JP5226411B2 - Laminated polyester film for skin material and composite molded body with improved tactile sensation using the same - Google Patents

Description

  The present invention relates to a laminated polyester film for a skin material capable of improving the tactile sensation of a molded body, and more specifically, a laminated polyester film for a skin material excellent in adhesiveness and heat-resistant water adhesion between a silicone rubber layer and a polyester film, and this The present invention relates to a composite molded body with improved tactile sensation.

  In order to improve the feel of a hard plastic film, a rubber composite film in which a silicone rubber layer and a plastic film are combined is known (for example, Patent Documents 1 and 2). Further, in order to improve the surface properties of the molded body, insert molding is performed in which a liquid silicone rubber composition is injection-molded and cured in a mold in which a pre-molded resin molded body is inserted. (For example, patent document 3 etc.). However, in the method performed in Patent Document 3 and the like, a resin molding step and a liquid silicone rubber injection molding step are required, which leads to complication of the mold and a long molding cycle. There's a problem. Moreover, since the adhesiveness of a silicone rubber and a resin molding is inferior, or when a high decoration is given, since the tactile sensation of the rubber layer is lowered, the design is also inferior.

  On the other hand, film insert molding that can obtain a molded body in which the film and the resin are integrated by placing the film in a mold and then injection molding the resin has attracted attention (Patent Document 4, 5). In film insert molding, the interior of the film can be decorated, so there is an advantage that a molded body with high designability can be obtained at a stretch, and the molding cycle is also short, so a highly designed molded body can be produced with high efficiency. Can be mass produced.

  Further, a polyester film having high moldability used for a composite of a polyester film and rubber and a laminate using the film are disclosed (see Patent Documents 6 and 7).

  However, for example, when various films such as rubber and polyester are bonded with an adhesive, the moldability may be inferior or the cost is high. Therefore, a rubber composite film in which the silicone rubber layer described in Patent Document 1 is laminated on a polyester film without using an adhesive is desirable. However, there is a problem that the adhesion between the polyester film and the rubber layer is reduced when a solvent is used when decorating printing, painting, etc. on the opposite side of the silicone rubber layer lamination surface of the polyester film. It was. Further, even under severe conditions, for example, use under high temperature and high humidity, the adhesion and durability between the film and the rubber layer may be insufficient.

  In addition, the method described in Patent Document 2 is an unstretched sheet in which the hard plastic layer is mainly composed of a polycarbonate resin, and is poor in solvent resistance. Therefore, when decorating printing, painting, etc., whitening with a solvent is performed. There was a problem that deformation occurred.

As described above, each of the conventionally known methods has problems, and there is a problem that even when these known techniques are combined, it is not possible to meet the high demands of the market.
Japanese Patent Laid-Open No. 10-226022 JP 2002-178478 A JP 2001-240746 A Japanese Patent Laying-Open No. 2005-305786 JP 2006-175639 A JP 2001-322167 A JP 2001-330881 A

  In the present invention, a silicone rubber layer and a polyester are used as a laminated polyester film for a skin material that can be applied to a surface of a molded body with a double-sided adhesive sheet or used for film insert molding to soften the hard feel of the molded body. An object was to provide a laminated polyester film for a skin material excellent in adhesiveness to a film, its durability, and particularly in hot water adhesion.

  The laminated polyester film for skin material of the present invention that has solved the above problems is a laminated polyester film for skin material in which a silicone rubber layer is formed on one side of a polyester film having a degree of surface orientation of more than 0.15 to less than 0.20. When the hot water adhesion is evaluated by the method defined in the specification, the silicone rubber layer does not peel off.

  A heat resistant water adhesion improving layer is formed between the silicone rubber layer and the polyester film, the thickness of the heat resistant water adhesion improving layer is 0.01 to 0.5 μm, and the heat resistant water adhesion improving layer. However, being formed on both sides of the polyester film is a preferred embodiment of the present invention.

  A decorative layer may be formed on the side opposite to the silicone rubber layer forming surface of the polyester film, or an adhesion improving layer may be formed on the side opposite to the silicone rubber layer forming surface of the polyester film. Good.

  An adhesive layer may be formed on the surface opposite to the silicone rubber layer forming surface of the polyester film. The pressure-sensitive adhesive layer may be a single layer, or the pressure-sensitive adhesive layer may be a double-sided pressure-sensitive adhesive sheet in which a substrate is sandwiched between two layers of pressure-sensitive adhesive layers. In this double-sided pressure-sensitive adhesive sheet, it is preferable that the adhesive force of the adhesive layer corresponding to the outermost layer of the laminated polyester film for skin agent is smaller than the adhesive force of the inner adhesive layer. At this time, the adhesive force of the outermost adhesive layer of the double-sided adhesive sheet is preferably 0.05 to 12 N / 25 mm, and the adhesive force of the inner adhesive layer is preferably 12 to 30 N / 25 mm. A separate film may be laminated on the surface of the outermost adhesive layer.

  In the present invention, the laminated polyester film for the skin material having no adhesive layer is inserted into the mold so that the silicone rubber layer becomes the outermost surface of the molded body, and then the mold is closed and the resin is injected, Composite molded body with improved tactile sensation obtained by insert molding, and composite molding with improved tactile sensation obtained by sticking a laminated polyester film for skin material having an adhesive layer to the surface of the molded body with the adhesive layer The tactile sensation obtained by pasting the body and the laminated polyester film for skin material without an adhesive layer on the surface of the molded body with a separate double-sided adhesive sheet so that the silicone rubber layer is the outermost surface is improved Each composite molded body is included.

  In composite moldings using separate double-sided PSA sheets, the adhesive strength of each PSA layer of this double-sided PSA sheet is different, and a low-adhesive adhesive layer is adhered to the surface of the molded body It is preferable that the adhesive strength of the adhesive layer on one side is 0.05 to 12 N / 25 mm, and the adhesive strength of the adhesive layer on the other side is preferably 12 to 30 N / 25 mm.

  The laminated polyester film for skin material of the present invention is excellent in heat resistance and the like because the plane orientation degree of the polyester film is controlled in an appropriate range. Moreover, it is excellent in the adhesiveness of a silicone rubber layer and a polyester film, its durability, heat-resistant water adhesiveness, etc. A laminated polyester film of the type having an adhesive layer adheres well to a resin molded body. Furthermore, by decorating the polyester film side of the film for the skin material, it has become possible to efficiently produce a composite molded body to which a sophisticated design has been imparted. In addition, the silicone rubber layer is arranged on the outermost surface, so that a soft and soft feel can be obtained, and the silicone rubber layer relaxes the external force, so that the durability of the resulting composite molded body can be improved. It was. By placing the silicone rubber layer on the outermost surface and controlling the surface shape of this silicone rubber layer with the basis weight method, the silicone rubber layer surface slipperiness, grip and tactile properties can be changed. These functions can be imparted to the body surface.

  Therefore, the laminated polyester film for the skin material of the present invention is a casing, protective case, keypad, etc. for mobile phones, mobile PCs, portable game machines, portable audio devices, etc .; It is useful as a skin material when it is attached to automobile interior members, etc., or when these are produced by insert molding.

  In the laminated polyester film for skin material of the present invention, a silicone rubber layer is formed on one side of a polyester film having a specific degree of plane orientation. By laminating this laminated polyester film for skin material as a skin material, placing the film in the mold so that the silicone rubber layer is in contact with the mold, and then integrating the resin by injection molding A composite molded body with improved tactile sensation can be obtained. In the following description, “molded body” means a cured resin after molding that does not include a laminated polyester film for skin material, and “composite molded body” means a laminated polyester film for skin material according to the present invention. It means a composite body in which the film and the molded body are integrated.

[Laminated polyester film for skin material]
The laminated polyester film for skin material of the present invention (hereinafter sometimes simply referred to as “film for skin material”) has a silicone rubber layer formed on one side of a polyester film.

[Silicone rubber layer]
The silicone rubber for forming the silicone rubber layer is preferably an uncrosslinked organopolysiloxane represented by an average unit formula: R _a SiO _{(4-a) / 2} . In the above formula, R is a substituted or unsubstituted monovalent hydrocarbon group, for example, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, vinyl group, allyl group, Alkenyl groups such as butenyl group, pentenyl group, hexenyl group, aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, aralkyl groups such as benzyl group, phenethyl group, Examples include halogenated alkyl groups such as 3-chloropropyl group and 3,3,3-trifluoropropyl group. A methyl group, a vinyl group, a phenyl group, and a 3,3,3-trifluoropropyl group are preferable. In the above formula, a is a number in the range of 1.9 to 2.1.

The silicone rubber is represented by the above average unit formula. Specific examples of the siloxane units constituting the silicone rubber include R ₃ SiO _1/2 units, R ₂ SiO _2/2 units, and RSiO _3/2 units. And SiO _4/2 units. R ₂ (HO) SiO _1/2 units may also be used.

The main component of silicone rubber is a linear polymer essentially comprising R ₂ SiO _2/2 units and R ₃ SiO _1/2 units or R ₂ (HO) SiO _1/2 units. RSiO _3/2 units and / or R ₃ SiO _1/2 units may be contained, and some of them may have a branched structure. Further, as a part of the silicone rubber component, a dendritic (dendrimer-like) polymer composed of R ₃ SiO _1/2 units and SiO _4/2 units can also be used. Thus, the silicone rubber may be a mixture of two or more polymers.

Further, the molecular structure of the silicone rubber is not particularly limited, and examples thereof include a straight chain, a partially branched straight chain, a branched chain, and a dendritic chain. It is preferable that the polymer is a linear polymer or a mixture containing a linear polymer as a main component. Examples of such uncrosslinked silicone rubber include, for example, molecular chain both ends trimethylsiloxy group-capped dimethylpolysiloxane, molecular chain both ends trimethylsiloxy group-capped methylvinylpolysiloxane, molecular chain both ends trimethylsiloxy group-capped methylphenylpolysiloxane. , A trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, a molecular chain both-ends trimethylsiloxy group-capped dimethylsiloxane / methylphenylsiloxane copolymer, a molecular chain both-ends trimethylsiloxy group-capped dimethylsiloxane / methyl ( 3,3,3-trifluoropropyl) siloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethyl Ruvinylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylvinylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylphenylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane methyl Vinylsiloxane copolymer, dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group copolymer at both ends of molecular chain, dimethylvinylsiloxy group-blocked dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane at both ends of molecular chain Copolymer, dimethylvinylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, both ends of molecular chain silanol group-capped dimethylpolysiloxane, Silanol group-blocked methyl vinyl polysiloxane at both ends of the chain, Silanol group-blocked methyl phenyl polysiloxane at both ends of the molecular chain, Silanol group-blocked dimethyl siloxane / methyl vinyl siloxane copolymer, Silanol group-blocked dimethyl siloxane at both ends of the molecular chain Methylphenylsiloxane copolymer, silanol group-capped dimethylsiloxane / methyl (3,3,3-trifluoropropyl) siloxane copolymer, silanol group-capped dimethylsiloxane / methylvinylsiloxane / methylphenyl Siloxane copolymer, trimethoxysiloxy group-capped dimethylpolysiloxane with molecular chain at both ends, trimethoxysiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with molecular chain at both ends, trimethoxysilane Roxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends trimethoxysiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, R ₃ SiO _1/2 unit and SiO _4/2 unit An organopolysiloxane copolymer comprising R ₂ SiO _2/2 units and RSiO _3/2 units, an R ₃ SiO _1/2 unit, R ₂ SiO _2/2 units and RSiO _3/2 Examples thereof include an organopolysiloxane copolymer comprising units, and a mixture of two or more of these. The viscosity of the silicone rubber at 25 ° C. is not particularly limited, but is practically preferably 100 centistokes or more, particularly 1,000 centistokes or more.

  The silicone rubber is usually used as a silicone rubber compound containing additives such as reinforcing materials and processing aids. In the present invention, it is preferable to use a highly transparent material as the silicone rubber compound. For example, it is preferable to use a compound containing silica having a small particle diameter. Further, the rubber may be mixed with other rubber to improve the characteristics. The other rubber may be either natural rubber or synthetic rubber, and examples of the synthetic rubber include butadiene, isoprene, styrene, nitrile, ethylene propylene, fluorine, etc., depending on the properties to be added. Selected.

  The silicone rubber preferably has a hardness measured by durometer type A of 20 to 80 degrees, more preferably 30 to 60 degrees. Within this range, it is preferable to select according to required characteristics such as tactile sensation and durability. If the durometer type A hardness is less than 20 degrees, the silicone rubber strength becomes weak, and the durability such as wear resistance of the silicone rubber layer may be lowered, which is not preferable. Conversely, when the durometer type A hardness exceeds 80 degrees, the effect of improving the tactile sensation is lowered, which is not preferable.

  In order to improve the adhesion between the silicone rubber layer and the polyester film described later, it is preferable to add an adhesion improver to the silicone rubber when the silicone rubber layer is formed. As the adhesion improver, it is preferable to use a compound containing a reactive group active against radical reaction. Examples of such compounds include (meth) acrylic acid derivatives and allyl derivatives. Among them, derivatives having 2 or more, particularly 3 or more unsaturated bonds are preferable. These compounds are widely used as rubber co-crosslinking agents. For example, polyhydric alcohol acrylic acid esters and methacrylic acid esters (hereinafter sometimes referred to as (meth) acrylic acid esters), many Examples include allyl esters of divalent carboxylic acids, triallyl isocyanurate, triallyl cyanurate and the like.

