total amount of the conjugated diene compound unit and the other copolymerizable monomer units. % Or less, more preferably 5% by mass or less.
- the bonding form of the conjugated diene constituting the polymer block (a2) is not particularly limited.
- 1,2-bond and 1,4-bond can be formed, and in the case of isoprene, 1,2-bond, 3,4-bond and 1,4-bond can be formed.
- the amount of 1,2-bond in the polymer block composed of conjugated diene compound units and the total amount of 3,4-bonds is more preferably 35 to 98 mol%, further preferably 40 to 90 mol%, and still more preferably 50 to 80 mol%.
- the total amount of 1,2-bond and 3,4-bond can be calculated by 1 H-NMR measurement. Specifically, the integrated value of the peak existing at 4.2 to 5.0 ppm derived from 1,2-bonds and 3,4-bond units and 5.0 to 5.5 derived from 1,4-bond units. It can be calculated from the ratio with the integrated value of the peak existing at 45 ppm.
- the bonding form of the polymer block (a1) composed of the aromatic vinyl compound unit and the polymer block (a2) composed of the conjugated diene compound unit in the thermoplastic elastomer (A) is not particularly limited, and is linear, branched, Either a radial form or a combination form in which two or more of these are combined may be used, but a linear form is preferable.
- linear bond forms include a diblock copolymer represented by ab when the polymer block (a1) is represented by a and the polymer block (a2) is represented by b, ab A triblock copolymer represented by -a or b-a-b, a tetrablock copolymer represented by abbab, abbaba or babb -A-b pentablock copolymer, ( While-b) nX type copolymer (X represents a coupling residue, n represents an integer of 2 or more), and mixtures thereof It is done.
- a triblock copolymer is preferable, and a triblock copolymer represented by aba is more preferable.
- the content of the polymer block (a1) composed of the aromatic vinyl compound unit in the thermoplastic elastomer (A) is preferably 5 to 5 with respect to the entire thermoplastic elastomer (A) from the viewpoint of flexibility and mechanical properties. It is 75% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 40% by mass.
- thermoplastic elastomer (A) part or all of the polymer block (a2) is hydrogenated (hereinafter sometimes abbreviated as “hydrogenated”) from the viewpoint of improving heat resistance and weather resistance. It is preferable.
- the hydrogenation rate at that time is preferably 80% or more, more preferably 85% or more.
- the hydrogenation rate is a value obtained by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.
- the weight average molecular weight of the thermoplastic elastomer (A) is preferably 30,000 to 500,000, more preferably 50,000 to 400,000, more preferably 60, from the viewpoints of mechanical properties and moldability. 000 to 200,000, more preferably 70,000 to 200,000, particularly preferably 70,000 to 190,000, and most preferably 80,000 to 180,000. It is.
- the weight average molecular weight is a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) measurement.
- GPC gel permeation chromatography
- a thermoplastic elastomer (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
- thermoplastic elastomer (A) it can manufacture by an anionic polymerization method. Specifically, (i) a method of sequentially polymerizing the aromatic vinyl compound, the conjugated diene compound, and then the aromatic vinyl compound using an alkyl lithium compound as an initiator; (ii) using an alkyl lithium compound as an initiator A method of sequentially polymerizing the aromatic vinyl compound and the conjugated diene compound, and then coupling by adding a coupling agent; (iii) using the dilithium compound as an initiator, the conjugated diene compound, and then the aromatic vinyl Examples include a method of polymerizing compounds sequentially.
- thermoplastic elastomer (A) by adding an organic Lewis base, the amount of 1,2-bonds and 3,4-bonds of the thermoplastic elastomer (A) can be increased, and depending on the amount of the organic Lewis base added, The 1,2-bond amount and 3,4-bond amount of the thermoplastic elastomer (A) can be easily controlled.
- the hydrogenated product of the thermoplastic elastomer (A) can be produced by subjecting the unhydrogenated thermoplastic elastomer (A) obtained above to a hydrogenation reaction.
- the unhydrogenated thermoplastic elastomer (A) obtained above is dissolved in a solvent inert to the reaction and the hydrogenation catalyst, or the unhydrogenated thermoplastic elastomer (A) is dissolved.
- a thermoplastic elastomer (A) a commercial item can also be used as a thermoplastic elastomer (A).
- thermoplastic polymer composition constituting the thermoplastic polymer composition layer (Y) may further contain a polypropylene resin (B).
- a polypropylene resin (B) By containing the polypropylene resin (B), the thermoplastic polymer composition is excellent in film forming property compared to the case where it is not included, and the resulting multilayer film is excellent in coextrusion film forming property.
- polypropylene-based resin (B) known polypropylene-based resins can be used, but those having a content of structural units derived from propylene of 60 mol% or more are preferable.
- the content of the structural unit derived from propylene is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, still more preferably 95 to 99 mol%.
- structural units derived from other than propylene include structural units derived from ethylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1-nonene and 1-decene.
- structural units derived from modifiers described later are also included.
- polypropylene resin (B) examples include homopolypropylene, block polypropylene, propylene-ethylene random copolymer, propylene-butene random copolymer, propylene-ethylene-butene random copolymer, propylene-pentene random copolymer. , Propylene-hexene random copolymers, propylene-octene random copolymers, propylene-ethylene-pentene random copolymers, propylene-ethylene-hexene random copolymers, and modified products thereof.
- the modified product include those obtained by graft copolymerizing a modifier with a polypropylene resin, and those obtained by copolymerizing a modifier with the main chain of the polypropylene resin.
- the polypropylene resin (B) a polar group-containing polypropylene resin (B1) which is a modified product is preferable.
- the polar group-containing polypropylene resin (B1) as the polypropylene resin (B), not only the film forming property is excellent, but also the adhesive force of the thermoplastic polymer composition is improved, and the intermediate layer (Y) is a metal component.
- it exhibits good adhesion performance, can firmly bond the polypropylene resin layer (X) and the decorative layer (Z), and can prevent delamination.
- Examples of the polar group possessed by the polar group-containing polypropylene resin (B1) include (meth) acryloyloxy group; hydroxyl group; amide group; halogen atom such as chlorine atom; carboxyl group; acid anhydride group.
- polar group containing polypropylene resin (B1) Propylene and the polar group containing copolymerizable monomer which is a modifier are random copolymerization, block copolymerization, or grafting by a well-known method. Obtained by copolymerization.
- the polar group contained in the polar group-containing polypropylene resin (B1) may be post-treated after polymerization. For example, it may be neutralized with a metal ion of a (meth) acrylic acid group or a carboxyl group to form an ionomer, or may be esterified with methanol or ethanol. Further, hydrolysis of vinyl acetate or the like may be performed.
- the ratio of the polar group-containing structural unit of the polar group-containing polypropylene resin (B1) to the total structural unit of the polar group-containing polypropylene resin (B1) is preferably 0.01 to 20% by mass. If it is 0.01 mass% or more, adhesiveness will become higher. If the ratio of a polar group containing structural unit is 20 mass% or less, affinity with a thermoplastic elastomer (A) will improve, a mechanical characteristic will become favorable, and the production
- the thermoplastic polymer composition constituting the thermoplastic polymer composition layer (Y) contains 0 to 50 parts by mass of the polypropylene resin (B) with respect to 100 parts by mass of the thermoplastic elastomer (A). preferable.
- the content of the polypropylene resin (B) is preferably 1 part by mass or more and preferably 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A). More preferably, it is 5 to 45 mass parts. More preferably, it is 10 to 30 mass parts.
- thermoplastic polymer composition constituting the thermoplastic polymer composition layer (Y) is an olefin polymer or styrene polymer as required, as long as the effects of the present invention are not significantly impaired.
- other thermoplastic polymers such as polyphenylene ether resin and polyethylene glycol may be contained.
- the olefin polymer include polyethylene, polypropylene, polybutene, block copolymers of propylene and other ⁇ -olefins such as ethylene and 1-butene, and random copolymers.
- the content of the thermoplastic elastomer (A) is preferably not less than 50% by mass.
- the content thereof is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, more preferably 20 parts per 100 parts by mass of the thermoplastic elastomer (A). It is not more than part by mass, more preferably not more than 10 parts by mass, particularly preferably not more than 5 parts by mass.
- thermoplastic polymer composition constituting the thermoplastic polymer composition layer (Y) is a tackifying resin, a softening agent, an antioxidant, a lubricant, and a light stabilizer as necessary, as long as the effects of the invention are not impaired.
- Processing aids, colorants such as pigments and pigments, flame retardants, antistatic agents, matting agents, silicone oil, antiblocking agents, UV absorbers, mold release agents, foaming agents, antibacterial agents, antifungal agents, perfumes Etc. may be contained.
- tackifying resins include aliphatic unsaturated hydrocarbon resins, aliphatic saturated hydrocarbon resins, alicyclic unsaturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, aromatic hydrocarbon resins, and hydrogenated aromatic carbons. Hydrogen resin, rosin ester resin, hydrogenated rosin ester resin, terpene phenol resin, hydrogenated terpene phenol resin, terpene resin, hydrogenated terpene resin, aromatic hydrocarbon modified terpene resin, coumarone indene resin, phenol resin, xylene resin, etc. Is mentioned.
- softeners generally used for rubber and plastics can be used.
- the antioxidant include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, hindered phenol antioxidants are preferable.