  The (meth) acrylic acid ester of the polyhydric alcohol is an ester compound obtained by esterifying two or more alcoholic hydroxyl groups of a polyhydric alcohol having two or more alcoholic hydroxyl groups with (meth) acrylic acid. Specifically, ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 2,2'-bis (4- (meth) acryloxydiethoxyphenyl) propane, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetramethylolmethane di (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetra Chirorutetora (meth) acrylate, dimer diol di (meth) acrylate and the like, particularly compounds containing three or more (meth) acryloyl group is preferred. In addition, although said compound illustrated each single ester compound of acrylic acid and methacrylic acid, the form of mixed ester of acrylic acid and methacrylic acid may be sufficient.

  Examples of the allyl ester of polyvalent carboxylic acid include phthalic acid diarylate, trimellitic acid diarylate, and pyromellitic acid tetraarylate.

  Any one of the above-mentioned adhesiveness improvers may be used alone, or two or more thereof may be used in combination. In addition, the adhesive improvement agent used for this invention is not limited to said exemplary compound.

  It is preferable that the compounding quantity of the said adhesive improvement agent shall be 0.2-20 mass parts with respect to 100 mass parts of all the silicone rubber components, More preferably, it is 0.5-10 mass parts. If the blending amount is less than 0.2 parts by mass, the adhesive strength with the base film tends to be insufficient. On the other hand, even if blending exceeds 20 parts by mass, the effect of improving the adhesive strength commensurate with the blending amount is obtained. The physical properties of silicone rubber tend to deteriorate rather.

  Moreover, in order to make the adhesive improvement effect by the above-described adhesive improver more remarkable, a peroxide compound may be added to the silicone rubber layer. The heat resistant water adhesion of the skin material film is further improved.

  The peroxide compound may be either acyl-based or alkyl-based, such as benzoyl peroxide, monochlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-bis-t-butylperoxy-3,3,5 -Trimethylcyclohexane, di-t-butyl peroxide, t-butylcumyl peroxide and the like are exemplified.

  The compounding amount of the peroxide compound is preferably 0.05 to 10 parts by mass, particularly 1 to 8 parts by mass with respect to 100 parts by mass of the total silicone rubber component. If the blending amount is less than 0.05 parts by weight, it is difficult to see the contribution to the effect of improving the adhesiveness. Even if the blending amount exceeds 10 parts by weight, the above-mentioned adhesiveness improving effect is saturated, rather, Physical properties may deteriorate.

  In order to form a silicone rubber layer, if necessary, the above-mentioned adhesion improver, peroxide compound, solvent or the like is added to a silicone rubber layer raw material composition such as the above-mentioned silicone rubber compound, and a two-roll, Banbury After kneading with a kneader such as a mixer or a dough mixer (kneader), it is laminated on the polyester film after the heat resistant water adhesion improving layer described later is formed. At this time, it is preferable to crosslink after laminating an uncrosslinked silicone rubber layer. In the present invention, if the heat resistant water adhesion improving layer is provided, the adhesion between the silicone rubber layer and the polyester film is improved. Thereby, since the use of the adhesive for bonding the polyester film and the silicone rubber layer and the bonding step can be omitted, it is economically advantageous. Moreover, the characteristic fall of the film for skin materials by an adhesive bond layer can also be suppressed. If necessary, the silicone rubber layer contains reinforcing fillers, pigments, dyes, antioxidants, antioxidants, mold release agents, flame retardants, thixotropic agents, dispersants for fillers, etc. May be.

  The method for laminating the silicone rubber layer may be arbitrarily selected from conventionally known methods. For example, a solution obtained by dissolving a silicone rubber layer raw material composition in an organic solvent is used as a polyester after the heat resistant water adhesion improving layer is formed. Examples include a method of coating and drying on a film; a method of extruding a silicone rubber layer raw material composition under high pressure on the surface of a heat resistant water adhesion improving layer of a polyester film; a calendering method and the like. Moreover, when using liquid rubber like liquid silicone rubber, it can apply without diluting with a solvent.

  When an adhesion improver or a peroxide is blended, it is preferably crosslinked by heating in order to cause a crosslinking reaction with the silicone rubber. Moreover, you may irradiate high energy active rays, such as an electron beam and a gamma ray. In particular, the method using actinic radiation does not require the addition of additives for generating radicals such as peroxides. Therefore, contamination of the adherend and residue of the silicone rubber layer due to the residue of these additives is suppressed, and it is not necessary to consider the pot life after adding a crosslinking catalyst, etc., and it is efficient in a short time. There are merits such as high productivity because the crosslinking is completed. Among the actinic rays, the electron beam cross-linking method is preferable because of the availability of the irradiation device (EB irradiation device). As an electron beam irradiation amount in an EB irradiation apparatus, the range of 5-50 Mrad is preferable. By setting the electron beam irradiation amount to 5 Mrad or more, the crosslinking reaction of the silicone rubber can be promoted. On the other hand, by setting the electron beam irradiation amount to 50 Mrad or less, it is possible to suppress a decrease in elasticity due to excessive progress of the crosslinking reaction.

  The thickness of the silicone rubber layer is preferably 5 to 200 μm. 10-150 micrometers is more preferable, and 20-100 micrometers is further more preferable. If the thickness of the silicone rubber layer is less than 5 μm, the tactile sensation improving effect is lowered, which is not preferable. On the contrary, when it exceeds 200 μm, the tactile sensation improving effect is saturated, which is disadvantageous economically.

  Depending on the intended use of the film for skin material of the present invention, there are cases where it is desired to change the surface shape of the silicone rubber layer in various ways. For example, when the purpose is to improve tactile sensation, the surface roughness of the silicone rubber layer should be appropriately controlled. On the other hand, when imparting grip properties, a smooth surface is preferred. As a method for controlling the surface shape of the rubber sheet, it is preferable to employ a weighting method which is generally performed. That is, a weighting material made of a film or fabric having a different surface roughness or surface shape is superimposed on the surface of the uncrosslinked rubber layer, and the surface shape of the weighting material is transferred to the surface of the silicone rubber layer. Examples of the weighting material include plastic films such as polyethylene film, polyester film, and polyvinyl chloride film subjected to mat processing and emboss processing, and filament fabric such as nylon taffeta and polyester taffeta. The basis material is not limited to these, but it is a preferred embodiment to use a polyester film (hereinafter, sometimes referred to as a basis weight polyester film) that has been subjected to matting or embossing. In this case, it is preferable to apply the weight after applying a surfactant such as an alkali metal alkyl sulfonate to the mat processed surface or the embossed surface. Since the peeling force is reduced by the surfactant when peeling the basis weight polyester film after the basis weight processing, smooth peeling becomes possible.

  When the center line average roughness Ra (JIS B0601: '82) is 0.15 to 1.0 μm as the surface roughness after the weighting treatment, the tactile sensation when the skin touches the surface of the silicone rubber layer is remarkably improved. Therefore, this is a preferred embodiment. If it is less than 0.15 μm, the slimy feeling increases and the tactile sensation improving effect decreases, which is not preferable. On the other hand, when the thickness exceeds 1.0 μm, the feeling of roughness increases and the effect of improving tactile sensation decreases, which is not preferable. The centerline average roughness Ra is more preferably 0.20 to 0.80 μm. The center line average roughness Ra of the present invention is “SE-200 type” surface roughness meter manufactured by Kosaka Laboratory Ltd., longitudinal magnification: 1000, lateral magnification: 20, cut-off: 0.08 mm, measurement length: 8 mm Measurement speed: a value measured under conditions of 0.1 mm / min.

  The above-mentioned basis weight materials such as polyester film for weight are overlapped on the surface when the silicone rubber layer is cross-linked and peeled off after the cross-linking is completed. As described above, the adhesive strength between the silicone rubber layer and the polyester film is improved. If an adhesion improver for blending is added, even if an attempt is made to peel off the weighting material after cross-linking, the adhesion strength between the rubber layer and the weighting material will increase, making it difficult to peel off the weighting material. is there. However, if the massaging material is peeled off before the crosslinking treatment, a part of the silicone rubber layer may be chipped off and adhere to the massaging material.

  Therefore, in order to improve the peelability of the weighting material, it is preferable to perform a surface treatment on the weighting surface of the weighting material using a surfactant as described above. Moreover, you may use the raw material with a low adhesive force with respect to a silicone rubber layer, for example, the film which consists of a poly-4-methylpentene-1 or an ethylene methylmethacrylate copolymer as a fabric weight. Further, the rubber layer can be multilayered so that the compounding amount of the adhesion improver on the rubber layer on the side opposite to the polyester film can be made smaller on the basis weight side than the rubber layer on the polyester film side. Moreover, when performing bridge | crosslinking by electron beam irradiation, it is also one method to perform the irradiation from the polyester film side, and this case is preferable at the point which the adhesive force of a rubber layer and a polyester film improves.

  On the other hand, when using the film for skin material of the present invention in order to impart grip properties to the surface of the molded body, the center line average roughness Ra of the film for skin material is preferably less than 0.15 μm. Ra is more preferably 0.1 μm or less, and even more preferably 0.05 μm or less. In order to obtain such a film for a skin material having a smooth surface, a transparent polyester film may be used as a polyester film for weighting. Even in this case, it is preferable to perform a surface treatment with a surfactant in order to improve the peelability of the weighting material after weighting.

  Further, a release layer containing a binder resin, a polymer wax component and an antistatic agent may be laminated on the surface of the basis polyester film. The thickness of the release layer is preferably about 0.03 to 1 μm.

  The binder resin is preferably at least one polymer selected from the group consisting of polyesters, polyurethanes and acrylic polymers, and these polymers may be used alone, or two or three different types may be used. You may use combining a seed.

  As the polyester, polyurethane, and acrylic polymer, the same polymers as those exemplified as the constituent polymer of the heat resistant water adhesion improving layer described later can be used. Although the binder resin has a low necessity for crosslinking, a crosslinking agent (described later) may be used in combination with the heat resistant water adhesion improving layer, or a self-crosslinking type (described later) polymer may be used.

  A conventionally known material can be used for the polymer wax component. For example, wax emulsions such as polyethylene, polypropylene, acrylic, and fatty acid are shown, but a polymer wax agent that is particularly hard and does not have a sticky feeling and has excellent thermal decomposition stability is effective in improving peelability. Further, it is preferable because the transfer of wax to the opposite surface can be suppressed during film winding. Moreover, the preferable number average molecular weights of these wax agents are 1000-10000, More preferably, it is the range of 1500-6000.

  The polymer wax component is preferably contained in a solid content of 2 to 10% by mass when the total with the binder resin is 100% by mass. More preferably 3 to 8% by mass is contained. By making the addition amount of the polymer wax component 2% by mass or more, the peelability of the basis material becomes good. On the other hand, when the addition amount of the polymer wax component is 10% by mass or less, an appropriate peeling force can be imparted to the basis material.

  The antistatic agent is not particularly limited as long as it is miscible with the binder resin or is compatible with the binder resin, and conventionally known commercially available materials can be used. Cationic, nonionic, amphoteric surfactants, polymer surfactants, and the like can be used. Preferably, a polymer type antistatic agent with little bleed out to the laminated surface is preferred.

  As the polymer type antistatic agent, any of anionic type, cationic type and nonionic type can be used, and among them, anionic type and nonionic type polymeric antistatic agents are suitable.

  As the anionic polymer antistatic agent, for example, a polar polymer having at least one polar group selected from a sulfonic acid group, a carboxyl group, and a sulfate ester group or a salt thereof is preferable. The polar group needs 5 mol% or more per polymer molecule. These polar polymers having electrical conductivity may contain hydroxyl groups, amino groups, epoxy groups, aziridine groups, active methylene groups, sulfinic acid groups, aldehyde groups, and vinyl sulfone groups as polar groups. Among these, an antistatic agent containing styrene sulfonic acid or a salt thereof as a repeating unit is preferable.

  Examples of such an antistatic agent include polystyrene sulfonic acid or a salt thereof. Examples of the salt include ammonium salt, lithium salt, and sodium salt. Polystyrene sulfonic acid or a salt thereof is, for example, commercially available from Nippon SC under the trade name VERSA-TL (registered trademark) and various types of unneutralized salts having different molecular weights. Further, as an antistatic agent containing styrene sulfonic acid or a salt thereof as a repeating unit, a styrene sulfonic acid-maleic acid copolymer can also be used and is commercially available from Nippon SC.

  On the other hand, nonionic high molecular surfactants include aniline or derivatives thereof, pyrrole or derivatives thereof, isothianaphthene or derivatives thereof, acetylene or derivatives thereof, thiophene or derivatives thereof, and the like. Is preferred. Among them, a π-electron conjugated conductive polymer containing thiophene or a derivative thereof as a structural unit is preferable because it is less colored. The π-electron conjugated conductive polymer may be a homopolymer containing only one type of structural unit as a repeating unit or a copolymer containing two or more types of structural units as a repeating unit.

  Examples of the conductive polymer containing thiophene or a derivative thereof as a constitutional unit include, for example, “BYTRON (registered trademark) P” series manufactured by Starck Vitech, and “Denatron (registered trademark) P-502RG” manufactured by Nagase ChemteX. "Denatron (registered trademark) P-502S", Conisole F202, F205, F210, P810 (above, trade name) manufactured by Instectech, CPS-AS-X03 (trade name) manufactured by Shin-Etsu Polymer, etc. are commercially available. .

[Polyester film]
The polyester film constituting the skin material film of the present invention has a degree of plane orientation of more than 0.15 and less than 0.20. Preferably it is 0.16-0.19, More preferably, it is 0.17-0.18. When the degree of surface orientation of the polyester film is 0.15 or less, the thickness fluctuation of the polyester film may increase, or the thermal shrinkage rate may increase and the dimensional stability may decrease. On the other hand, when it becomes 0.20 or more, the interlaminar adhesion between the polyester film and the hot water adhesion improving layer described later deteriorates, and the whitening of the film due to delamination and the durability of the adhesive strength and the adhesive strength with the rubber layer decrease. There is a risk.

Here, the degree of plane orientation is the following formula (1) based on the longitudinal direction refractive index (Nx), width direction refractive index (Ny), and thickness direction refractive index (Nz) of the film measured using an Abbe refractometer or the like. It is a value calculated from
Plane orientation degree = (Nx + Ny) / 2−Nz (1)

  Although the adjustment method of the degree of plane orientation is not limited, in the production process of the polyester film, for example, by setting the draw ratio to 3.2 to 4.0 times in both length and width, and the heat setting temperature to 210 to 225 ° C, The degree of plane orientation of the film can be adjusted to the above range. Moreover, you may perform the said heat processing, relaxing a film to the longitudinal direction and / or the width direction. Furthermore, redrawing may be performed once or more in each direction, and then heat treatment may be performed. The heat treatment temperature can be confirmed by the peak temperature of the crystal melting sub-peak caused by the heat treatment observed by DSC.

  The film for skin material of the present invention is limited to a thin range of 0.01 to 0.5 μm in thickness of the heat resistant water adhesion improving layer laminated on the polyester film as described later, and the heat resistant water adhesion improving layer. Therefore, in the present invention, the degree of surface orientation is calculated by regarding the refractive index of the film for skin material as the refractive index of the polyester film. Moreover, the refractive index of the polyester film in the laminated body in which a plurality of layers are laminated can be measured using, for example, a prism coupler refractive index measurement method or an ellipsometer.

  In the polyester film according to the present invention, the thickness unevenness measured by the method described in the examples described later is preferably 3.0% or less (more preferably 2.0% or less), and the heat shrinkage (150 C) is preferably 0 to 1.5% (more preferably 0 to 1.3%). When the thickness unevenness and the heat shrinkage rate are within the above ranges, a film for skin material excellent in heat resistance and dimensional stability can be obtained even when a silicone rubber layer is formed on a polyester film.

  The polyester film can be arbitrarily used as long as it has polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, or the like as a main component (80% by mass or more). Among these, those containing polyethylene terephthalate as the main component are preferable, and those using homopolyesters of saray and polyethylene terephthalate are preferably used.

  As the polyester film, a biaxially stretched film is preferable. Although it does not specifically limit as a manufacturing method of a biaxially stretched polyester film, For example, after drying polyester as needed, it supplies to a well-known melt extruder, it extrudes in a sheet form from a slit-like die, an electrostatic application etc. In this manner, the unstretched sheet may be stretched after being brought into close contact with the casting drum and cooled and solidified to obtain an unstretched sheet. The biaxial stretching method may be either simultaneous biaxial stretching or sequential biaxial stretching.

  Although the thickness of a polyester film is not specifically limited, About 10-300 micrometers is preferable, More preferably, it is 70-260 micrometers. If the film thickness is less than 10 μm, the mechanical strength is insufficient and handling becomes difficult, which is not preferable. On the other hand, when the thickness exceeds 300 μm, the rigidity of the film for the skin material becomes too high, and the followability to the shape of the molded body may be deteriorated.

  The polyester film may be subjected to known adhesion improving treatment such as corona treatment, flame treatment, plasma treatment and the like.

  The haze of the polyester film is preferably 0.1 to 3.0%. The lower limit of haze is more preferably 0.3%, still more preferably 0.5%. On the other hand, the upper limit of haze is more preferably 2.5%, still more preferably 2.0%. If the haze is 0.1% or more, a film can be produced on an industrial scale with good productivity. On the other hand, if the haze of the film is 3.0% or less, metal gloss, printed characters, images, etc. when the vapor deposition surface, sputtering surface, or printing surface of metal is viewed from the opposite side of these surfaces. Becomes clear and good design properties can be secured. A method of incorporating particles in the film to form irregularities on the film surface and improving the handleability of the film is widely used. However, with this method, it is difficult to obtain a film having a haze of 2.0% or less.

  The center line average roughness Ra of at least one surface of the film (surface on which the decorative layer is formed) is preferably 0.005 to 0.030 μm. The lower limit value of Ra is more preferably 0.006 μm, still more preferably 0.007 μm. On the other hand, the upper limit of Ra is more preferably 0.025 μm, and still more preferably 0.015 μm. When Ra on at least one side of the film is 0.005 μm or more, blocking or tearing of the film does not occur when winding the film or unwinding the film once wound into a roll. Moreover, if Ra is 0.03 micrometer or less, in post-processing processes, such as vapor deposition, sputtering, and printing, defects, such as a protrusion, do not generate | occur | produce and design property is ensured.

  The polyester film has known additives such as antioxidants, heat stabilizers, weathering stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents. In addition, a nucleating agent or the like may be added.

  In the film for skin material used in the present invention, the polyester film and the silicone rubber layer are preferably firmly bonded. That is, even when a cutter knife is inserted between the silicone rubber layer and the polyester film and the film is peeled off by applying force with a finger (interface alignment), it is preferable that the interface cannot be aligned. Hereinafter, this characteristic is sometimes referred to as adhesiveness. In particular, it is desirable that the silicone rubber layer does not peel even when the composite molded body is used under high temperature and high humidity.

  Moreover, it is preferable that the said adhesiveness is maintained even if the film for skin materials of this invention is preserve | saved for a long time in hot water. Hereinafter, adhesive hot water durability is referred to as heat resistant water adhesion.

[Heat resistant water adhesion]
The method for evaluating hot water adhesion, which is an important effect of the film for skin material used in the present invention, will be described. Cut the film for skin material (or composite molding) into 50 mm x 50 mm and place the sample in a cylindrical glass container with a lid of 400 cc containing distilled water, with the silicone rubber layer on the bottom. The container is covered with the sample immersed in water. In the case where the sample is not immersed in water by its own weight, for example, a polyester film having a size of 60 mm × 60 mm and a thickness of 188 μm may be placed on the sample and weighted. The size and material of the weight are not particularly limited, and the entire sample may be immersed in water. The container containing the sample is placed in a gear oven set at 80 ° C. and allowed to stand for 24 hours. After heat treatment, remove the container from the oven, quickly remove the sample, apply force with the finger pad from the silicone rubber layer side to the end and rub it 10 times, and evaluate whether the silicone rubber layer peels from the polyester film side. The case where the rubber layer was not peeled was marked with ◯, and the case where the rubber layer was peeled was marked with x.

[Heat resistant water adhesion improvement layer]
In the present invention, a method for satisfying the hot water adhesion is not limited, but it is preferable to form a hot water adhesion improving layer as described below between the silicone rubber layer and the polyester film.

  In the evaluation of the hot water adhesion, the heat resistant water adhesion improving layer is preferably provided because the silicone rubber layer does not peel from the polyester film. The thickness of the heat resistant water adhesion improving layer is preferably 0.01 to 0.5 μm. If the thickness of the heat resistant water adhesion improving layer is 0.01 to 0.5 μm, good heat resistant water adhesion is exhibited. However, if the thickness is outside the above range, the heat resistant water adhesion may not be good. A more preferable thickness range is 0.03 to 0.4 μm, and 0.05 to 0.3 μm is even more preferable.

  Preferred as the hot water adhesion improving layer is a crosslinked polymer layer (crosslinked polymer layer), which may be a layer obtained by crosslinking a polymer with a crosslinking agent or a layer using a self-crosslinking polymer.

  The polymer that can be used in the method of crosslinking with a crosslinking agent is not particularly limited, but is preferably at least one selected from the group consisting of polyesters, polyurethanes, and acrylic polymers. The above polymers may be used alone or in combination of two or three different types.

[Polyester for heat resistant water adhesion improvement layer]
The polyester has an ester bond in the main chain or side chain, and is obtained by polycondensation of polyvalent carboxylic acid and glycol.

  As the polyvalent carboxylic acid component constituting the polyester, aromatic, aliphatic, and alicyclic dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, and ester derivatives thereof can be used.

  Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bisphenoxy Ethane-p, p′-dicarboxylic acid, phenylindanedicarboxylic acid and the like can be used. From the viewpoint of the strength and heat resistance of the heat resistant water adhesion improving layer, these aromatic dicarboxylic acids are preferably at least 30 mol%, more preferably at least 35 mol%, even more preferably at 100 mol% of the polyvalent carboxylic acid component. It is preferable to use polyester occupying 40 mol% or more.

  Examples of the aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like, and ester-forming derivatives thereof can be used.

  Examples of the glycol component of polyester include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol Neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2, 4-trimethyl-1,6-hexanediol, 1,2-cyclo Xanthodimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4′-thiodiphenol, bisphenol A, 4,4′-methylenediphenol, 4,4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4′-isopropylidenephenol 4,4′-isopropylidenediol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, and the like can be used.

  In addition, when using polyester as an aqueous liquid as a coating liquid, a compound containing a carboxylic acid (salt) group or a compound containing a sulfonic acid (salt) group is used to facilitate water-solubilization or water-dispersion of the polyester. It is preferable to copolymerize a compound containing a phosphonic acid (salt) group.

  Examples of the compound containing a carboxylic acid (salt) group include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, 1 , 2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 5- (2,5-dioxotetrahydro Furfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-cyclohexene-1,2-dicarboxylic acid, cyclopentanetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol bistrimellite 2,2 ′, 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid, etc., or alkali metal salts, alkaline earth metal salts thereof, An ammonium salt etc. can be mentioned.

  Examples of the compound containing a sulfonic acid (salt) group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfo-p-xylylene glycol, 2-sulfo-1,4-bis (hydroxyethoxy) benzene or the like, or an alkali metal salt, alkaline earth metal salt, or ammonium salt thereof can be used.

  Examples of the compound containing a phosphonic acid (salt) group include phosphoterephthalic acid, 5-phosphoisophthalic acid, 4-phosphoisophthalic acid, 4-phosphonaphthalene-2,7-dicarboxylic acid, phospho-p-xylylene glycol, 2-phospho-1,4-bis (hydroxyethoxy) benzene or the like, or an alkali metal salt, alkaline earth metal salt, or ammonium salt thereof can be used.

  In the present invention, for example, a modified polyester copolymer such as a block copolymer or a graft copolymer modified with acrylic, urethane, epoxy, or the like can be used as the polyester.

  Preferred polyesters include those selected from terephthalic acid, isophthalic acid, sebacic acid, 5-sodium sulfoisophthalic acid as the acid component, and ethylene glycol, diethylene glycol, 1,4-butanediol, and neopentyl glycol as the glycol component. And the like. When water resistance is required, a copolymer or the like containing trimellitic acid as its copolymer component can be suitably used instead of 5-sodium sulfoisophthalic acid.

  The polyester can be produced by the following production method. For example, a polyester having a dicarboxylic acid component consisting of terephthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid and a glycol component consisting of ethylene glycol and neopentyl glycol can be directly esterified with these monomers. Or it can manufacture by the method etc. which manufacture by the 1st step which transesterifies, and the 2nd step which carries out the polycondensation reaction of the reaction product of this 1st step.

  At this time, for example, alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compound, or the like can be used as the reaction catalyst.

  Further, as a method for obtaining a polyester having many carboxyl groups at the terminal and / or side chain, JP-A-54-46294, JP-A-60-209073, JP-A-62-240318, JP JP 53-26828, JP 53-26829, JP 53-98336, JP 56-116718, JP 61-124684, JP 62-240318 Although it can be produced by copolymerizing a trivalent or higher polyvalent carboxylic acid described in the gazette, etc., other methods may be used.

  Further, as the water-dispersed polyester resin, for example, a commercially available “Vaironal (registered trademark)” series (manufactured by Toyobo Co., Ltd.) can also be used.

  The intrinsic viscosity of the polyester is not particularly limited, but is preferably 0.3 dl / g or more in terms of adhesiveness, more preferably 0.35 dl / g or more, and most preferably 0.4 dl / g or more. It is. The glass transition temperature (hereinafter sometimes abbreviated as Tg) of the polyester is preferably 0 to 130 ° C, more preferably 10 to 85 ° C. Using a polyester having a Tg of 0 ° C. or higher improves the hot water adhesion, and after the heat resistant water adhesion improving layer is laminated on the surface of the polyester film, it can suppress the blocking phenomenon such as winding one end. it can. Moreover, stability and water dispersibility can be favorably maintained by using polyester with Tg of 130 ° C. or lower.