- thermoplastic polymer composition constituting the thermoplastic polymer composition layer (Y)
- any method can be used as long as the components can be mixed uniformly.
- a melt-kneading method is used.
- the melt kneading can be performed using a melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, a batch mixer, a roller, a Banbury mixer, and the melt kneading is usually performed preferably at 170 to 270 ° C.
- a thermoplastic polymer composition can be obtained.
- the thermoplastic polymer composition thus obtained preferably has a melt flow rate (MFR) measured by a method according to JIS K 7210 under conditions of a temperature of 230 ° C. and a load of 2.16 kg (21.2 N). It is in the range of 1 to 50 g / 10 minutes, more preferably 1 to 30 g / 10 minutes, still more preferably 1 to 20 g / minute. When the MFR is within this range, good moldability is obtained, and the production of the thermoplastic polymer composition layer (Y) becomes easy.
- MFR melt flow rate
- the adhesive strength of the thermoplastic polymer composition is preferably 15 N / 25 mm or more, more preferably 30 N / 25 mm or more in the compression molding method (molding temperature: 230 ° C., compression time: 5 minutes), more preferably 60 N / 25 mm or more is more preferable.
- the thermoplastic polymer composition should have low tack at room temperature and does not exhibit adhesive strength at that temperature.
- the adhesive strength is a value measured according to JIS K 6854-2.
- thermoplastic polymer composition layer (Y) with respect to the MFR of the intermediate layer (X) measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg (21.2 N) by a method according to JIS K 7210 described above.
- the MFR ratio MFR (Y) / MFR (X) is preferably in the range of 1 to 15 for reasons of production described later.
- a resin film, a nonwoven fabric, artificial leather, natural leather, or the like can be used.
- the resin constituting the resin film include polyolefin resin, polystyrene resin, polyvinyl chloride resin, acrylonitrile styrene resin, acrylonitrile butadiene styrene resin, polycarbonate resin, (meth) acrylic resin, polyethylene terephthalate (PET), and polybutylene.
- polyester resins such as terephthalate; polyamides such as nylon 6, nylon 66 and polyamide elastomer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride, and polyurethane.
- (meth) acrylic resins are preferred from the viewpoints of transparency, weather resistance, surface gloss, and scratch resistance.
- a (meth) acrylic resin including a methacrylic resin and an elastic body is more preferable.
- the methacrylic resin has a structural unit derived from methyl methacrylate, preferably 80 mass% or more, more preferably 90 mass% or more.
- the methacrylic resin is a polymer having a structural unit derived from a monomer other than methyl methacrylate, preferably 20% by mass or less, more preferably 10% by mass or less, and using only methyl methacrylate as a monomer. There may be.
- the method for producing the methacrylic resin is not particularly limited, and can be obtained by polymerizing a monomer (mixture) containing 80% by mass or more of methyl methacrylate or copolymerizing with a monomer other than methyl methacrylate. Moreover, you may use a commercial item as a methacryl resin.
- Examples of such commercially available products include “Parapet H1000B” (MFR: 22 g / 10 min (230 ° C., 37.3 N)), “Parapet GF” (MFR: 15 g / 10 min (230 ° C., 37.3 N)), “ “Parapet EH” (MFR: 1.3 g / 10 min (230 ° C., 37.3 N)), “Parapet HRL” (MFR: 2.0 g / 10 min (230 ° C., 37.3 N)), “Parapet HRS” ( MFR: 2.4 g / 10 min (230 ° C., 37.3 N)) and “Parapet G” (MFR: 8.0 g / 10 min (230 ° C., 37.3 N)) [all trade names, manufactured by Kuraray Co., Ltd. ] Etc. are mentioned.
- Elastic body examples include butadiene rubbers, chloroprene rubbers, block copolymers, multilayer structures and the like, and these may be used alone or in combination. Among these, from the viewpoint of transparency, impact resistance, and dispersibility, a block copolymer or a multilayer structure is preferable, and an acrylic block copolymer or a multilayer structure is more preferable.
- the acrylic block copolymer has a methacrylate polymer block and an acrylic ester polymer block.
- the block copolymer may have only one methacrylic acid ester polymer block and one acrylic acid ester polymer block, or may have a plurality thereof.
- the multilayer structure has at least two layers of an inner layer and an outer layer, and has at least one layer structure in which the inner layer and the outer layer are arranged in this order from the center layer toward the outermost layer.
- the multilayer structure may further have a crosslinkable resin layer inside the inner layer or outside the outer layer.
- An inner layer is a layer comprised from the crosslinked elastic body formed by copolymerizing the monomer mixture which has an alkyl acrylate ester and a crosslinkable monomer.
- an acrylic acid alkyl ester an acrylic acid alkyl ester having an alkyl group having 2 to 8 carbon atoms is preferably used, and examples thereof include butyl acrylate and 2-ethylhexyl acrylate.
- the ratio of the alkyl acrylate ester in the total monomer mixture used to form the inner layer copolymer is preferably in the range of 70 to 99.8% by mass, more preferably. Is 80 to 90% by mass.
- the method for producing the multilayer structure is not particularly limited, but is preferably produced by emulsion polymerization from the viewpoint of controlling the layer structure of the multilayer structure.
- the content of the methacrylic resin is 55 to 90 parts by mass and the content of the elastic body is 45 to 10 parts by mass with respect to a total of 100 parts by mass of the methacrylic resin and the elastic body. More preferably, the content of the methacrylic resin is 70 to 90 parts by mass, and the content of the elastic body is 30 to 10 parts by mass.
- the (meth) acrylic resin is a variety of additives such as antioxidants, heat stabilizers, lubricants, processing aids, antistatic agents, thermal degradation inhibitors, ultraviolet absorbers, light stabilizers, polymer processing aids. , Coloring agents, impact aids and the like may be included.
- the method of adjusting the resin that is the raw material of the resin film there is no particular limitation on the method of adjusting the resin that is the raw material of the resin film, and any method can be used as long as the components can be mixed uniformly, but a method of melt-kneading and mixing is preferable.
- the decorative layer (Z) may be colored.
- a coloring method a method in which a resin or a resin constituting a resin film contains a pigment or a dye and the resin itself before being formed into a film is colored; a dyeing method in which a resin film is immersed in a liquid in which the dye is dispersed and colored
- a coloring method a method in which a resin or a resin constituting a resin film contains a pigment or a dye and the resin itself before being formed into a film is colored
- a dyeing method in which a resin film is immersed in a liquid in which the dye is dispersed and colored
- the decorative layer (Z) may be printed. Patterns and colors such as pictures, characters and figures are added by printing.
- the pattern may be chromatic or achromatic. Printing may be performed on the side in contact with the thermoplastic polymer composition layer (Y) in order to prevent discoloration of the printing layer.
- the decoration layer (Z) may be subjected to vapor deposition.
- metallic tone and gloss are imparted by indium vapor deposition.
- Vapor deposition may be performed on the side in contact with the thermoplastic polymer composition layer (Y).
- the surface is JIS pencil hardness (thickness 75 ⁇ m), preferably HB or harder, more preferably F or harder, Preferably it is H or harder than that.
- the method for producing the multilayer film of the present invention has the thermoplastic polymer composition layer (Y) on both sides of the intermediate layer (X), and the decorative layer (Z) is disposed on any side of (Y).
- the production method is not particularly limited as long as these can be produced so as to be laminated in the order of (Y)-(X)-(Y)-(Z).
- extrusion coating method for example, extrusion coating method, solution coating method, extrusion lamination method, co-extrusion method, heat laminating method, pressure bonding method and the like can be mentioned, and in particular, a multilayer film of (Y)-(X)-(Y) structure by co-extrusion method And (Y)-(X)-(Y)-(Z) is preferred from the viewpoint of process simplification and production cost.
- coextrusion method will be described in detail as an example of the production method.
- a film having the thermoplastic polymer composition layer (Y) on both sides of the intermediate layer (X) is laminated with a melt of the intermediate layer (X) and the thermoplastic polymer composition layer (Y) in a die.
- Manufactured by coextrusion method can be performed using a known method such as a T-die method or an inflation method.
- Examples of the T-die method include a multi-manifold method and a feed block method. In particular, from the viewpoint of thickness accuracy, coextrusion molding by a multi-manifold method is preferable.
- a method including a step of extruding the melt-kneaded material from a T die in a molten state and bringing the surface into contact with the cast roll surface is preferable.
- the opposite surface side is preferably in contact with the touch roll so that the molten resin is in close contact with the cast roll.
- the cast roll used at this time preferably has a hydrophobic resin on the surface.
- the hydrophobic resin include a silicone resin, a fluorine-based resin, and the like. Specifically, for example, a form in which a silicone rubber having a thickness of 3 to 5 mm is wound around the roll surface can be given.
- the hardness of the silicone rubber is preferably 60 to 90A.
- Another example includes a form in which a fluorine-based surface treatment agent is coated on the surface of a metal roll and a fluorine-based resin layer is provided on the surface.
- a fluorine-based surface treatment agent is coated on the surface of a metal roll and a fluorine-based resin layer is provided on the surface.
- (Y) / (X) is preferably 1 to 15, and more preferably 3 to 15. If the MFR ratio is less than 1, film thickness and width may become unstable.
- the decorative layer (Z) is bonded to the laminated film having the intermediate layer (X) and the thermoplastic polymer composition layer (Y) by thermal lamination using two heating rolls.
- a multilayer film can be obtained.
- the thickness T (X) of the intermediate layer (X) is preferably 400 ⁇ m or less. If it is thicker than 400 ⁇ m, the secondary workability such as laminating property, handling property, cutting property, punching property will deteriorate, it will be difficult to use as a multilayer film, and the unit price per unit area will increase, which is economically disadvantageous. Therefore, it is not preferable.
- the thickness of the intermediate layer (X) is more preferably 50 to 300 ⁇ m, particularly preferably 100 to 250 ⁇ m.
- the thickness T (Y) of the thermoplastic polymer composition layer (Y) is preferably 500 ⁇ m or less. When the thickness is greater than 500 ⁇ m, secondary processability such as laminating property, handling property, cutting property and punching property is deteriorated, and the unit price per unit area is increased, which is not preferable because it is economically disadvantageous.
- the thickness of the thermoplastic polymer composition layer (Y) is preferably 10 to 200 ⁇ m, more preferably 30 to 150 ⁇ m, and particularly preferably 50 to 150 ⁇ m.
- the ratio T (Y) / T (X) of the thickness of the thermoplastic polymer composition layer (Y) to the intermediate layer (X) is preferably 0.4 to 1.5.
- the total thickness of the multilayer film of the present invention is preferably less than 1000 ⁇ m. If the thickness of the multilayer film is less than 1000 ⁇ m, it is more preferable that the thickness of the multilayer film is 600 ⁇ m or less when the molded body described later is manufactured. . On the other hand, when the thickness is less than 50 ⁇ m, the shape retention of the film is small, and decorative molding may be difficult.
- the molded article of the present invention is a molded article formed by coating the adherend having a three-dimensional surface with the multilayer film of the present invention, or the preform molded article of the multilayer film of the present invention or the film as an injection mold.
- the adherend is preferably made of a polyolefin resin, ABS resin, or PC / ABS resin.
- the method for producing the molded body of the present invention is not particularly limited as long as the multilayer film of the present invention adheres and covers the surface of the adherend having a three-dimensional curved surface.
- the multilayer film of the present invention is bonded to the surface of an adherend having a three-dimensional curved surface by heating under vacuum forming / pressure forming / vacuum / pressure forming / compression forming to obtain a formed body.
- the multilayer film of the present invention or a preform molded body of the film can be inserted into an injection mold and injection molded to obtain a molded body having a surface decorated with a three-dimensional curved surface.
- This is a method generally called a film insert injection molding method.
- the multilayer film of the present invention and the molded body obtained by laminating the multilayer film on an adherend can be applied to articles requiring design properties.
- billboard parts such as advertising towers, stand signboards, sleeve signboards, billboard signs, rooftop signboards
- display parts such as showcases, partition plates, store displays
- Lighting parts such as chandeliers
- interior parts such as furniture, pendants, mirrors; doors, domes, safety window glass, partitions, staircases, balconies, building parts such as roofs for leisure buildings, automobile interior and exterior components, Transport equipment-related parts such as automobile exterior parts such as bumpers
- electronic equipment parts such as nameplates for audio images, stereo covers, vending machines, mobile phones, personal computers; incubators, rulers, dials, greenhouses, large tanks, box tanks , Bathroom parts, clock panels, bathtubs, sanitary, desk mats, game parts, toys, wallpaper; marking films, various home appliances Suitably used in decorative
- thermoplastic polymer composition layer (Y) The following were used as the thermoplastic polymer composition layer (Y).
- the thermoplastic polymer composition (Y-1) is the composition described in Production Example 1 using the thermoplastic elastomer (A-1) produced in Synthesis Example 1 below.
- the storage elastic modulus under the condition of 120 ° C. was 1750 kPa.
- the tensile elasticity modulus E in 23 degreeC was 58300 kPa.
- the thermoplastic elastomer (Y-2) was the thermoplastic elastomer (A-1) produced in Synthesis Example 1 below, and the storage elastic modulus at 120 ° C. was 828 kPa.
- the tensile elasticity modulus E in 23 degreeC was 13480 kPa.
- adherend As the adherend, one made of the following resin was used. ⁇ Polyolefin resin Polypropylene resin Novatec MA3 (Nippon Polypro Co., Ltd.) ABS resin Clastic MTH2 (manufactured by Japan A & L Co., Ltd.)
- thermoplastic polymer composition (Y) the pellets were formed into a film having a width of 5 mm, a length of 30 mm, and a thickness of 75 ⁇ m by press molding, and using a dynamic viscoelasticity measuring device (DVE-V4 FT Rheospectr manufactured by Rheology). Measurement was performed in a temperature-dependent mode at a frequency of 1 Hz.
- DVE-V4 FT Rheospectr manufactured by Rheology
- the bending rigidity K in the present invention is defined by the following formula.
- K (E ⁇ h 3 ) / 12 [unit: kPa ⁇ mm 3 ]
- E the tensile modulus at 23 ° C.
- h the film thickness.
- Multiplying the flexural modulus K by the film width b is the flexural rigidity of a film having a thickness h having an arbitrary width b.
- the resin pellets constituting the intermediate layer (X) and the resin pellets constituting the thermoplastic polymer composition layer (Y) were each made of a single-screw extruder (manufactured by GM ENGINEERING; VGM25-28EX) hopper and co-extruded using a multi-manifold die to obtain a two-layer film having a width of 300 mm and a thickness of 325 ⁇ m.
- thermoplastic polymer composition layer (Y) and intermediate layer (X) Adhesive strength between thermoplastic polymer composition layer (Y) and intermediate layer (X)
- a peeling angle of 90 ° was applied to the produced multilayer film in accordance with JIS K 6854-2 using a tabletop precision universal testing machine (manufactured by Shimadzu Corporation; AGS-X).
- the peel strength (N / 25 mm) between the thermoplastic polymer composition layer (Y) and the intermediate layer (X) in the multilayer film was measured according to the following criteria under the conditions of a tensile speed of 300 mm / min and an environmental temperature of 23 ° C. evaluated.
- ⁇ Material destruction
- ⁇ Strong adhesion
- thermoplastic polymer composition layer (Y) and decorative layer (Z) thermo lamination
- a multilayer film was produced in the same manner as in the evaluation of the following coextrusion film forming property. Subsequently, using a thermal lamination apparatus (manufactured by Taisei Laminator Co., Ltd .; VAII-700 type), the resin film constituting the decorative layer (Z) between the heating rolls at 120 ° C. and 40 ° C. and the multilayer film, One side was bonded by heat laminating through a roll with a protective film attached. At this time, the resin film side which comprises a decoration layer (Z) was made into the roll side of 120 degreeC.
- the obtained multilayer film was cut out and cut using a cross-cut jig in accordance with JIS K 5400 to produce 100 grids (1 mm long x 1 mm wide) at 25 ° C. and 50% RH environment. Then, the cellophane tape (manufactured by Nichiban Co., Ltd.) was pressed and pulled up in the direction of 90 degrees to evaluate the peel strength according to the following criteria. ⁇ : No peeling ⁇ : There is peeling
- thermoplastic polymer composition layer (Y) was in direct contact with the mold, it was molded with a protective film attached.
- ⁇ Can be molded without problems
- ⁇ There is a problem with molding (film deflection / wrinkle, poor shaping)
- the polyolefin resin or ABS resin side of the obtained sample is fixed to a stainless steel (SUS) plate with a strong adhesive tape (manufactured by Nitto Denko Corporation; Hyper Joint H9004), and a desktop precision universal testing machine (manufactured by Shimadzu Corporation; AGS- X), a thermoplastic polymer composition layer (Y) and an adherend in a multilayer film under the conditions of a peel angle of 90 °, a tensile speed of 300 mm / min, and an environmental temperature of 23 ° C.
- SUS stainless steel
- a strong adhesive tape manufactured by Nitto Denko Corporation; Hyper Joint H9004
- a desktop precision universal testing machine manufactured by Shimadzu Corporation; AGS- X
- Y thermoplastic polymer composition layer
- adherend in a multilayer film under the conditions of a peel angle of 90 °, a tensile speed of 300 mm / min, and an environmental temperature of 23 ° C.
- the obtained reaction liquid was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-polyisoprene-polystyrene.
- 10 kg of a triblock copolymer composed of polystyrene-polyisoprene-polystyrene was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was 5% by mass with respect to the copolymer.
- the reaction was carried out for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150 ° C.
- thermoplastic elastomer a triblock copolymer consisting of polystyrene-polyisoprene-polystyrene (hereinafter referred to as “thermoplastic elastomer”).
- the resulting thermoplastic elastomer (A-1) has a weight average molecular weight of 107,000, a styrene content of 21% by mass, a hydrogenation rate of 85%, a molecular weight distribution of 1.04, and a polyisoprene block containing 1,1.
- the total amount of 2-bond and 3,4-bond was 60 mol%.
- the maleic anhydride concentration is a value obtained by titration using a methanol solution of potassium hydroxide.
- fusing point is the value calculated
- the obtained copolymer dispersion was washed with an appropriate amount of ion-exchanged water, the bead-shaped copolymer was taken out with a bucket-type centrifuge, dried for 12 hours with a hot air dryer at 80 ° C., and the weight average molecular weight Mw (F ) And a bead-like methacrylic resin (F-1) having a Tg of 128 ° C. were obtained.