[Polyurethane for heat resistant water adhesion improving layer]
Next, polyurethane will be described. The polyurethane is not particularly limited as long as it has a urethane bond, and the main component is obtained by polymerizing a polyol compound and a polyisocyanate compound.

  Examples of the polyol compound include polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polycaprolactone, polyhexamethylene. Adipate, polytetramethylene adipate, trimethylolpropane, trimethylolethane, glycerin, acrylic polyol and the like can be used.

  Examples of the polyisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, an adduct of tolylene diisocyanate and trimethylolpropane, an adduct of hexamethylene diisocyanate and trimethylolethane, and the like. it can.

  In the synthesis of the polyurethane, a known chain extender, a crosslinking agent, and the like may be included in addition to the polyol compound and the polyisocyanate compound. As the chain extender or crosslinking agent, ethylene glycol, propylene glycol, butanediol, diethylene glycol, ethylenediamine, diethylenetriamine, or the like can be used.

  In order to obtain a stable polyurethane water dispersion, it is preferable to synthesize polyurethane having an increased affinity for water. Specifically, an appropriate amount of anionic groups may be introduced into the polyurethane. For example, a method of using a compound having an anionic group for polyol, polyisocyanate, chain extender, etc., a method of reacting an unreacted isocyanate group of the produced polyurethane with a compound having an anionic group, or having an active hydrogen of polyurethane It can be produced by a method of reacting a group with a specific compound.

  The anionic group in the polyurethane is preferably used as a sulfonic acid group, a carboxylic acid group, and an ammonium salt, lithium salt, sodium salt, potassium salt or magnesium salt thereof.

  The amount of the unit having an anionic group in the polyurethane is preferably 0.05% by mass to 15% by mass from the viewpoint of water dispersibility of the polyurethane.

  For example, as a polyurethane water dispersion, “Hydran (registered trademark)” series (manufactured by Dainippon Ink & Chemicals, Inc.) can be used.

[Acrylic polymer for heat-resistant water adhesion improvement layer]
Examples of the monomer component constituting the acrylic polymer include, for example, alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. Hydroxy group-containing monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate), 2-ethylhexyl group, lauryl group, stearyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.) ; (Meth) acrylamide N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-phenyl (meth) acrylamide, etc. Amino group-containing monomer such as N, N-diethylaminoethyl (meth) acrylate; epoxy group-containing monomer such as glycidyl (meth) acrylate; (meth) acrylic acid and salts thereof (lithium salt, sodium salt, A monomer containing a carboxyl group such as potassium salt or the like or a salt thereof can be used, and these are (co) polymerized using one kind or two or more kinds. Furthermore, these can be used in combination with other types of monomers.

  Examples of other types of monomers include epoxy group-containing monomers such as allyl glycidyl ether; sulfonic acids such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, etc.) Monomer containing a group and a salt thereof; a monomer containing a carboxyl group or a salt thereof such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, etc.) Monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid monoe Ether, acrylonitrile, methacrylonitrile, alkyl itaconic acid monoester, vinylidene chloride, vinyl acetate, may be used vinyl chloride.

  Moreover, as said acrylic polymer, a modified acrylic polymer, for example, a block copolymer modified with polyester, polyurethane, epoxy resin, etc., a graft copolymer, etc. can be used.

  The lower limit of the acrylic polymer Tg is preferably −10 ° C. from the viewpoints of heat resistant water adhesion and blocking resistance, more preferably the lower limit is 0 ° C., and the most preferable lower limit is 10 ° C. On the other hand, the Tg of the acrylic polymer is preferably 90 ° C. from the viewpoint of heat resistant water adhesion and film-forming property, more preferably 50 ° C., and most preferably 40 ° C. Further, the weight average molecular weight (Mw) of the acrylic polymer is preferably 50,000 or more, and more preferably 300,000 or more from the viewpoint of adhesiveness to hot water.

  Preferable examples of the acrylic polymer include copolymers composed of monomers selected from methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, acrylamide, N-methylol acrylamide, and acrylic acid.

  It is preferable to dissolve, emulsify, or suspend an acrylic polymer in water and use it as an aqueous liquid from the viewpoint of environmental pollution and explosion-proof properties during coating. Such water-based acrylic polymers are copolymerized with monomers having a hydrophilic group (acrylic acid, methacrylic acid, acrylamide, vinyl sulfonic acid and salts thereof, etc.) and emulsion polymerization using reactive emulsifiers and surfactants, It can be prepared by a method such as suspension polymerization or soap-free polymerization.

  Commercially available acrylic emulsions may also be used, for example, “Jonkrill (registered trademark)” series (manufactured by BASF Japan).

[Crosslinking agent used for heat resistant water adhesion improving layer]
In the present invention, the polyester, polyurethane and acrylic polymer are preferably crosslinked. When the above polymer is cross-linked using a cross-linking agent, the cross-linking agent may be any one that can cross-link with a functional group present in the above-described polymer, such as a carboxyl group, a hydroxyl group, a methylol group, an amide group, or the like. . For example, melamine crosslinking agent, oxazoline crosslinking agent, isocyanate crosslinking agent, aziridine crosslinking agent, epoxy crosslinking agent, methylolated or alkylolized urea crosslinking agent, acrylamide crosslinking agent, polyamide resin, amide Epoxy compounds, various silane coupling agents, various titanate coupling agents, and the like can be used. In particular, a melamine-based crosslinking agent and an oxazoline-based crosslinking agent can be suitably used from the viewpoints of compatibility with the above polymer and adhesiveness to hot water.

  The melamine-based crosslinking agent is not particularly limited, but is a melamine, a methylolated melamine derivative obtained by condensing melamine and formaldehyde, a compound partially or completely etherified by reacting a methylolated melamine with a lower alcohol, or these A mixture of the above can be used. Moreover, as a melamine type crosslinking agent, a monomer, the condensate which consists of a multimer more than a dimer, these mixtures, etc. can be used. As the lower alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like can be used. Methylolated melamine resins such as methylated trimethylolmelamine and butylated hexamethylolmelamine are preferred. Furthermore, in order to accelerate | stimulate the thermosetting of a melamine type crosslinking agent, you may use acidic catalysts, such as p-toluenesulfonic acid, for example.

  Further, the oxazoline-based crosslinking agent is not particularly limited as long as it has an oxazoline group as a functional group in the compound, but includes at least one monomer containing an oxazoline group, and at least one kind of What consists of an oxazoline group containing copolymer obtained by copolymerizing another monomer is preferable.

  Monomers containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like can be used, and one or a mixture of two or more thereof can also be used. Of these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.

  In the oxazoline group-containing copolymer, the at least one other monomer used together with the oxazoline group-containing monomer is not particularly limited as long as it is a monomer copolymerizable with the oxazoline group-containing monomer. (Meth) acrylates or methacrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; non-acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc. Saturated carboxylic acids; unsaturated nitriles such as (meth) acrylonitrile; unsaturated amides such as (meth) acrylamide and N-methylol (meth) acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; methyl vinyl ether and ethyl Vinyl ethers such as nyl ether; olefins such as ethylene and propylene; halogen-containing α-β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; α, β-unsaturated such as styrene and α-methylstyrene Saturated aromatic monomers etc. can be used and these can use 1 type, or 2 or more types of mixtures.

  As the oxazoline group-containing polymer, for example, “Epocross (registered trademark)” series (manufactured by Nippon Shokubai Co., Ltd.) is available.

  The isocyanate-based crosslinking agent is not particularly limited as long as it has an isocyanate group as a functional group in the compound, but it is preferable to use a polyfunctional isocyanate compound containing two or more isocyanate groups in one molecule. .

  As the polyfunctional isocyanate compound, a low-molecular or high-molecular aromatic or aliphatic diisocyanate or a trivalent or higher polyisocyanate can be used. Examples of the polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and trimers of these isocyanate compounds. Furthermore, an excess amount of these isocyanate compounds and low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, or polyester polyols, poly The terminal isocyanate group containing compound obtained by making it react with polymer active hydrogen compounds, such as ether polyols and polyamides, can be mentioned.

  In addition, when using an isocyanate compound as a crosslinking agent, it is also possible to use a blocked isocyanate compound. The blocked isocyanate can be prepared by subjecting the above isocyanate compound and blocking agent to an addition reaction by a conventionally known appropriate method. Examples of the isocyanate blocking agent include phenols such as phenol, cresol, xylenol, resorcinol, nitrophenol and chlorophenol; thiophenols such as thiophenol and methylthiophenol; oximes such as acetoxime, methylethylketoxime and cyclohexanone oxime; Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; -Lactams such as caprolactam, δ-valerolactam, γ-butyrolactam, β-propyllactam; aromatic amines; imides; acetylacetone, acetoacetate, malonic acid Active methylene compounds such as glycol ester; mercaptans; imines; ureas; diaryl compounds; can be mentioned sodium bisulfite and the like.

  The epoxy-based crosslinking agent is not particularly limited as long as it has an epoxy group as a functional group in the compound. However, it is preferable to use a polyfunctional epoxy compound having two or more epoxy groups in one molecule. .

  Examples of the polyfunctional epoxy compound include diglycidyl ether of bisphenol A and oligomer thereof, diglycidyl ether of hydrogenated bisphenol A and oligomer thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene Glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and Polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl Examples include ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like.

  As the cross-linking agent, a phenol formaldehyde resin of a condensate with formaldehyde such as alkylated phenols and cresols; an adduct of urea, melamine, benzoguanamine and the like with formaldehyde, this adduct and an alcohol having 1 to 6 carbon atoms An amino resin such as an alkyl ether compound consisting of can also be used.

  Examples of the phenol formaldehyde resin include alkylated (methyl, ethyl, propyl, isopropyl or butyl) phenol, p-tert-amylphenol, 4,4′-sec-butylidenephenol, p-tert-butylphenol, o-, m-, p-cresol, p-cyclohexylphenol, 4,4'-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecylphenol, phenol, phenyl-o-cresol, p-phenylphenol, xylenol, etc. And the condensates of phenols and formaldehyde.

  Examples of amino resins include methoxylated methylol urea, methoxylated methylol N, N-ethylene urea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like. Are preferably methoxylated methylol melamine, butoxylated methylol melamine, methylolated benzoguanamine, and the like.

  The polymer (polyester, polyurethane, acrylic polymer) and the crosslinking agent can be mixed and used in an arbitrary ratio. However, in order to express the hot water adhesion effect of the present invention more remarkably, the crosslinking agent is: The addition of 2 to 50 parts by mass with respect to 100 parts by mass of the polymer is preferred, more preferably 3 to 25 parts by mass. When the addition amount of the crosslinking agent is less than 2 parts by mass, the effect of the addition is small, and when it exceeds 50 parts by mass, the hot water adhesion tends to decrease.

[Self-crosslinking polymer for heat resistant water adhesion improving layer]
In the present invention, in addition to the above-described method, for example, the heat resistant water adhesion improving layer may be formed using a self-crosslinking type polymer in which a crosslinkable functional group is introduced into the above-described polymer. In the case of using a self-crosslinking type polymer, the crosslinking method may be, for example, thermal crosslinking, or may be crosslinking with high energy active rays such as ultraviolet rays, electron beams and γ rays.

  Hereinafter, a specific method will be illustrated for the case of polyester as the self-crosslinking polymer.

  The self-crosslinking type polyester preferably used in the present invention is a polyester graft copolymer obtained by grafting a hydrophobic copolymer polyester with a compound having at least one radical polymerizable double bond. The “grafting” of the polyester-based graft copolymer in the present invention is to introduce a branched polymer made of a polymer different from the main chain into the backbone polymer which is the main chain. Graft polymerization is usually carried out by reacting at least one radically polymerizable monomer using a radical initiator in a state where a hydrophobic copolyester is dissolved in an organic solvent. Hydrophobic copolyesters are essentially water-insoluble polyesters that do not inherently dissolve in water, so they are more heat resistant than using polyester resins that are soluble in water as the backbone polymer for graft polymerization. Excellent water adhesion.

  The hydrophobic copolyester is composed of 60 to 99.5 mol% of aromatic dicarboxylic acid, 0 to 39.5 mol% of aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid in 100 mol% of dicarboxylic acid component, radical It is preferable that the dicarboxylic acid containing a polymerizable double bond is 0.5 to 10 mol%. More preferably, the aromatic dicarboxylic acid is 68 to 98 mol%, the aliphatic dicarboxylic acid and / or the alicyclic dicarboxylic acid is 0 to 30 mol%, and the dicarboxylic acid containing a polymerizable unsaturated double bond is 2 to 7 Mol%.

  When the aromatic dicarboxylic acid is 60 mol% or more and the aliphatic dicarboxylic acid and / or the alicyclic dicarboxylic acid is 39.5 mol% or less, the hot water adhesion is good. Moreover, the grafting of the radically polymerizable monomer with respect to the polyester resin can be efficiently performed by using 0.5 mol% or more of the dicarboxylic acid containing a radically polymerizable double bond. On the other hand, the content of 10 mol% or less is preferable because the viscosity of the reaction solution can be prevented from significantly increasing in the later stage of the grafting reaction, and the reaction can proceed uniformly.