- thermoplastic polymer composition (Y-1) 80 parts by mass of the thermoplastic elastomer (A-1) obtained in Synthesis Example 1 and 20 parts by mass of the polar group-containing polypropylene resin (B-1) obtained in Synthesis Example 2 were mixed with a twin-screw extruder (Toshiba Machine Co., Ltd .; TEM -28, all the same in the following production examples) were melt kneaded at 230 ° C., extruded into strands and cut to produce pellets of the thermoplastic polymer composition (Y-1). The MFR of the resin was 7.4 g / 10 minutes.
- Example 1 The pellet of the thermoplastic polymer composition (Y-1) and the pellet of the intermediate layer resin (X-1) obtained in Production Example 1 were each single screw extruder (manufactured by GM ENGINEERING; VGM25-28EX). And coextruded using a multi-manifold die to obtain a two-type three-layer film having a width of 300 mm and a thickness of 300 ⁇ m. The thickness of each layer was controlled by the extrusion flow rate, and the thickness of the thermoplastic polymer composition (Y-1) was 50 ⁇ m, and the thickness of the intermediate layer resin (X-1) was 200 ⁇ m.
- thermoplastic polymer composition (Y-1) layer had low tack at room temperature and did not adhere at that temperature.
- (meth) acrylic resin (Z-1) obtained in Production Example 2 and using a single-screw extruder and a single-layer T-die, (meth) acrylic resin A film (thickness 75 ⁇ m) was obtained.
- a multilayer film having a three-kind four-layer structure was manufactured by thermally laminating the two-layer film obtained above and a (meth) acrylic resin film.
- the thermal laminate uses a thermal lamination apparatus (manufactured by Taisei Laminator Co., Ltd .; VAII-700 type) and a (meth) acrylic resin film that constitutes a decorative layer (Z) between heating rolls at 120 ° C. and 40 ° C.
- the two types and three layers film were laminated by heat laminating and pasting so that the resin film was arranged on the thermoplastic polymer composition layer (Y) side.
- a protective film was attached to one side of the thermoplastic polymer composition layer, and the (meth) acrylic resin film side was set to the roll side at 120 ° C.
- the multilayer film obtained above and a polyolefin resin or ABS resin the multilayer film is made into a gold of a direct pressure hydraulic molding machine (M-100C-AS-DM, manufactured by Meiki Seisakusho Co., Ltd.). It is accommodated in a mold, the movable mold and the fixed mold are clamped, and a polyolefin resin or ABS is injected into the cavity by injecting a molten resin of polyolefin resin at 230 ° C. and a molten resin temperature of ABS resin at 260 ° C. A molded body in which a multilayer film was laminated using the resin as an adherend was produced.
- M-100C-AS-DM direct pressure hydraulic molding machine
- Example 2 A multilayer film and a molded body were obtained in the same manner as in Example 1 except that the thickness of the polypropylene resin (X-1) in the intermediate layer was 150 ⁇ m. The results are shown in Table 1.
- Example 3 a multilayer film and a molded body were obtained in the same manner as in Example 2 except that the polypropylene resin (X-2) was used instead of the polypropylene resin (X-1). The results are shown in Table 1.
- Example 4 a multilayer film and a molded product were obtained in the same manner as in Example 2 except that the polypropylene resin (X-3) was used instead of the polypropylene resin (X-1). The results are shown in Table 1.
- Example 5 a multilayer film and a molded body were obtained in the same manner as in Example 2 except that the (meth) acrylic resin (X-5) was used instead of the intermediate layer polypropylene resin (X-1). .
- the results are shown in Table 1.
- Example 6 a multilayer film and a molded body were obtained in the same manner as in Example 1 except that the thermoplastic polymer composition (Y-2) was used instead of the thermoplastic polymer composition (Y-1). .
- the results are shown in Table 1.
- the thermoplastic polymer composition (Y-2) layer had low tackiness at room temperature and did not adhere at that temperature.
- Example 7 a multilayer film and a molded body were obtained in the same manner as in Example 2 except that the polypropylene resin (X-4) was used instead of the intermediate layer polypropylene resin (X-1). The results are shown in Table 1.
- Example 8> A multilayer film and a molded body were obtained in the same manner as in Example 3, except that the thickness of the polypropylene resin (X-2) in the intermediate layer was 85 ⁇ m. The results are shown in Table 1.
- Example 9 a multilayer film and a molded body were obtained in the same manner as in Example 3, except that the thickness of the polypropylene resin (X-2) of the intermediate layer was 500 ⁇ m. The results are shown in Table 1.
- Example 10 A multilayer film and a molded body were obtained in the same manner as in Example 1, except that the thickness of the polypropylene resin (X-1) in the intermediate layer was changed to 300 ⁇ m. The results are shown in Table 1.
- Example 11 A multilayer film and a molded body were obtained in the same manner as in Example 3, except that the thickness of the polypropylene resin (X-2) in the intermediate layer was changed to 610 ⁇ m. The results are shown in Table 1.
- thermoplastic polymer composition layer (Y-1) was produced by compression molding (molding temperature: 230 ° C., compression time: 5 minutes), and items other than film forming properties were evaluated. The results are shown in Table 1.
- thermoplastic polymer composition (Y-2) was used in the same manner as in Comparative Example 2 except that the thermoplastic polymer composition (Y-2) was used instead of the thermoplastic polymer composition (Y-1). An attempt was made to obtain a Y-2) single-layer film, but the thermoplastic polymer composition layer (Y-2) was too close to the surface of the metal roll to release, and a film could not be obtained. Therefore, a thermoplastic polymer composition layer (Y-2) was prepared by compression molding (molding temperature: 230 ° C., compression time: 5 minutes), and items other than film forming properties were evaluated. The results are shown in Table 1.
- Example 3 a multilayer film and a molded body were obtained in the same manner as in Example 1 except that the thickness of the polypropylene resin (X-1) of the intermediate layer was 500 ⁇ m. The results are shown in Table 1.
- the multilayer film has the thermoplastic polymer resin composition layer (Y) on the front and back, so that it adheres to the (meth) acrylic resin in thermal lamination, and in vacuum molding and film insert injection molding.
- a molded article having extremely high adhesive strength with a polyolefin resin or ABS resin was obtained.
- the thermoplastic polymer resin composition layer (Y) was low tack at normal temperature and did not adhere at that temperature.
- Examples 1 to 4, 6 and 7 using a polypropylene resin as the intermediate layer (X) were particularly firmly bonded as a multilayer film.
- thermoplastic polymer resin composition layer (Y) in Examples 1 to 6 in which the MFR ratio (Y) / (X) of the intermediate layer (X) and the thermoplastic polymer resin composition layer (Y) is 1 to 15, in particular, the intermediate layer (X) and The coextrusion film forming property of the thermoplastic polymer resin composition layer (Y) was also excellent. Further, since it has the intermediate layer (X), it was excellent in handling property at the time of preforming the multilayer film and mold setting property (shape retaining property of the preform molded product) at the time of insert injection molding of the preform molded product.
- Example 7 where the MFR ratio (Y) / (X) is 0.6, the coextrusion film-forming property between the intermediate layer (X) and the thermoplastic polymer resin composition layer (Y) is poor.
- the film was slightly inferior in properties and thickness uniformity.
- Comparative Examples 1 and 2 which are single layers of the thermoplastic polymer resin composition (Y) that does not have the intermediate layer (X), the film cannot be released due to over-adhering to the surface of the metal roll and cannot be formed. It was.
- the film formed by compression molding was used to evaluate the handleability during preforming and the shape retention during insert injection molding of the preform molded body. Occasionally, wrinkles were generated, and in the injection molding, the preform molded body was deformed, and there was a problem in mold setting.