  As the aromatic dicarboxylic acid, aliphatic and / or alicyclic dicarboxylic acid, any of the compounds exemplified above can be used. Examples of the dicarboxylic acid containing a radically polymerizable double bond include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and other α, β-unsaturated dicarboxylic acids; 2,5-norbornene dicarboxylic acid anhydride And alicyclic dicarboxylic acids containing unsaturated double bonds such as tetrahydrophthalic anhydride. Of these dicarboxylic acids containing a polymerizable unsaturated double bond, fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid are preferred from the viewpoint of polymerizability.

  As the glycol component, any of the compounds exemplified above can be used. Two or more glycol components may be used in combination. Especially, C2-C10 aliphatic glycol, C6-C12 alicyclic glycol, etc. are preferable.

  The hydrophobic copolymerized polyester may be copolymerized with 0 to 5 mol% of a trifunctional or higher polycarboxylic acid and / or polyol. The tri- or higher functional polycarboxylic acid includes (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (an Hydrotrimellitate) and the like. As the trifunctional or higher functional polyol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, or the like is used.

  The tri- or higher functional polycarboxylic acid and / or polyol is copolymerized in the range of 0 to 5 mol%, preferably 0 to 3 mol%, based on the total acid component or the total glycol component. Gelation can be suppressed.

  In addition, the lower limit of the weight average molecular weight of the hydrophobic copolyester is preferably 5,000 from the viewpoint of hot water adhesion. Moreover, it is preferable that an upper limit is 50,000 at points, such as gelatinization at the time of superposition | polymerization.

  After the hydrophobic copolyester is synthesized, graft polymerization is performed. Graft polymerization is performed by reacting at least one radical polymerizable monomer using a radical initiator in a state where the hydrophobic copolyester is dissolved in an organic solvent. The reaction product after completion of the grafting reaction is not limited to the graft copolymer of the desired hydrophobic copolymerized polyester and the radically polymerizable monomer, but also the hydrophobic copolymerized polyester and the hydrophobic copolymer that were not subjected to grafting. It also contains a (co) polymer obtained from a radically polymerizable monomer that has not been grafted to the polyester. The polyester-based graft copolymer in the present invention includes not only the above-described polyester-based graft copolymer, but also a hydrophobic copolymerized polyester that has not been grafted, and a radically polymerizable monomer that has not been grafted. Also included are reaction mixtures containing the resulting (co) polymer and monomer (residual monomer).

In the present invention, the acid value of a reaction product obtained by graft polymerization of a radically polymerizable monomer to a hydrophobic copolymerized polyester is preferably 600 eq / 10 ⁶ g or more from the viewpoint of hot water adhesion. More preferably, the acid value of the reactant is 1200 eq / 10 ⁶ g or more. When the acid value of the reaction product is less than 600 eq / 10 ⁶ g, the hot water adhesion may be lowered.

  The mass ratio of the desired hydrophobic copolymerized polyester and the radical polymerizable monomer suitable for the purpose of the present invention is preferably in the range of polyester / radical polymerizable monomer = 40/60 to 95/5, more preferably 55/45. ~ 93/7, most desirably in the range of 60/40 to 90/10.

  By setting the mass ratio of the hydrophobic copolyester to 40% by mass or more, the excellent adhesiveness of the polyester can be exhibited. On the other hand, when the mass ratio of the hydrophobic copolymerized polyester is 95% by mass or less, the blocking resistance can be improved and the acid value of the reaction product can be adjusted to the above range.

  The graft polymerization reaction product is in the form of an organic solvent solution or dispersion or an aqueous solvent solution or dispersion. In particular, a dispersion of an aqueous solvent, that is, a form of an aqueous dispersion is preferable in terms of working environment and applicability. Therefore, as the radical polymerizable monomer to be grafted, it is preferable to use a radical polymerizable monomer that essentially contains a hydrophilic radical polymerizable monomer. And after carrying out the graft polymerization in an organic solvent, the aqueous dispersion can be obtained by distilling off the organic solvent and adding water.

  The hydrophilic radical polymerizable monomer means a radical polymerizable monomer having a hydrophilic group or a group that can be changed to a hydrophilic group later. Examples of the radical polymerizable monomer having a hydrophilic group include a radical polymerizable monomer containing a carboxyl group, hydroxyl group, phosphoric acid group, phosphorous acid group, sulfonic acid group, amide group, quaternary ammonium base and the like. . On the other hand, examples of the radical polymerizable monomer having a group that can be changed into a hydrophilic group include radical polymerizable monomers containing an acid anhydride group, a glycidyl group, a chloro group, and the like. Among these, from the viewpoint of water dispersibility, a carboxyl group is preferable, and a radical polymerizable monomer having a carboxyl group or a group capable of generating a carboxyl group is preferable.

  In order to make the acid value of the graft reaction product within the above preferred range, it is preferable that a radical polymerizable monomer containing a carboxyl group or having a group capable of generating a carboxyl group is contained. Such monomers include fumaric acid, monoethyl fumarate; maleic acid and its anhydride, monoethyl maleate; itaconic acid and its anhydride, monoester of itaconic acid; acrylic acid, methacrylic acid; and salts thereof (sodium Salt, potassium salt, ammonium salt) and the like. Maleic anhydride is preferable. The said monomer can be copolymerized using 1 type, or 2 or more types.

  The radically polymerizable monomer to be grafted may contain other types of monomers as long as the acid value is within the above-mentioned preferable range. As other types of monomers, monomers that can be used when synthesizing the acrylic polymer described above can be used as they are.

  Examples of the graft polymerization initiator used in the present invention include organic peroxides and organic azo compounds known to those skilled in the art. Examples of the organic peroxide include benzoyl peroxide, t-butyl peroxypivalate, and examples of the organic azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethyl pareronitrile). The amount of the polymerization initiator used for the graft polymerization is at least 0.2% by mass, preferably 0.5% by mass or more, based on the radical polymerizable monomer.

  In addition to the polymerization initiator, a chain transfer agent for adjusting the chain length of the branched polymer, for example, octyl mercaptan, mercaptoethanol, 3-t-butyl-4-hydroxyanisole may be used as necessary. In this case, it is desirable to add in the range of 0 to 5% by mass with respect to the polymerizable monomer.

  The grafting reaction product is preferably neutralized with a basic compound, and can be easily dispersed in water by neutralization. As the basic compound, a compound that volatilizes at the time of coating film formation is desirable, and ammonia, organic amines, and the like are preferable. Desirable compounds include, for example, triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine , 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanol An amine etc. can be mentioned.

  The basic compound has a pH value of the aqueous dispersion in the range of 5.0 to 9.0 by at least partial neutralization or complete neutralization, depending on the carboxyl group content contained in the grafting reaction product. It is desirable to use it. If a basic compound with a boiling point of 100 ° C. or lower is used, there are few residual basic compounds in the coating film after drying, for example, improved hot water adhesion in harsh environments such as high temperature and humidity To do.

  In the grafting reaction product, the weight average molecular weight of the polymer of the radical polymerizable monomer is preferably 500 to 50,000. It is generally difficult to control the weight average molecular weight of the polymer of the radical polymerizable monomer to be less than 500, the graft efficiency is lowered, and there is a tendency that hydrophilic groups are not sufficiently imparted to the copolymer polyester. In addition, the graft polymer of the radical polymerizable monomer forms a hydrated layer of dispersed particles. To obtain a stable aqueous dispersion with a sufficient thickness of the hydrated layer, the graft polymer of the radical polymerizable monomer is used. The weight average molecular weight of is desirably 500 or more.

  The upper limit of the weight average molecular weight of the graft polymer of the radical polymerizable monomer is preferably 50,000 from the viewpoint of polymerizability in solution polymerization. In order to make the weight average molecular weight of the graft polymer of the radical polymerizable monomer within the range of 500 to 50,000, the initiator amount, the monomer dropping time, the polymerization time, the reaction solvent, the monomer composition, or the chain as necessary. It is preferable to carry out by appropriately combining a transfer agent and a polymerization inhibitor.

  The glass transition temperature of the graft copolymer is not particularly limited, but is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, considering the hot water adhesion.

  In the present invention, a reaction product obtained by graft polymerization of a radically polymerizable monomer to a hydrophobic copolymerized polyester has a self-crosslinking property because a hydroxyl group in the polyester and a carboxyl group present in the graft portion react. Moreover, although it does not bridge | crosslink at normal temperature, it carries out intermolecular reaction, such as a hydrogen abstraction reaction by a thermal radical, with the heat at the time of drying at the time of coating-film formation, and bridge | crosslinks without a crosslinking agent. Thereby, a high degree of heat resistant water adhesion is exhibited. The degree of crosslinking of the coating film can be evaluated by various methods, and examples thereof include a method of measuring the insoluble fraction in a chloroform solvent or the like that dissolves both the hydrophobic copolymerized polyester and the grafted polymer.

  The insoluble fraction of the coating film obtained by drying at about 80 ° C. and heat-treating at 120 ° C. for 5 minutes is preferably 50% by mass or more, more preferably 70% by mass from the viewpoints of hot water adhesion and blocking resistance. That's it.

  As the self-crosslinking polyester resin aqueous dispersion, for example, a commercially available product such as “Vylonal (registered trademark) AGN702” (manufactured by Toyobo Co., Ltd.) can be used.

  In addition, a grafted polyurethane can be prepared by a method similar to the above.

[Additive for heat resistant water adhesion improving layer]
Various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments are included in the heat resistant water adhesion improving layer as long as the effects of the present invention are not impaired. , Dyes, organic or inorganic particles, fillers, antistatic agents, nucleating agents and the like may be incorporated.

  In particular, when the inorganic particles are added to the heat resistant water adhesion improving layer, for example, when the heat resistant water adhesion improving layer is laminated on the surface of the polyester film and wound once, the slipperiness and blocking resistance are improved. Since it improves, it is preferable. In this case, silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, or the like can be used as the inorganic particles to be added. The average particle size used is preferably 0.005 to 5 μm, more preferably 0.01 to 3 μm, and most preferably 0.05 to 2 μm. Although the usage-amount of an inorganic particle is not specifically limited, It is preferable to mix 0.05-10 mass parts with solid content with respect to 100 mass parts of polymers in a heat-resistant water adhesive improvement layer, More preferably, it is 0.1-5. Part by mass.

[Method for forming heat resistant water adhesion improving layer]
The heat resistant water adhesion improving layer is composed of an aqueous dispersion of a mixture of at least one polymer selected from the group consisting of polyester, polyurethane and acrylic polymer and a crosslinking agent, or an aqueous dispersion of a self-crosslinking polymer. Since it is formed, it is most convenient to form it by a coating method. What is necessary is just to apply the coating liquid for heat resistant water adhesion improvement layers to the surface which forms at least a silicone rubber layer of a polyester film. The heat resistant water adhesion improving layer is preferably formed on the opposite side of the silicone rubber layer. That is, the heat resistant water adhesion improving layer is preferably formed on both sides of the polyester film. Adhesion between the decorative layer and the polyester film and adhesion to hot water are improved.

  In the coating step, any method such as a method of applying to an unstretched film of a polyester film and then stretching in at least one direction, a method of applying after longitudinal stretching, a method of applying to the film surface after the orientation treatment, etc. Is possible. In particular, when producing a polyester film, a so-called in-line coating method, in which the film is applied before the crystal orientation of the film is completed and then stretched in at least one direction and then the crystal orientation of the polyester film is completed, is easily formed into a thin film. Therefore, the effects of the present invention can be expressed more significantly, which is preferable.

  When applying the coating solution for the heat resistant water adhesion improving layer to the unstretched film of the polyester film, various coating methods such as gravure coating method, rod coating method, bar coating method, Mayer bar coating method, reverse kiss coating Method, die coating method, spray coating method and the like can be used.

[Decoration layer]
It is desirable to provide a decorative layer in the skin material film of the present invention. A composite molded body having a high degree of design can be produced only by a process of sticking a film for skin material to a molded body or an insert (injection) molding process. Examples of the decorative layer include a printed layer, a metal thin film layer, an inorganic thin film layer, and the like, and it is preferable to form one or more of these layers. The decorative layer is desirably formed on the surface of the polyester film opposite to the silicone rubber layer via the heat resistant water adhesion improving layer. Adhesion between the decorative layer and the polyester film is improved.

  For the formation of the printing layer, known printing methods such as gravure printing, flat printing, flexographic printing, dry offset printing, pad printing, and screen printing can be used depending on the product shape and printing application. In particular, offset printing and gravure printing are suitable for multicolor printing and gradation expression. Moreover, when the film for skin material is used for insert molding which is molded into a complicated shape, it is preferable to use a printing ink having excellent spreadability, and the binder resin is mainly composed of a flexible resin such as a polyurethane resin. Inks are preferred.