- Comparative Example 3 shaping failure occurred during preforming, and the mold setting property during insert injection molding was poor. *
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Abstract
Description
特許文献1に記載のフィルムでは、バッキング層の材質によって、射出成形樹脂の材質、すなわち3次元立体形状の被着体の材質が限定される。そのため、被着体の材質ごとにバッキング層、バッキング層に適用する接着剤の材質を変更したフィルムを用意する必要がある。この場合、銘柄数が増えるために、切り替えや管理上の手間等が問題になる。また、特許文献1に記載のフィルムは、加飾工法としてフィルムインサート射出成形法にしか対応しておらず、加飾工法が限定される。多種多様な被着体形状に対応させるためには、真空成形法や圧空成形法、真空圧空成形法、圧縮成形法などの工法に対応できる必要があるが、従来知られているバッキングフィルム構成では、前述した各種工法でフィルムを被着体と接着させることができない。
本発明の多層フィルムは、曲げ剛性率が60~30000kPa・mm3である熱可塑性樹脂層を中間層(X)とし、芳香族ビニル化合物単位からなる重合体ブロック(a1)および共役ジエン化合物単位からなる重合体ブロック(a2)を含有するブロック共重合体またはその水素添加物である熱可塑性エラストマー(A)100質量部に対してポリプロピレン系樹脂(B)0~50質量部を含有する熱可塑性重合体組成物からなる層(Y)を両面に有する多層フィルムに、加飾層(Z)が(Y)のいずれかの面に密着して配置されてなる少なくとも4層構造の多層フィルムであって、前記中間層(X)に対する前記熱可塑性重合体組成物層(Y)の温度230℃、荷重2.16kg(21.2N)下におけるMFR比(Y)/(X)が1~15である多層フィルムである。以下、各層について順に説明する。
中間層(X)で用いられる熱可塑性樹脂としては、公知のフィルム基材に用いられるものであれば限定されることはない。例えばポリオレフィン系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル樹脂、アクリロニトリルスチレン樹脂、ABS樹脂(アクリロニトリルブタジエンスチレン樹脂)、ポリカーボネート樹脂、ポリエステル系樹脂、(メタ)アクリル系樹脂、日本ゼオン製のゼオノア(登録商標)、ゼオネックス(登録商標)およびJSR製のアートン(登録商標)などが挙げられる。中でも機械物性、接着性、取り扱い性の観点から、ポリオレフィン系樹脂、ポリエステル系樹脂が好ましく、特にポリプロピレン系樹脂が好ましい。
中でも、比較的安価、かつ容易に入手できるという観点から、ホモポリプロピレン、プロピレン-エチレンランダム共重合体、ブロックポリプロピレンが好ましい。さらに、ポリオレフィン系樹脂との接着力の観点および多層フィルムの反り低減の観点から、プロピレン-エチレンランダム共重合体が特に好ましい。
ポリプロピレン系樹脂は、1種を単独で使用してもよいし、2種以上を併用してもよい。また、中間層(X)は前記ポリプロピレン系樹脂の他に、本発明の効果を損ねない範囲で、他の樹脂を含有してもよい。
なお、本明細書および特許請求の範囲に記載の「メルトフローレート」は全て、JIS K 7210に準拠して測定した値である。
また、前記熱可塑性樹脂の流動開始温度は、特に制限されるものではないが、好ましくは120~190℃、より好ましくは120~180℃である。通常、流動開始温度は非晶性樹脂において定義されるが、本明細書において結晶性樹脂の流動開始温度は融点で代表されるものとする。
熱可塑性重合体組成物層(Y)を構成する熱可塑性重合体組成物は、芳香族ビニル化合物単位からなる重合体ブロック(a1)および共役ジエン化合物単位からなる重合体ブロック(a2)を含有するブロック共重合体またはその水素添加物である熱可塑性エラストマー(A)を含有する。前記熱可塑性重合体組成物における熱可塑性エラストマー(A)の含有量は50質量%以上であることが好ましく、65質量%以上がより好ましい。
前記熱可塑性エラストマー(A)に含まれる芳香族ビニル化合物単位からなる重合体ブロック(a1)を構成する芳香族ビニル化合物としては、例えば、スチレン、α-メチルスチレン、2-メチルスチレン、3-メチルスチレン、4-メチルスチレン、4-プロピルスチレン、4-シクロヘキシルスチレン、4-ドデシルスチレン、2-エチル-4-ベンジルスチレン、4-(フェニルブチル)スチレン、1-ビニルナフタレン、2-ビニルナフタレンなどが挙げられる。芳香族ビニル化合物単位を含有する重合体ブロックは、これらの芳香族ビニル化合物の1種のみに由来する構造単位からなっていてもよいし、2種以上に由来する構造単位からなっていてもよい。中でも、スチレン、α-メチルスチレン、4-メチルスチレンが好ましい。
共役ジエン化合物単位を含有する重合体ブロック(a2)は、これらの共役ジエン化合物の1種のみに由来する構造単位からなっていてもよいし、2種以上に由来する構造単位からなっていてもよい。特に、ブタジエンまたはイソプレンに由来する構造単位、またはブタジエンおよびイソプレンに由来する構造単位からなっていることが好ましい。
なお、1,2-結合量および3,4-結合量の合計量は、1H-NMR測定によって算出できる。具体的には、1,2-結合および3,4-結合単位に由来する4.2~5.0ppmに存在するピークの積分値および1,4-結合単位に由来する5.0~5.45ppmに存在するピークの積分値との比から算出できる。
直鎖状の結合形態の例としては、重合体ブロック(a1)をaで、重合体ブロック(a2)をbで表したとき、a-bで表されるジブロック共重合体、a-b-aまたはb-а-bで表されるトリブロック共重合体、a-b-a-bで表されるテトラブロック共重合体、a-b-a-b-aまたはb-a-b-a-bで表されるペンタブロック共重合体、(а-b)nX型共重合体(Xはカップリング残基を表し、nは2以上の整数を表す)、およびこれらの混合物が挙げられる。これらの中でも、トリブロック共重合体が好ましく、a-b-aで表されるトリブロック共重合体であることがより好ましい。
熱可塑性エラストマー(A)は、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
また、熱可塑性エラストマー(A)としては、市販品を使用することもできる。
熱可塑性重合体組成物層(Y)を構成する熱可塑性重合体組成物は、さらにポリプロピレン系樹脂(B)を含有してもよい。ポリプロピレン系樹脂(B)を含有することにより、含有しない場合に比べて熱可塑性重合体組成物は製膜性に優れ、得られる多層フィルムは共押出製膜性に優れるものとなる。
極性基含有ポリプロピレン系樹脂(B1)が有する極性基としては、例えば、(メタ)アクリロイルオキシ基;水酸基;アミド基;塩素原子などのハロゲン原子;カルボキシル基;酸無水物基などが挙げられる。
熱可塑性重合体組成物層(Y)を構成する熱可塑性重合体組成物は、本発明の効果を著しく損なわない範囲で、必要に応じてオレフィン系重合体、スチレン系重合体、ポリフェニレンエーテル系樹脂、ポリエチレングリコールなど、他の熱可塑性重合体を含有していてもよい。オレフィン系重合体としては、例えば、ポリエチレン、ポリプロピレン、ポリブテン、プロピレンとエチレンや1-ブテンなどの他のα-オレフィンとのブロック共重合体やランダム共重合体などが挙げられる。それらが含まれることによって、熱可塑性エラストマー(A)の含有量が50質量%を下回らないのが好ましい。
すなわち、他の熱可塑性重合体を含有させる場合、その含有量は、熱可塑性エラストマー(A)100質量部に対して、好ましくは100質量部以下、より好ましくは50質量部以下、より好ましくは20質量部以下、さらに好ましくは10質量部以下、特に好ましくは5質量部以下である。
酸化防止剤としては、例えばヒンダードフェノール系、リン系、ラクトン系、ヒドロキシル系の酸化防止剤などが挙げられる。これらの中でも、ヒンダードフェノール系酸化防止剤が好ましい。
上記したJIS K 7210に準じた方法で、温度230℃、荷重2.16kg(21.2N)の条件下で測定した前記中間層(X)のMFRに対する前記熱可塑性重合体組成物層(Y)のMFRの比MFR(Y)/MFR(X)は後述する製造上の理由から1~15の範囲であるのが好ましい。
加飾層(Z)としては、樹脂フィルム、不織布、人工皮革、天然皮革などを用いることができる。中でも、加飾層(Z)としては樹脂フィルムからなる層を少なくとも有するものが特に好ましい。
前記樹脂フィルムを構成する樹脂としては、例えばポリオレフィン系樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、アクリロニトリルスチレン樹脂、アクリロニトリルブタジエンスチレン樹脂、ポリカーボネート樹脂、(メタ)アクリル系樹脂、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレートなどのポリエステル樹脂;ナイロン6、ナイロン66、ポリアミドエラストマーなどのポリアミド、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、エチレン-ビニルアルコール共重合体、ポリアセタール、ポリフッ化ビニリデン、ポリウレタンなどが挙げられる。中でも透明性、耐候性、表面光沢性、耐擦傷性の観点から(メタ)アクリル系樹脂が好ましい。かかる(メタ)アクリル系樹脂としては、メタクリル樹脂および弾性体を含む(メタ)アクリル系樹脂がより好ましい。