  The decorative layer may be not only a printed layer but also a metal or metal oxide thin film layer, or may be a combination of a printed layer and a metal (oxide) thin film layer. When a thin film layer of metal or metal oxide is formed, the permeation of water vapor or oxygen to the resin molded body is suppressed, so that the durability of the resin molded body can be improved. Examples of the method for forming a metal (oxide) thin film layer include vapor deposition, thermal spraying, and plating.

  As the vapor deposition method, either physical vapor deposition or chemical vapor deposition can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method. Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method. Examples of the plating method include an electroless plating (chemical plating) method, a hot dipping method, and an electroplating method. In the electroplating method, a laser plating method or the like can also be used. Among these, the vapor deposition method and the plating method are preferable for forming the metal layer, and the vapor deposition method is preferable for forming the metal oxide layer. The vapor deposition method and the plating method can be used in combination.

  As the metal used for vapor deposition, aluminum, chromium, silver, gold, and combinations or alloys thereof are preferable. When the film for skin material is used for insert molding that is molded into a complicated shape, a metal excellent in spreadability is preferable, for example, aluminum mixed with indium or the like is preferable.

  When a metal (oxide) thin film layer is partially formed on the decorative layer, a solvent-soluble resin layer is formed on a portion that does not require the thin film layer, and then a thin film layer is formed on the entire surface. Then, it is sufficient to remove the unnecessary metal thin film together with the solvent-soluble resin layer by performing solvent cleaning, and the solvent often used in this case is water or a mixed solution of water and a hydrophilic solvent. Another method is to form a metal (oxide) thin film on the entire surface, then form a resist layer on the portion where this thin film is to be left, etch the thin film with acid or alkali, and finally form a resist layer. The method of removing is mentioned.

[Adhesion improvement layer]
The film for skin material used in the present invention may be provided with an adhesive improvement layer for enhancing the adhesiveness with the molded body at the time of insert molding on the outermost layer opposite to the silicone rubber layer, if necessary. The adhesive used for this adhesion improving layer is not particularly limited as long as it has a function of enhancing the adhesion between the skin material film and the molded body. For example, a thermosetting type or a hot melt type can be used.

  As the thermosetting type, laminate adhesives such as polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, and the like can be used. The crosslinking agent is not limited. For example, the cross-linking agent described in the heat resistant water adhesion improving layer can be used. The aging conditions for the purpose of curing in this case are not particularly limited. For example, the temperature is preferably 45 to 65 ° C., and the time is preferably 24 to 48 hours. If the aging time is too short or the temperature is insufficient, the adhesive layer may be washed away during insert molding, leaving wavy ripples or hindering transparency. On the other hand, if the aging is excessive, the adhesiveness is deteriorated and floating occurs, and even if these disadvantages do not appear at room temperature, the heat resistance may be impaired.

  Hot melt types include natural rubber, acrylic resin, ethylene-vinyl acetate copolymer (EVA), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), etc. Various thermoplastic resins such as elastomers, polyamides, polyesters, polyolefins, and polyvinyl acetates can be exemplified. Further, a resin modified so as to include various functional groups or polar groups that enhance adhesion, such as a carboxyl group or an acid anhydride group, is more preferable. These modification | denaturation can be performed by a well-known method.

  Although the thickness of the said adhesive improvement layer is not specifically limited, 1-100 micrometers is preferable and 3-50 micrometers is more preferable. If it is less than 1 μm, the effect of improving adhesiveness is lowered, which is not preferable. On the other hand, when it exceeds 100 μm, the effect of improving the adhesiveness is saturated and the heat resistance and the like may be lowered. It is also economically disadvantageous.

  The formation method of the said adhesive improvement layer is not limited, either. For example, it may be formed by applying an adhesive as a solution, or by melting and extruding an adhesive resin. In addition, sheets made of an adhesive may be used in an overlapping manner.

[Adhesive layer]
In the film for skin material used in the present invention, an adhesive layer may be provided on the outermost layer opposite to the silicone rubber layer, if necessary. This pressure-sensitive adhesive layer can be used for attaching a skin material to an already formed molded body. The pressure-sensitive adhesive layer may be a single layer or a double-sided pressure-sensitive adhesive sheet in which two layers of pressure-sensitive adhesive layers sandwich a substrate.

  The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and any known pressure-sensitive adhesive can be used. Among these, an acrylic pressure-sensitive adhesive is preferable. The acrylic pressure-sensitive adhesive contains, for example, an acrylic polymer whose main monomer component is (meth) acrylate having 1 to 18 carbon atoms in the alkyl group as a main component or base polymer.

  Examples of the (meth) acrylate having an alkyl group having 1 to 18 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) Examples include acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl acrylate (meth) acrylate, decyl acrylate (meth) acrylate, and dodecyl (meth) acrylate. These (meth) acrylates can be used alone or in admixture of two or more.

  Moreover, the monomer component (copolymerizable monomer) which has a copolymerizability with the said (meth) acrylate may be used. In particular, when the acrylic polymer is cross-linked, the copolymerizable monomer is preferably a monomer for modifying the acrylic pressure-sensitive adhesive, and any known monomer for modifying can be used. The copolymerizable monomers can be used alone or in combination of two or more.

  Specifically, as the copolymerizable monomer, any of the monomer components constituting the acrylic polymer for the heat resistant water adhesion improving layer and the monomers exemplified as other types of monomers can be used, and further, ethylene, propylene, etc. Examples include α-olefin monomers.

  As the modifying monomer, the functional group-containing monomer is preferable, and among these, a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferable, and acrylic acid is particularly preferable. The acrylic polymer can be crosslinked using a functional group (particularly a polar group) derived from the modifying monomer.

  Polymerization methods for obtaining acrylic polymers include solution polymerization methods using emulsion initiators such as azo compounds and peroxides, emulsion polymerization methods and bulk polymerization methods, and light and radiation using photoinitiators. A polymerization method performed by irradiation can be employed. In the present invention, a method of polymerizing using a polymerization initiator that decomposes to generate radicals (radical polymerization method) can be suitably employed. In this radical polymerization, polymerization initiators such as peroxides such as benzoyl peroxide and tert-butyl permaleate, and azo compounds such as 2,2′-azobisisobutyronitrile and azobisisovaleronitrile are usually used. To do. The amount of the polymerization initiator used may be the amount usually used in the polymerization of the acrylic monomer, and for example, about 0.005 to 10 parts by mass, preferably 0.1 to 100 parts by mass of the total amount of monomer components. About 5 parts by mass.

  The ratio of the (meth) acrylate having an alkyl group having 1 to 18 carbon atoms as the main monomer component of the acrylic polymer is 50% by mass or more with respect to 100% by mass of the monomer component from the viewpoint of adhesive properties. preferable. 80 mass% or more is more preferable, and 90 mass% or more is further more preferable. Therefore, the proportion of the copolymerizable monomer other than the (meth) acrylate is 50% by mass or less in 100% by mass of the monomer component.

  The acrylic polymer obtained by polymerizing the monomer component can be used as it is. It is also possible to cure the acrylic polymer by crosslinking. When the polymer is crosslinked, the cohesive force of the pressure-sensitive adhesive can be further increased. For crosslinking, a crosslinking agent can be used. That is, the acrylic pressure-sensitive adhesive may contain a crosslinking agent together with the acrylic polymer. For the crosslinking of the polymer, a heat crosslinking method is preferably used.

  As the cross-linking agent, any of the cross-linking agents exemplified as the cross-linking agent that can be used in the heat resistant water adhesion improving layer can be used. As the crosslinking agent, melamine crosslinking agent, epoxy crosslinking agent, and isocyanate crosslinking agent are particularly preferable. A crosslinking agent can be used individually or in mixture of 2 or more types. The amount of the melamine crosslinking agent and / or epoxy crosslinking agent used is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the acrylic polymer. 0.01-20 mass parts is preferable with respect to 100 mass parts of acrylic polymers, and, as for the usage-amount of an isocyanate type crosslinking agent, 0.05-15 mass parts is more preferable.

  You may add various additives to an acrylic adhesive as needed. For example, a tackifier resin (for example, a rosin resin, a terpene resin, a petroleum resin, a coumarone / indene resin, a styrene resin, or the like) may be blended to adjust the adhesion characteristics. From the viewpoint of increasing the colorless transparency of the double-sided pressure-sensitive adhesive sheet and suppressing the change in color tone, a hydrogenated tackifying resin is preferable, and the blending ratio is preferably set in a range that does not increase the haze of the double-sided pressure-sensitive adhesive sheet. Further, as additives other than the tackifying resin, various known additives such as plasticizers, fillers such as fine powder silica, colorants, ultraviolet absorbers, surfactants and the like can be blended. The amount of these additives used may be a normal amount applied to the acrylic pressure-sensitive adhesive.

  The adhesive force of the acrylic pressure-sensitive adhesive layer can be controlled by a method such as a modification monomer (functional group-containing copolymerizable monomer), a ratio adjustment of a crosslinking agent, or a method using a surfactant. The thickness of the acrylic pressure-sensitive adhesive layer is not particularly limited, and in the case of a one-layer configuration, for example, in the case of a two-layer configuration, for example, 3 to 200 μm is preferable. 5-50 micrometers is more preferable and 10-30 micrometers is further more preferable.

  In addition, as the acrylic pressure-sensitive adhesive, for example, “SK Dyne” series manufactured by Soken Chemical Co., Ltd. can be used. Among these, use of a brand of optical pressure-sensitive adhesive is preferable.

  As a base material in the case of providing a double-sided double-sided pressure-sensitive adhesive sheet type adhesive layer on the skin material film, the above-described polyester film can be suitably used.

  The formation method of the said acrylic adhesive layer is not limited. If it is a single-layer adhesive layer, at any stage of the manufacturing process of the film for skin material, for example, a solution-type coating solution of an organic solvent or a coating solution in the form of an aqueous dispersion is prepared, A method of applying by a coating method is simple. When providing a double-sided PSA sheet type pressure-sensitive adhesive layer, it is convenient to prepare a double-sided PSA sheet separately and then incorporate it into the skin material film. In the case of providing a double-sided PSA sheet type adhesive layer, a layer having the same composition as the heat resistant water adhesion improving layer is provided between the acrylic adhesive layer and the base material. You may comprise so that adhesiveness with a material may be improved.

  In the case of a film for a skin material provided with a double-sided double-sided adhesive sheet type adhesive layer, the adhesive force of the adhesive layer on the side (inner side) that contacts the polyester film provided with the silicone rubber layer, and affixed to the molded body It is preferable that the adhesive strength on the side to be applied (outermost layer) is different, and it is preferable to set the adhesive strength of the outermost layer small. In the present invention, the attachment of the film for the skin material is also included when the molded product is assembled as a product, and if the skin material film is failed to be adhered, it leads to loss of an expensive product. If the adhesive strength of the surface layer is set small, it is preferable because it can be re-applied when it fails to adhere. The preferable range of the adhesive force of a specific outermost layer is 0.05 to 12 N / 25 mm. On the other hand, if the adhesive strength on the side that contacts the polyester film with the silicone rubber layer (inner side) is small, the adhesive layer will be exposed when peeling occurs at this interface, which may cause discomfort to the user of the product. become. Accordingly, the inner adhesive strength is preferably larger than that of the outermost layer, and is preferably about 12 to 30 N / 25 mm. This adhesive strength is the peel strength of a 180 degree peel test against SUS304 under an atmosphere of 23 ° C.

  A commercially available double-sided PSA sheet can also be used in the film for skin material provided with the double-sided PSA type adhesive layer having the above two-layer structure. It is preferable to use a double-sided pressure-sensitive adhesive sheet in which pressure-sensitive adhesive layers having different adhesive forces are laminated on both sides of a polyester film substrate. Examples thereof include a PET-based double-sided pressure-sensitive adhesive sheet “412D50” manufactured by Kyori Giken Chemical Co., Ltd. Although the method of sticking the film for the skin material to the surface of the molded body with the double-sided pressure-sensitive adhesive sheet having the above two-layer structure is not limited, first, the film for the skin material is stuck on the surface of the pressure-sensitive adhesive layer having the larger adhesive force of the double-sided pressure-sensitive adhesive sheet. After attaching, it is a preferable embodiment to stick to the surface of the molded body with another adhesive layer.

  On the other hand, when a single-layer type adhesive layer is used, an adhesive layer having a low initial adhesive force at the time of sticking and increasing the adhesive force with time or heat treatment (hereinafter sometimes referred to as an adhesive strength improving treatment) is formed. It is preferable to do this. By using such a pressure-sensitive adhesive layer, it is possible to reduce loss due to affixing mistakes, and in the end, the skin material can be firmly fixed to the molded body. This will reduce the trouble of peeling.

  The initial adhesive strength and the adhesive strength after the adhesive strength improving treatment in the one-layer type adhesive layer are not particularly limited, but the initial adhesive strength is preferably less than 8 N / 25 mm, and more preferably 6 N / 25 mm or less. The lower limit is not particularly limited, but is about 0.05 N / 25 mm. The adhesive strength after the adhesive strength improving treatment is preferably 8 N / 25 mm or more, more preferably 10 N / 25 mm or more, and further preferably 12 N / 25 mm or more. The upper limit is not particularly limited, but is about 30 N / 25 mm.