また、加飾層(Z)の厚みについて、何ら限定するわけではないが、成形加工性、経済性の観点から薄いことが好ましい。
メタクリル樹脂はメタクリル酸メチルに由来する構造単位を好ましくは80質量%以上、より好ましくは90質量%以上有する。換言すると、メタクリル樹脂はメタクリル酸メチル以外の単量体に由来する構造単位を好ましくは20質量%以下、より好ましくは10質量%以下有し、メタクリル酸メチルのみを単量体とする重合体であってもよい。
弾性体としてはブタジエン系ゴム、クロロプレン系ゴム、ブロック共重合体、多層構造体などが挙げられ、これらを単独でまたは組み合わ・BR>ケて用いてもよい。これらの中でも透明性、耐衝撃性、分散性の観点からブロック共重合体または多層構造体が好ましく、アクリル系ブロック共重合体または多層構造体がより好ましい。
多層構造体は内層および外層の少なくとも2層を有し、内層および外層が中心層から最外層方向へこの順に配されている層構造を少なくとも一つ有している。多層構造体は内層の内側または外層の外側にさらに架橋性樹脂層を有してもよい。
係るアクリル酸アルキルエステルとしては、アルキル基の炭素数が2~8の範囲であるアクリル酸アルキルエステルが好ましく用いられ、ブチルアクリレート、2-エチルヘキシルアクリレートなどが挙げられる。内層の共重合体を形成させるために使用される全単量体混合物におけるアクリル酸アルキルエステルの割合は、耐衝撃性の点から、好ましくは70~99.8質量%の範囲であり、より好ましくは80~90質量%である。
加飾層(Z)を構成する(メタ)アクリル系樹脂がメタクリル樹脂および弾性体を含む場合、各成分の含有量は、メタクリル樹脂と弾性体との合計100質量部に対して、メタクリル樹脂の含有量が10~99質量部であり、弾性体の含有量が90~1質量部であることが好ましい。メタクリル樹脂の含有量が10質量部未満だと、加飾層(Z)の表面硬度が低下する傾向となる。より好ましくは、メタクリル樹脂と弾性体との合計100質量部に対して、メタクリル樹脂の含有量が55~90質量部であり、弾性体の含有量が45~10質量部である。さらに好ましくは、メタクリル樹脂の含有量が70~90質量部であり、弾性体の含有量が30~10質量部である。
本発明の多層フィルムを製造する方法は、中間層(X)の両面に熱可塑性重合体組成物層(Y)を有し、加飾層(Z)が(Y)のいずれかの面に配置されて、これらが(Y)-(X)-(Y)-(Z)の順で積層するように製造できる成形法であれば特に製造方法に制限はない。例えば、押出コーティング法、溶液塗工法、押出ラミネーション法、共押出法、熱ラミネート法、圧着法などが挙げられ、特に、共押出法により(Y)-(X)-(Y)構成の多層フィルムを製造し、熱ラミネート法により加飾層(Z)を貼合わせて(Y)-(X)-(Y)-(Z)とする方法が工程簡略化、製造コストの観点で好ましい。以下、製造方法の一例として共押出法について詳細に説明する。
本発明の成形体は、本発明の多層フィルムが3次元表面を有する被着体を被覆してなる成形体、または、本発明の多層フィルム若しくは該フィルムのプリフォーム成形体を射出成形金型に挿入し、射出成形によって被着体と一体成形してなる成形体であって、前記多層フィルム中の熱可塑性重合体組成物層(Y)を介して接着することを特徴とするものである。前記被着体は、ポリオレフィン系樹脂やABS樹脂、PC/ABS樹脂よりなるものであるのが好ましい。
本発明の成形体の製造方法は、3次元曲面の表面を有する被着体の表面を本発明の多層フィルムが接着し被覆してなる限り特に制限されない。例えば、本発明の多層フィルムを、3次元曲面の表面を有する被着体の表面に、加熱下で真空成形・圧空成形・真空圧空成形・圧縮成形して接着することにより、成形体を得ることができる。また例えば、シート状の被着体に本発明の多層フィルムを熱ラミネート等の既知の方法により接着した後、加熱下で真空成形・圧空成形・圧縮成形して3次元曲面が加飾された表面を有する成形体を得ることができる。
また例えば、本発明の多層フィルムまたは該フィルムのプリフォーム成形体を射出成形金型内に挿入し、射出成形して3次元曲面が加飾された表面を有する成形体を得ることができる。これは、フィルムインサート射出成形法と一般に呼ばれている方法である。
本発明の多層フィルムおよび該多層フィルムが被着体に積層した成形体は、意匠性の要求される物品に適用することができる。例えば、広告塔、スタンド看板、袖看板、欄間看板、屋上看板等の看板部品;ショーケース、仕切板、店舗ディスプレイ等のディスプレイ部品;蛍光灯カバー、ムード照明カバー、ランプシェード、光天井、光壁、シャンデリア等の照明部品;家具、ペンダント、ミラー等のインテリア部品;ドア、ドーム、安全窓ガラス、間仕切り、階段腰板、バルコニー腰板、レジャー用建築物の屋根等の建築用部品、自動車内外装部材、バンパーなどの自動車外装部材等の輸送機関係部品;音響映像用銘板、ステレオカバー、自動販売機、携帯電話、パソコン等の電子機器部品;保育器、定規、文字盤、温室、大型水槽、箱水槽、浴室部材、時計パネル、バスタブ、サニタリー、デスクマット、遊技部品、玩具、壁紙;マーキングフィルム、各種家電製品の加飾用途に好適に用いられる。
[多層フィルム]
<中間層(X)>
中間層(X)として、以下の樹脂を用いた。
・ポリプロピレン系樹脂(X-1) ポリプロピレン系樹脂CALP-E4361-1(タルク配合、融点=125℃、融解熱量=404mJ、結晶化度=27(ポリプロピレンマトリックスでの値とした)、MFR=0.9g/10分、23℃における引張弾性率E=2960000kPa)
・ポリプロピレン系樹脂(X-2) ポリプロピレン系樹脂ノバテックEG7FTB(ポリプロピレン-エチレンランダム共重合体、融点=149℃、融解熱量=437mJ、結晶化度=28、MFR=1.5g/10分、23℃における引張弾性率E=1150000kPa)
・ポリプロピレン系樹脂(X-3) ポリプロピレン系樹脂ノバテックEC9(ブロックポリプロピレン、融点=164℃、融解熱量=498mJ、結晶化度=30、MFR=0.9g/10分、23℃における引張弾性率E=1200000kPa)
・ポリプロピレン系樹脂(X-4) ポリプロピレン系樹脂ノバテックMA3(ホモポリプロピレン、融点=166℃、融解熱量=780mJ、結晶化度=40、MFR=13g/10分、23℃における引張弾性率E=1600000kPa)
・(メタ)アクリル系樹脂(X-5) 下記製造例2で得られた(メタ)アクリル系樹脂(ガラス転移点=128℃、MFR=3.4g/10分、23℃における引張弾性率E=1540000kPa)
なお、(X-1)は出光ライオンコンポジット株式会社製、(X-2)、(X-3)および(X-4)は日本ポリプロ株式会社製、(X-5)は下記製造例2で得られた(メタ)アクリル系樹脂である。上記のMFRはいずれも温度230℃、荷重2.16kg(21.2N)の条件下で測定した値である。
熱可塑性重合体組成物層(Y)として、以下のものを用いた。
・熱可塑性重合体組成物(Y-1)は、下記合成例1で製造した熱可塑性エラストマー(A-1)を用いた製造例1に記載の組成物である。120℃条件下での貯蔵弾性率は1750kPaであった。また、23℃における引張弾性率Eは58300kPaであった。
・熱可塑性エラストマー(Y-2)は下記合成例1で製造した熱可塑性エラストマー(A-1)であり、120℃条件下での貯蔵弾性率は828kPaであった。また、23℃における引張弾性率Eは13480kPaであった。
加飾層(Z)として、下記製造例2で得られた(メタ)アクリル系樹脂(Z-1)を用いた。
被着体として、以下の樹脂よりなるものを用いた。
・ポリオレフィン系樹脂 ポリプロピレン系樹脂 ノバテックMA3(日本ポリプロ株式会社製)
・ABS系樹脂 クララスチックMTH2(株式会社日本A&L製)
[重量平均分子量(Mw)および分子量分布(Mw/Mn)]
ゲルパーミエーションクロマトグラフィー(GPC)により標準ポリスチレン換算の分子量として求めた。
・装置:東ソー株式会社製GPC装置「HLC-8020」
・分離カラム:東ソー株式会社製「TSKgel GMHXL」、「G4000HX」および「G5000HXL」を直列に連結
・溶離剤:テトラヒドロフラン
・溶離剤流量:1.0ml/分
・カラム温度:40℃
・検出方法:示差屈折率(RI)
1H-NMR測定によって求めた。
・装置:核磁気共鳴装置「Lambda-500」(日本電子株式会社製)
・溶媒:重水素化クロロホルム
上記各中間層樹脂について、示差走査熱量測定装置(METTLER TLEDO社製;DSC30)を用いて、窒素雰囲気下で昇温法:25℃→190℃→25℃→190℃(速度10℃/min)によって測定した。評価は2nd-Runで実施し、融点は融解曲線における吸熱ピーク温度、融解熱量は吸熱ピーク面積から算出した。
各種樹脂について、JIS K 7210に準拠した方法で、MFR測定装置(TAKARA社製;MELT INDEXER L244)を用いて、測定温度:230℃、測定荷重:2.16kg(21.2N)の条件で測定した。
熱可塑性重合体組成物(Y)について、ペレットをプレス成形により幅5mm、長さ30mm、厚み75μmのフィルムとし、動的粘弾性測定装置(レオロジー社製DVE―V4 FTレオスペクトラー)を用いて温度依存性モード、周波数1Hzで測定した。