  In order to develop the adhesive properties as described above, the adhesive strength improving treatment may be a method of delaying the crosslinking reaction of the adhesive layer using a blocked crosslinking agent or the like, or curing with a catalyst using an oxidative curing type crosslinking agent. A method of adjusting time or the like may be employed. In addition, although the conditions of an adhesive force improvement process are not specifically limited, It is preferable that adhesive force improves by storage at room temperature. As a standard, it is a preferable embodiment that the adhesive strength after 144 hours at room temperature (about 20 to 30 ° C.) achieves the above numerical value after sticking.

[Separate film]
In the case where the skin material film has an adhesive layer, a separate film is preferably laminated on the adhesive layer surface. The separation film is not particularly limited as long as the peelability from the adhesive layer is good, and it is preferable to use a commercially available release polyester film in which a release layer made of a silicone compound or a fluorine compound is laminated. It is. Moreover, you may use the film which has a layer of the structure similar to the peeling layer for the above-mentioned polyester film for fabric weight as a mold release layer.

  The peel strength between the separate film and the adhesive layer is preferably 0.04 to 1.3 N / 25 mm. If it is 0.04N / 25mm or more, when winding up the film for skin materials in a manufacturing process etc., generation | occurrence | production of the float of a separate film can be suppressed and a high quality product can be manufactured. On the other hand, by setting the peel strength to 1.3 N / 25 mm or less, the peelability between the separate film and the adhesive layer is improved. In addition, the above-mentioned range is preferable also for the peeling strength of the above-mentioned basis weight polyester film.

[Composite molding]
A composite molded body with improved tactile sensation is obtained by using the film for skin material of the present invention and combining it with a resin molded body. The resin constituting the molded body is appropriately selected depending on market demands, and for example, a thermoplastic resin or a thermosetting resin can be used.

  Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene; polystyrene resins such as polystyrene, syndiotactic polystyrene, AS resin, and ABS resin; polyethylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and the like. Polyester resins; various acrylic resins; polycarbonate resins; polyamides, polyamideimides, polysulfones, polyacetals, polyphenylene ethers, polyphenylene sulfides, polyarylates, polyetherimides, polyethersulfones, polyether ketones, etc., and their blends Articles and alloy compositions can also be used. Specific examples of the thermosetting resin include unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin and the like. Of these, thermoplastic resins such as polyolefin resins, polystyrene resins, polyester resins, acrylic resins, and polycarbonate resins are preferable. A known reinforcing fiber may be included in the resin.

  There are three methods for compounding with a molded body. (1) a method of performing insert molding, (2) a method of using an adhesive layer of a film for skin material, and (3) a method of using a separate double-sided adhesive sheet.

  In the method of performing the insert molding of (1), there is no need to form an adhesive layer on the skin material film. It is desirable to provide an adhesion improving layer. In molding, the skin material film was previously molded by vacuum molding, pressure molding under low pressure, press molding, etc., and the film was placed in the mold so that the silicone rubber layer was in contact with the mold. Thereafter, the resin may be injection-molded and integrated, or a flat skin material film may be placed in a mold, and the resin may be injection-molded and integrated. The molding conditions and the like may be appropriately selected depending on the resin used.

  In (2), a film for skin material provided with an adhesive layer is used. What is necessary is just to peel a separate film from the adhesion layer of this film for skin materials, and to stick on the molded object surface.

  In (3), the molded body and the laminated polyester film for the skin material may be bonded using a separate double-sided pressure-sensitive adhesive sheet using a film for the skin material having no adhesive layer. The separate double-sided pressure-sensitive adhesive sheet may be any double-sided pressure-sensitive adhesive sheet, but the double-sided pressure-sensitive adhesive sheet described in the adhesive layer of the skin material film is preferable.

  Hereinafter, the present invention will be described in more detail with reference to examples. These are all included in the technical scope of the present invention. The measurement / evaluation methods employed in the examples are as follows. In the examples, “parts” means “parts by mass”, and “%” means “% by mass” unless otherwise specified.

1. Adhesiveness A cutter knife was inserted between the silicone rubber layer of the skin material film and the polyester film, and peeling was performed by applying force with a finger. The case where the peel strength was strong and the interface could not be evaluated was evaluated as ◯, and the case where the interface could be aligned was evaluated as ×.

2. Heat resistant water adhesion Cut the film for skin material into 50 mm x 50 mm and place the sample in water in a cylindrical glass container with a lid of 400 cc of distilled water so that the silicone rubber layer is on the lower side. Cap the container with the entire sample immersed in water. In the case where the sample is not immersed in water by its own weight, for example, a polyester film having a size of 60 mm × 60 mm and a thickness of 188 μm may be placed on the sample and weighted. The size and material of the weight are not particularly limited, and the entire sample may be immersed in water. The container containing the sample is placed in a gear oven set at 80 ° C. and allowed to stand for 24 hours. After heat treatment, remove the container from the oven, quickly remove the sample, apply force with the finger pad from the silicone rubber layer side to the end and rub it 10 times, and evaluate whether the silicone rubber layer peels from the polyester film side. The case where the rubber layer was not peeled was marked with ◯, and the case where the rubber layer was peeled was marked with x.

3. Ink adhesion strength In accordance with the adhesion (cross-cut method) test method described in JIS K5600-5-6 (former JIS K5400 8.5.1), the ink adhesion strength of the polyester film surface of the skin material film was evaluated. . Specifically, after printing the following ink on the polyester film surface of the insert film, using a cross-cut guide, 100 pieces of 1 mm squares were created on the printing surface with a cutter blade, and then an adhesive tape (manufactured by Nichiban Co., Ltd .: “Cello Tape”). (Registered Trademark) 31B ") was attached to the printing surface and completely adhered so that no air remained. Next, after the adhesive tape was peeled off vertically, the remaining number of squares on the printed surface was evaluated as adhesion (remaining number / 100), and 80/100 or more was evaluated as ○, and less than that was determined as ×. . As the ink, UV curable ink (“Best Cure (registered trademark) 161” manufactured by Toka Dye Co., Ltd.) was used, and the polyester film surface of the film for the skin material was printed with an RI tester and then irradiated with 100 mJ / cm ² of UV. .

4). Measurement of degree of plane orientation Using Abbe refractometer ("4T", manufactured by Atago Co., Ltd.), the longitudinal refractive index (Nx), the lateral refractive index (Ny) and the thickness direction of the polyester film before laminating the silicone rubber layer The refractive index (Nz) was measured, and the obtained value was substituted into the following formula (1) to calculate the degree of plane orientation.
Plane orientation degree = (Nx + Ny) / 2−Nz (1)

5. Anti-slip property of skin film Film put the silicone rubber layer surface of the skin material film on a glass plate and try to move it while pressing the film for skin material with a finger from the polyester film side, and sensory evaluation of the anti-slip property of the silicone rubber layer did.
Anti-slip effect Large: ○, Anti-slip effect Medium: △, Anti-slip effect Small: ×

6). Tactile sensation of the film for skin material The surface of the silicone rubber layer of the film for skin material was traced with a finger, and the tactile sensation was evaluated.
Tactile sensation Good: ○, Tactile sensation Medium: △, Tactile sensation Evil: ×

7). Centerline average roughness Ra
About the polyester film surface (surface opposite to the surface on which the silicone rubber layer is formed) of the film for the skin material before forming the decorative layer, using a “SE-200 type surface roughness meter” manufactured by Kosaka Laboratory Co., Ltd. Magnification: 1000, lateral magnification: 20, cut-off: 0.08 mm, measurement length: 8 mm, measurement speed: 0.1 mm / min.

8). Evaluation of thickness unevenness From a polyester film obtained in the following examples and comparative examples or a coated polyester film laminated with a heat resistant water adhesion improving layer, a continuous tape having a length of 3 m in the transverse direction and 5 cm in the longitudinal direction. A film sample is cut out, and the film thickness is measured with a continuous film thickness measuring machine (manufactured by Anritsu Co., Ltd.) and recorded on a recorder. From the obtained chart, the maximum value (Tmax), the minimum value (Tmin), and the average value (Tav) of the thickness were obtained, and the thickness unevenness (%) was calculated by the following formula. In addition, the measurement was performed 3 times and the average value was defined as thickness unevenness. When the length in the transverse stretching direction was less than 3 m, samples having a length in the transverse stretching direction of less than 3 m were joined to produce a tape-like sample. In this case, the measured value at the joint portion was excluded and was not used for calculation of thickness unevenness.
Unevenness of thickness (%) = ((Tmax−Tmin) / Tav) × 100

9. Evaluation of Heat Shrinkage A strip sample having a length of 250 mm and a width of 20 mm was cut out from the coated polyester film before lamination of the silicone rubber layer in the longitudinal direction (MD) and the width direction (TD), respectively (MD and TD). 3 samples). Two marks were made at intervals of 200 mm in the length direction of each sample, and the distance A between the two marks was measured under a constant tension of 5 gf (tension in the length direction). Subsequently, one end of each strip-shaped sample is hung with a clip under no load on the basket, placed in a gear oven set at 150 ° C., and after 30 minutes, the basket is taken out of the gear oven and kept at room temperature ( 23 ° C.). Next, for each sample, the interval B between the two marks is read in units of 0.25 mm under a constant tension of 5 gf (tension in the length direction). Using the read intervals A and B, the thermal shrinkage rate of each sample at 150 ° C. was calculated by the following equation.
Thermal contraction rate (%) = ((A−B) / A) × 100

  The coated polyester film is laminated with a heat resistant water adhesion improving layer, but since the thickness is as thin as 0.01 to 0.5 μm, the heat resistant water adhesion improving layer is a heat shrinkage of the polyester film of the substrate Since the influence on the rate is estimated to be small, the thermal shrinkage rate of the coated polyester film was regarded as the thermal shrinkage rate of the polyester film.

10. Adhesive strength About the film for skin materials which has an adhesive layer, the adhesive force with respect to SUS304 was measured by the 180 degree peeling method according to JISZ0237. The sample had a width of 25 mm, and adhesion to SUS was performed by reciprocating twice at a speed of about 29 mm / sec using a 2 kgf roller. Using a tensile tester ("Autograph"; manufactured by Shimadzu Corporation), a tensile test was performed in a 23 ° C atmosphere at a tensile (peeling) speed of 300 mm / min, and the maximum tensile strength was determined as the adhesive strength (N / 25 mm). It was.

11. Peel strength of a polyester film for basis weight or a separate film A test piece having a length of about 200 mm and a width of 25 mm is prepared. The surface (2 surfaces) whose peel strength is to be measured is exposed, each end is set on the chuck of the same tensile tester as above, and the distance between chucks is 50 mm and the temperature is 23 according to the method described in JIS K6256-1. T-type peel strength was measured at 50 ° C. and a tensile speed of 50 mm / min. During peeling, the end of the film was lifted with a bar so that the T-shape was maintained. The maximum strength at the time of T-type peeling was defined as the peeling strength.

Example 1
(1) Production of coated polyester film (1-1) Preparation of coating liquid for forming heat resistant water adhesion improving layer [Preparation of water-dispersible copolyester resin]
Water-dispersible copolymerization using antimony trioxide as a polycondensation catalyst in a batchwise manner using one pressure esterification reaction tank with a distillation column and two polycondensation reaction tanks with a vacuum generator Polyester was synthesized.

  The copolymer composition of the water-dispersible copolymer polyester is terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // neopentyl glycol / ethylene glycol = 50/43/7 // 70/30 (molar ratio). The reduced viscosity was 0.68 dl / g.

[Preparation of coating solution]
100 parts of the pulverized product of the water-dispersible copolyester resin was dispersed in water by a conventional method. With respect to 100 parts of the solid content of this aqueous dispersion, 5 parts of methylol melamine resin “Cymel (registered trademark) 303” (manufactured by Mitsui Cytec Co., Ltd.) is used as the catalyst, and “Catalyst 600” (Mitsui Cytec Co., Ltd.) as the catalyst. (0.025 parts) was added and stirred well to obtain a coating solution.

(1-2) Production of polyester film and lamination of improved hot water adhesion layer Polyethylene terephthalate containing 0.04% amorphous silica having an average particle size (SEM method) of 1.5 μm (inherent viscosity 0.65 dl / g) The pellets were sufficiently dried in vacuum, then supplied to an extruder heated to 280 ° C., extruded into a sheet form from a T-shaped die, and applied to a mirror casting drum having a surface temperature of 30 ° C. using an electrostatic application casting method. It was wound and solidified by cooling. The unstretched film was stretched 3.5 times in the longitudinal direction while passing through a heating roll group at 95 ° C. to obtain a uniaxially stretched film. Both surfaces of this film were subjected to corona discharge treatment, and the coating solution was applied to both treatment surfaces. The uniaxially stretched film was guided to a preheating zone while being held with a clip, dried at 110 ° C., and continuously stretched 3.5 times in the width direction in a heating zone at 125 ° C. Further, heat treatment was performed for 6 seconds at 225 ° C. while relaxing 6% in the width direction. A coated polyester film (i) having a thickness of 50 μm was obtained, in which both sides of the biaxially stretched polyethylene terephthalate film were coated with a 0.08 μm-thick crosslinked hot water adhesion improving layer. The obtained polyester film had a degree of surface orientation of 0.165 and good thickness accuracy. The evaluation results are shown in Table 1.