本発明における曲げ剛性率Kは、下記式によって定義されるものとした。
K=(E×h3)/12 [単位;kPa・mm3]
ここで、Eは23℃における引張弾性率、hはフィルム厚みである。曲げ剛性率Kにフィルム幅bをかけたものが、任意の幅bを有する厚さhのフィルムの曲げ剛性である。
各実施例および比較例において、中間層(X)を構成する樹脂ペレットと熱可塑性重合体組成物層(Y)を構成する樹脂ペレットとをそれぞれ単軸押出機(G.M.ENGINEERING社製;VGM25-28EX)のホッパーに投入し、マルチマニホールドダイを用いて共押出しし、幅300mmかつ厚さ325μmの2層フィルムを得た。このときのフィルムの厚み斑および端部の脈動の有無を目視によって観察し、共押出製膜性を下
記の基準により評価した。
○:フィルム外観に問題なく製膜可
×:フィルム外観に問題あり(厚み斑・脈動あり)、または製膜不可
前記共押出製膜性の評価と同様にして、作製した多層フィルムについて、卓上精密万能試験機(島津製作所社製;AGS-X)を使用し、JIS K 6854-2に準じて剥離角度90°、引張速度300mm/分、環境温度23℃の条件で、多層フィルムにおける熱可塑性重合体組成物層(Y)と中間層(X)との間の剥離強度(N/25mm)を下記の基準により評価した。
◎:材料破壊
○:強固に接着
×:剥がれあり
下記共押出製膜性の評価と同様にして、多層フィルムを作製した。
続いて、熱ラミネーション装置(大成ラミネーター株式会社製;VAII-700型)を用いて、120℃および40℃の加熱ロール間に加飾層(Z)を構成する樹脂フィルムと上記多層フィルムとを、片面は保護フィルムを貼付した状態でロールに通して熱ラミネートして貼り合せた。このとき、加飾層(Z)を構成する樹脂フィルム側が120℃のロール側とした。得られた多層フィルムを切り出し、JIS K 5400に準じて、クロスカット治具を用いて切り込みを入れ、100個の碁盤目(縦1mm×横1mm)を作製し、25℃、50%RH環境下でセロハンテープ(ニチバン株式会社製)を押し付けて90度方向に引き上げることで剥離強度を下記の基準により評価した。
○:剥がれ無し
×:剥がれあり
真空圧空成形機(布施真空社製;NGF0406成形機)の真空チャンバーボックス内において、加飾層(Z)がステージ上に配置された凸型の金型(縦250mm×横160mm×高さ25mm)の反対側になるように、前記熱ラミネーションによって得られた多層フィルム(縦210mm×横297mm)を挿入した後、該フィルムを真空下で110℃まで加熱し、チャンバーボックス内の圧力を0.3MPaとしてフィルムに加圧することによって、三次元表面加飾成形(Three dimension Overlay
Method:TOM成形)を行って、多層フィルムを箱型形状に賦形し、プリフォーム時のハンドリング性を下記の基準により評価した。なお、熱可塑性重合体組成物層(Y)が金型に直接接する場合は、保護フィルムを貼付した状態で成形した。
○:問題なく成形できる
×:成形に問題あり(フィルムたわみ・しわ、賦形不良)
前記プリフォーム成形体を、直圧式油圧成形機(株式会社名機製作所製;M-100C-AS-DM)の金型内に収容する際のセット性を下記の基準により評価した。
○:問題なく金型にセットでき、成形できる
×:金型へのセット性に問題あり(金型からの外れ落ち・射出成形樹脂の裏回り)
前記真空成形において、凸型の金型に代えて、前記ポリオレフィン系樹脂またはABS樹脂製の板状の被着体を設置して真空成形を行い、接着強度測定用試料を得た。得られた試料のポリオレフィン樹脂またはABS樹脂側をステンレス鋼材(SUS)板に強粘着テープ(日東電工社製;ハイパージョイントH9004)で固定して、卓上精密万能試験機(島津製作所社製;AGS-X)を使用し、JIS K 6854-2に準じて剥離角度90°、引張速度300mm/分、環境温度23℃の条件で、多層フィルムにおける熱可塑性重合体組成物層(Y)と被着体であるポリオレフィン樹脂またはABS樹脂よりなる試料の間の剥離強度をそれぞれ測定し、真空成形体における被着体に対する多層フィルムの接着強度(N/25mm)を下記の基準により評価した。
◎:材料破壊
○:強固に接着
×:剥がれあり
前記熱ラミネーションによって得られた多層フィルムと、ポリオレフィン系樹脂またはABS樹脂とを用いて、多層フィルムを、直圧式油圧成形機(株式会社名機製作所製;M-100C-AS-DM)の金型内に収容し、可動側型と固定側型とを型締めし、キャビティ内にポリオレフィン樹脂の溶融樹脂を230℃、ABS樹脂を260℃で射出することによって、ポリオレフィン樹脂またはABS樹脂をそれぞれ被着体として多層フィルムが積層された成形体を製造した。得られた多層フィルムが積層した成形体の物性について、前記した卓上精密万能試験機で剥離強度を下記の基準により評価した。
◎:材料破壊
○:強固に接着
×:剥がれあり
窒素置換し乾燥させた耐圧容器に、溶媒としてシクロヘキサン64Lを、開始剤としてsec-ブチルリチウム(10質量%シクロヘキサン溶液)0.20Lを、有機ルイス塩基としてテトラヒドロフラン0.3Lを仕込んだ。50℃に昇温した後、スチレン2.3Lを加えて3時間重合させ、引き続いてイソプレン23Lを加えて4時間重合を行い、さらにスチレン2.3Lを加えて3時間重合を行った。得られた反応液をメタノール80Lに注ぎ、析出した固体を濾別して50℃で20時間乾燥し、ポリスチレン-ポリイソプレン-ポリスチレンからなるトリブロック共重合体を得た。続いて、ポリスチレン-ポリイソプレン-ポリスチレンからなるトリブロック共重合体10kgをシクロヘキサン200Lに溶解し、水素添加触媒としてパラジウムカーボン(パラジウム担持量:5質量%)を該共重合体に対して5質量%添加し、水素圧力2MPa、150℃の条件で10時間反応を行った。放冷、放圧後、濾過によりパラジウムカーボンを除去し、濾液を濃縮し、さらに真空乾燥して、ポリスチレン-ポリイソプレン-ポリスチレンからなるトリブロック共重合体の水添物(以下、「熱可塑性エラストマー(A-1)」と称する)を得た。得られた熱可塑性エラストマー(A-1)の重量平均分子量は107,000、スチレン含有量は21質量%、水素添加率は85%、分子量分布は1.04、ポリイソプレンブロックに含まれる1,2-結合および3,4-結合の量の合計は60mol%であった。
ポリプロピレン(プライムポリマー社製;プライムポリプロF327)42kg、無水マレイン酸160gおよび2,5-ジメチル-2,5-ジ(tert-ブチルパーオキシ)ヘキサン42gを、バッチミキサーを用いて180℃およびスクリュー回転数40rpmの条件で溶融混練し、極性基含有ポリプロピレン系樹脂(B-1)を得た。極性基含有ポリプロピレン系樹脂(B-1)の温度230℃、荷重2.16kg(21.2N)におけるMFRは6g/10分であり、無水マレイン酸濃度は0.3%であり、融点は138℃だった。なお、無水マレイン酸濃度は、水酸化カリウムのメタノール溶液を用いて滴定して得られる値である。また、融点は10℃/minで昇温した際の示差走査熱量測定曲線の吸熱ピークから求めた値である。
メタクリル酸メチル95質量部およびアクリル酸メチル5質量部からなる単量体混合物に重合開始剤(2,2’-アゾビス(2-メチルプロピオニトリル)、水素引抜能:1%、1時間半減期温度:83℃)0.1質量部および連鎖移動剤(n-オクチルメルカプタン)0.28質量部を加え溶解させて原料液を得た。また、別の容器にイオン交換水100質量部、硫酸ナトリウム0.03質量部および懸濁分散剤0.45質量部を混ぜ合わせて混合液を得た。耐圧重合槽に前記混合液420質量部と前記原料液210質量部を仕込み、窒素雰囲気下で撹拌しながら温度を70℃にして重合反応を開始させた。重合反応開始後3時間経過時に温度を90℃に上げ、撹拌を引き続き1時間行って、ビーズ状共重合体が分散した液を得た。得られた共重合体分散液を適量のイオン交換水で洗浄し、バケット式遠心分離機によりビーズ状共重合体を取り出し、80℃の熱風乾燥機で12時間乾燥させ、重量平均分子量Mw(F)が30,000、Tgが128℃であるビーズ状のメタクリル樹脂(F-1)を得た。
攪拌機、温度計、窒素ガス導入管、単量体導入管および還流冷却器を備えた反応器に、イオン交換水1050質量部、ジオクチルスルホコハク酸ナトリウム0.5質量部および炭酸ナトリウム0.7質量部を仕込み、容器内を窒素ガスで十分に置換した後、内温を80℃に設定した。そこに過硫酸カリウム0.25質量部を投入して5分間攪拌した後、メタクリル酸メチル:アクリル酸メチル:メタクリル酸アリル=94:5.8:0.2(質量比)からなる単量体混合物245質量部を50分かけて連続的に滴下し、滴下終了後、さらに30分間重合反応を行った。
次いで同反応器にペルオキソ2硫酸カリウム0.32質量部を投入して5分間攪拌した後、アクリル酸ブチル80.6質量%、スチレン17.4質量%およびメタクリル酸アリル2質量%からなる単量体混合物315質量部を60分間かけて連続的に滴下し、滴下終了後、さらに30分間重合反応を行った。
続いて同反応器にペルオキソ2硫酸カリウム0.14質量部を投入して5分間攪拌した後、メタクリル酸メチル:アクリル酸メチル=94:6(質量比)からなる単量体混合物140質量部を30分間かけて連続的に滴下供給し、滴下終了後、さらに60分間重合反応を行って、多層構造体(E-1)を得た。
合成例1で得た熱可塑性エラストマー(A-1)80質量部および合成例2で得た極性基含有ポリプロピレン系樹脂(B-1)20質量部を二軸押出機(東芝機械社製;TEM-28、以下の製造例において全て同様)を用いて230℃で溶融混練した後、ストランド状に押出して切断し、熱可塑性重合体組成物(Y-1)のペレットを製造した。当該樹脂のMFRは7.4g/10分であった。
合成例3で得たメタクリル樹脂(F-1)88質量部、および合成例4で得た多層構造体(E-1)20質量部を二軸押出機を用いて230℃で溶融混練した後、ストランド状に押出して切断し、Tgが129℃である(メタ)アクリル系樹脂(X-5,Z-1)のペレットを得た。
製造例1で得られた熱可塑性重合体組成物(Y-1)のペレットおよび中間層樹脂(X-1)のペレットをそれぞれ単軸押出機(G.M.ENGINEERING社製;VGM25-28EX)のホッパーに投入し、マルチマニホールドダイを用いて共押出しし、幅300mmかつ厚さ300μmの2種3層フィルムを得た。各層の厚さは押出流量により制御し、熱可塑性重合体組成物(Y-1)の厚さを50μm、中間層樹脂(X-1)の厚さを200μmとした。ここで、熱可塑性重合体組成物(Y-1)層は、常温において低タック性であり、当該温度で接着することはなかった。
これとは別に、製造例2で得られた(メタ)アクリル系樹脂(Z-1)のペレットを用いて、単軸押出機および単層用Tダイを用いることにより、(メタ)アクリル系樹脂フィルム(厚さ75μm)を得た。
得られた多層フィルムおよび該多層フィルムが積層した成形体の物性について上記に従って評価した。結果を表1に示す。
実施例1において、中間層のポリプロピレン系樹脂(X-1)の厚みを150μmとした以外は実施例1と同様にして、多層フィルムおよび成形体を得た。結果を表1に示す。
実施例2において、ポリプロピレン系樹脂(X-1)のかわりにポリプロピレン系樹脂(X-2)を使用した以外は実施例2と同様にして多層フィルムおよび成形体を得た。結果を表1に示す。
実施例2において、ポリプロピレン系樹脂(X-1)のかわりにポリプロピレン系樹脂(X-3)を使用した以外は実施例2と同様にして多層フィルムおよび成形体を得た。結果を表1に示す。
実施例2において、中間層のポリプロピレン系樹脂(X-1)のかわりに(メタ)アクリル系樹脂(X-5)を使用した以外は実施例2と同様にして多層フィルムおよび成形体を得た。結果を表1に示す。
実施例2において、熱可塑性重合体組成物(Y-1)のかわりに熱可塑性重合体組成物(Y-2)を使用した以外は実施例1と同様にして多層フィルムおよび成形体を得た。結果を表1に示す。ここで、熱可塑性重合体組成物(Y-2)層は、常温において低タック性であり、当該温度で接着することはなかった。
実施例2において、中間層のポリプロピレン系樹脂(X-1)のかわりにポリプロピレン系樹脂(X-4)を使用した以外は実施例2と同様にして多層フィルムおよび成形体を得た。結果を表1に示す。
実施例3において、中間層のポリプロピレン系樹脂(X-2)の厚みを85μmとした以外は実施例3と同様にして、多層フィルムおよび成形体を得た。結果を表1に示す。
実施例3において、中間層のポリプロピレン系樹脂(X-2)の厚みを500μmとした以外は実施例3と同様にして、多層フィルムおよび成形体を得た。結果を表1に示す。
実施例1において、中間層のポリプロピレン系樹脂(X-1)の厚みを300μmとした以外は実施例1と同様にして、多層フィルムおよび成形体を得た。結果を表1に示す。
実施例3において、中間層のポリプロピレン系樹脂(X-2)の厚みを610μmとした以外は実施例3と同様にして、多層フィルムおよび成形体を得た。結果を表1に示す。
製造例1で得られた熱可塑性重合体組成物(Y-1)のペレットをそれぞれ単軸押出機(G.M.ENGINEERING社製;VGM25-28EX)のホッパーに投入し、マルチマニホールドダイを用いて押出しし、幅300mmかつ厚さ100μmの単層フィルムを得ようと試みたが、熱可塑性重合体組成物層(Y-1)が金属ロール表面に過密着して離型できずフィルムを得られなかった。そこで、熱可塑性重合体組成物層(Y-1)を圧縮成形(成形温度:230℃、圧縮時間:5分)により作製し、製膜性以外の項目について評価した。結果を表1に示す。
比較例2において、熱可塑性重合体組成物(Y-1)のかわりに熱可塑性重合体組成物(Y-2)を使用した以外は比較例2と同様にして、熱可塑性重合体組成物(Y-2)の単層フィルムを得ようと試みたが、熱可塑性重合体組成物層(Y-2)が金属ロール表面に過密着して離型できずフィルムを得られなかった。そこで、熱可塑性重合体組成物層(Y-2)を圧縮成形(成形温度:230℃、圧縮時間:5分)により作製し、製膜性以外の項目について評価した。結果を表1に示す。
実施例1において、中間層のポリプロピレン系樹脂(X-1)の厚みを500μmとした以外は実施例1と同様にして、多層フィルムおよび成形体を得た。結果を表1に示す。
実施例3において、中間層のポリプロピレン系樹脂(X-2)の厚みを75μmとした以外は実施例3と同様にして、多層フィルムおよび成形体を得た。結果を表1に示す。
一方、MFR比(Y)/(X)が0.6である実施例7では、中間層(X)と熱可塑性重合体樹脂組成物層(Y)の共押出製膜性が悪いため、意匠性および厚み均一性が若干劣る多層フィルムとなった。
Claims (12)
- 3次元立体表面を有する被着体の加飾成形用であって、曲げ剛性率が60~30000kPa・mm3である熱可塑性樹脂層を中間層(X)とし、芳香族ビニル化合物単位からなる重合体ブロック(a1)および共役ジエン化合物単位からなる重合体ブロック(a2)を含有するブロック共重合体またはその水素添加物である熱可塑性エラストマー(A)100質量部に対してポリプロピレン系樹脂(B)0~50質量部を含有する熱可塑性重合体組成物からなる層(Y)を両面に有する多層フィルムに、加飾層(Z)が(Y)のいずれかの面に密着して配置されてなる多層フィルム。
- 前記熱可塑性エラストマー(A)における重合体ブロック(a2)を構成する共役ジエン化合物が、ブタジエン、イソプレン、またはブタジエンおよびイソプレンであり、前記重合体ブロック(a2)中の1,2-結合量および3、4-結合量の合計が35~98モル%である請求項1に記載の多層フィルム。
- 前記熱可塑性重合体組成物における熱可塑性エラストマー(A)の含有量が50質量%以上である請求項1または2に記載の多層フィルム。
- 前記熱可塑性重合体組成物における粘着付与樹脂の含有量が1質量%未満である、請求項1~3のいずれかに記載の多層フィルム。
- 前記ポリプロピレン系樹脂(B)が極性基含有ポリプロピレン系樹脂(B1)である請求項1~4のいずれかに記載の多層フィルム。
- 前記中間層(X)で用いられる熱可塑性樹脂が、温度230℃、荷重2.16kg(21.2N)の条件下で測定されるメルトフローレート(MFR)が0.1~20g/10分であり、前記中間層(X)に対する前記熱可塑性重合体組成物層(Y)の温度230℃、荷重2.16kg(21.2N)の条件下で測定されるMFR比(Y)/(X)が1~15である、請求項1~5のいずれかに記載の多層フィルム。
- 前記中間層(X)に対する前記熱可塑性重合体組成物層(Y)の厚さの比(Y)/(X)が0.1~18である請求項1~6のいずれかに記載の多層フィルム。
- 真空成形法や圧空成形法、真空圧空成形法、圧縮成形法、またはプリフォームおよびフィルムインサート射出成形法のいずれかに適用される請求項1~7のいずれか1項に記載の多層フィルム。
- 請求項1~7のいずれかに記載の、中間層(X)の両面に熱可塑性重合体組成物層(Y)を有する多層フィルムの製造方法であって、表層となる前記熱可塑性樹脂層(Y)が溶融状態で、表面が疎水性樹脂であるロールに接触することを特徴とする多層フィルムの製造方法。
- 請求項1~7のいずれかに記載の、中間層(X)の両面に熱可塑性重合体組成物層(Y)を有する多層フィルムの製造方法であって、前記中間層(X)と前記熱可塑性樹脂層(Y)とを共押出によって積層する工程を含むことを特徴とする多層フィルムの製造方法。
- 前記積層する工程に次いで、表層の前記熱可塑性樹脂層(Y)が溶融状態で、表面が疎水性樹脂であるキャストロールに接触する工程を含むことを特徴とする請求項10に記載の多層フィルムの製造方法。
- 請求項1~8のいずれかに記載の多層フィルムを製造する方法であって、前記中間層(X)の両面に前記熱可塑性重合体組成物層(Y)を有する多層フィルムのいずれか一方の面に、二本の加熱ロールを用いた熱ラミネートによって加飾層(Z)を貼合わせることを特徴とする多層フィルムの製造方法。
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EP3636431A4 (en) | 2021-03-10 |
JP7163286B2 (ja) | 2022-10-31 |
US20200139599A1 (en) | 2020-05-07 |
KR20200014382A (ko) | 2020-02-10 |
CN110719843B (zh) | 2022-09-23 |
CN110719843A (zh) | 2020-01-21 |
KR102378165B1 (ko) | 2022-03-23 |
JPWO2018225780A1 (ja) | 2020-04-09 |
EP3636431A1 (en) | 2020-04-15 |
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