(2) Formation of Silicone Rubber Layer (2-1) Preparation of Silicone Rubber Layer Forming Coating Liquid Highly Transparent Silicone Rubber Compound (“TSE260-5U”; Rubber Hardness 55 °; Momentive Performance Materials Japan) The product was weighed so that the mass ratio with respect to toluene was 23%, and was put together with toluene into a stirrer equipped with a vacuum defoaming device, and stirred at room temperature for 15 hours under atmospheric pressure to dissolve in toluene. Trimethylolpropane trimethacrylate was added to the resulting solution so as to be 2 parts with respect to 100 parts of the rubber compound, and after stirring uniformly, the vacuum deaerator was driven and the gauge pressure: -750 mmHg vacuum The mixture was further stirred for 20 minutes and degassed.

(2-2) Lamination of silicone rubber layer The above-mentioned coating solution for forming a silicone rubber layer is applied to the coated polyester film (i) obtained by the above method so that the thickness after drying becomes 30 μm, and then placed in an oven. It was introduced and dried at 80 ° C. Separately, a sodium dodecylbenzenesulfonate solution was applied by a microgravure method to a matted surface of a polyester film having a thickness of 50 μm that had been sand-matted as a polyester film for weighting, and dried. The thickness after drying was about 30 nm. The surface-treated surface of the basis weight polyester film was overlaid on the surface of the silicone rubber layer, and was continuously laminated while pressing with a pressure roll at a pressure of 30 N / cm ² .

  Next, the laminate is introduced into an electron beam irradiation apparatus, irradiated with an electron beam of 200 KV and 15 Mrad from the coated polyester film side, and crosslinked to obtain a silicone rubber layer laminated polyester film which is wound into a roll. It was. In addition, the peeling force of the polyester film for fabric weight of the obtained silicone rubber layer lamination | stacking polyester film was 0.5 N / 25mm.

(3) Formation of decoration layer By performing offset printing on the opposite side of the silicone rubber layer-laminated surface of the silicone rubber layer laminated polyester film obtained by the above method using the UV curable ink, the decoration layer Formed.

(4) Formation of Adhesive Improvement Layer “Takelac (registered trademark) A-310” and “Takenate (registered trademark)” as a polyester-based adhesive on the decorative layer surface of the decorative layer-containing laminated film produced by the above method A-3 "(both made by Takeda Pharmaceutical Co., Ltd. (currently Mitsui Takeda Polyurethane) Co., Ltd.) is applied and applied by a coating machine to about 3 g / m ² to form an adhesive layer, and the adhesive layer is cured. For this purpose, aging was performed at 50 ° C. for 24 hours to form an adhesion improving layer. Thereby, the roll-shaped original fabric of the film for skin materials provided with the decorating layer and the adhesive improvement layer was obtained. The evaluation results of the polyester film and the film for the skin material are shown in Table 1.

(5) Pre-molding of the film for the skin material After peeling off the polyester film for weighting from the raw material of the film for the skin material as described above and applying it to a cutting machine, Was drawn using a drawing die heated to 110 ° C. and the lower die heated to 90 ° C. to obtain a pre-molded body for insert having a slightly curved periphery.

(6) Production of composite molded body Next, the pre-molded body for inserts was punched into a predetermined shape, and placed in a mold having a film gate having a rectangular cross section. The molding conditions were set to mold temperature: 100 ° C., nozzle resin temperature: 300 ° C., injection speed: 2 mm / sec, and insert molding was performed using a polycarbonate resin. A composite molded body in which the film for the skin material was integrated on the surface of the resin molded product was obtained.

  The film for skin material obtained in this example was excellent in tactile sensation, and was excellent in adhesion between the polyester film and the silicone rubber layer and in hot water adhesion. Further, the obtained composite molded article was excellent in tactile sensation, had a clear print design, and had a high-grade appearance that was matte by the silicone rubber layer.

Comparative Example 1
In the method of Example 1, a polyester film, a film for skin material, and a composite molded body were obtained in the same manner as in Example 1 except that the lamination of the silicone rubber layer was stopped. The evaluation results of the polyester film and the film for the skin material are shown in Table 1.

  The skin material film and composite molded body obtained in Comparative Example 1 were inferior in tactile sensation and anti-slip effect because the silicone rubber layer was not laminated.

Comparative Example 2
In Example 1, the polyester film production process was carried out in the same manner as in Example 1 except that the longitudinal stretching temperature was changed to 105 ° C., the longitudinal and lateral stretching ratios were changed to 3.0 times, and the heat treatment temperature was changed to 185 ° C. A film, a film for skin material, and a composite molded body were obtained. The evaluation results of the polyester film and the film for the skin material are shown in Table 1. In addition, the plane orientation degree of the polyester film obtained at this time was 0.130. Since the polyester film obtained in this Comparative Example 2 has a low degree of plane orientation of 0.130, the thickness accuracy of the film and the heat shrinkage rate at 150 ° C. are inferior to those of the polyester film obtained in Example 1. It was.

Comparative Example 3
In Example 1, in the same manner as in Example 1 except that the longitudinal stretching temperature in the polyester film production process was changed to 105 ° C., the longitudinal and lateral stretching ratios were changed to 3.9 times, and the heat treatment temperature was changed to 230 ° C. A film, a film for skin material, and a composite molded body were obtained. The evaluation results of the polyester film and the film for the skin material are shown in Table 1. In addition, the plane orientation degree of the polyester film obtained at this time was 0.205.

  The plane orientation degree of the polyester film obtained in this Comparative Example 3 was as high as 0.205, and the delamination resistance was poor. Therefore, compared with the film for skin materials obtained in Example 1, adhesiveness, heat-resistant water adhesion, and ink adhesion were inferior.

Comparative Example 4
In the polyester film manufacturing process of Example 1, a polyester film, a film for a skin material, and a composite molded body were obtained in the same manner as Example 1 except that the application of the coating solution for the heat resistant water adhesion improving layer was stopped. The evaluation results of the polyester film and the film for the skin material are shown in Table 1. The skin material film obtained in this Comparative Example had good tactile sensation, but was inferior in adhesiveness and hot water adhesion.

Comparative Example 5
In the method of Example 1, a polyester film and a film for skin material were obtained in the same manner as in Example 1 except that the coating solution used in the polyester film production process was not blended with a methylol melamine resin as a crosslinking agent. And the composite molding was obtained. The evaluation results of the polyester film and the film for the skin material are shown in Table 1. The skin material film obtained in this Comparative Example had good tactile sensation, but was inferior in hot water adhesion.

Example 2
In the method of Example 1, a film for skin material and a composite molded article were produced in the same manner as in Example 1 except that a smooth-surfaced polyester film with improved peelability prepared by the following method was used as the basis polyester film. Got. The evaluation results of the polyester film and the film for the skin material are shown in Table 1. The film for skin material obtained in this example had good anti-slip properties, and good adhesion and hot water adhesion. In addition, the printed image is clear.

(Preparation of release layer coating solution)
“Vylonal (registered trademark) MD-1900” (manufactured by Toyobo Co., Ltd.) which is a water-dispersible copolyester resin as a resin component, and styrene-benzoguanamine-based spherical organic particles having an average particle diameter of 2 μm as a surface roughening substance “Eposter (Registered trademark) MS ”(manufactured by Nippon Shokubai Co., Ltd.), colloidal silica having an average particle diameter of 0.05 μm, a polyethylene emulsion wax agent as a polymer wax component, and an anionic antistatic agent (dodecyl diphenyl oxide disulfonic acid as an antistatic agent) Sodium).

  Using a homogenizer, the organic spherical particles of the surface-roughening material are sufficiently dispersed in a mixed solution of water and isopropyl alcohol (mass ratio 80/20), and then the resin component with respect to the total mass of the coating solution Thorough mixing so that 2.5%, organic spherical particles of surface roughening substance 0.025%, colloidal silica 0.3%, polymer wax component 0.13%, antistatic agent 0.13% Thus, a coating solution was prepared.

[Manufacture of polyester film for basis weight]
The said coating liquid was apply | coated on the polyester film (38 micrometers) using the wire bar (No. 5). The coating amount of the coating solution was about 8 to 10 g (wet state) per 1 m ^{2 of the} base film. The coating solution was dried at 160 ° C. for about 60 seconds to obtain a basis polyester film.

Example 3
In the method of Example 1, the silicone rubber compound forming the silicone rubber layer (as “TSE260-3U” (rubber hardness 30 degrees; manufactured by Momentive Performance Materials Japan)) is the same as in Example 1. A film for a skin material and a composite molded body were obtained by the method described in Table 1. The results are shown in Table 1.

  The film for a skin material and the composite molded body obtained in this example had the same characteristics as those obtained in Example 1 and were of high quality.

Examples 4-5
A film for a skin material and a composite molded body were obtained in the same manner as in Example 1 except that the coating liquid for the hot water resistant adhesion improving layer of Example 1 was changed to the following composition. The evaluation results are shown in Table 2.

  The films for skin materials and composite moldings obtained in these examples had the same or higher characteristics as those of Example 1 and were of high quality.

[Coating liquid of Example 4]
10 parts of the “Cymel 303” and 0.04 part of the “Catalyst 600” with respect to 100 parts of the solid content of the acrylic emulsion (“Joncrill (registered trademark) PDX-7630A”; manufactured by BASF Japan). Were mixed to obtain a coating solution for a heat resistant water adhesion improving layer.

[Coating liquid of Example 5]
As an oxazoline-based cross-linking agent ("Epocross (registered trademark) WS-700"; Nippon Shokubai Co., Ltd.) with respect to 100 parts of a solid content of a polyurethane-based aqueous dispersion ("Hydran (registered trademark) AP40"; manufactured by Dainippon Ink and Industry). Product) was added in a solid content of 3 parts to obtain a coating solution for a heat resistant water adhesion improving layer.

Example 6
In Example 1, the rubber component was changed to a highly transparent silicone rubber compound (“TSE260-3U”; rubber hardness 30 degrees; manufactured by Momentive Performance Materials Japan) and 2 parts of trimethylolpropane trimethacrylate A film for a skin material and a composite molded body were obtained in the same manner as in Example 1 except that pentaerythritol tetraacrylate was used in an amount of 3 parts with respect to 100 parts of the total amount of the silicone rubber compound. . The evaluation results are shown in Table 2.

  The skin material film and composite molded body obtained in Example 6 had the same characteristics as the skin material film and composite molded body obtained in Example 1 and were of high quality. In particular, the film for skin material obtained in Example 6 was excellent in adhesiveness.

Example 7
In Example 1, the same procedure as in Example 1 was used, except that a self-crosslinking type polyester resin made of a graft-modified polyester resin prepared by the following method was used as the coating solution for forming the heat resistant water adhesion improving layer. A film for a skin material and a composite molded body were obtained. The evaluation results are shown in Table 2.

  The film for a skin material and the composite molded body obtained in Example 7 had characteristics higher than those of Example 1 and were of high quality.

[Preparation of coating solution for forming a layer for improving heat resistant water adhesion]
(Preparation of copolyester resin)
Self-crosslinking polyester resin aqueous dispersion “Vironal (registered trademark) AGN702” (Toyobo Co., Ltd.) 40 parts, water 24 parts and isopropyl alcohol 36 parts were mixed, and further 10% aqueous solution of anionic surfactant 0.6 Part, propionate 1 part, colloidal silica particles (average particle size 40 nm) 20% aqueous dispersion 1.8 parts, dry process silica particles (average particle size 200 nm; average primary particle size 40 nm) 4% aqueous dispersion 1 .1 part was added to obtain a coating solution for the heat resistant water adhesion improving layer.

Example 8
In Example 1, a skin material film and a composite molded body were obtained in the same manner as in Example 1 except that the surface treatment of the basis weight polyester was omitted. The evaluation results are shown in Table 2. The film for a skin material and the composite molded body obtained in Example 8 had the same characteristics as Example 1 and were of high quality. However, the peel strength of the polyester film for basis weight was 1.2 N / 25 mm, and the peelability was slightly inferior to the film for skin material of Example 1.

Example 9
The film for the skin material obtained in Example 1 is a PET-based double-sided pressure-sensitive adhesive sheet (“412D50” manufactured by Kyori Giken Chemical Co., Ltd.) having a single-sided adhesive strength of 10 N / 25 mm and the other side of 14 N / 25 mm: substrate thickness of 12 μm. : Total thickness of 50 μm) and attached to the surface of the portable game machine. The operation unit and the display unit of the game machine were previously punched and pasted so that only the other portions were covered. As a result, the feel on the surface of the game machine could be improved. In addition, the double-sided pressure-sensitive adhesive sheet was attached so that the one having a lower adhesive force was placed on the game machine surface side, so that it could be peeled off even when it was stuck, and contamination and damage of the game machine was avoided.

Example 10
The adhesive layer forming coating solution having the following composition was applied to the surface of the adhesion improving layer of the skin material film obtained in Example 1 so that the thickness after drying was 30 μm, and dried, and a separate film was laminated. Thus, a film for a skin material having an adhesive layer was obtained. This skin material film was punched in the same manner as in Example 10 and attached to the surface of the portable game machine. As a result, the feel on the surface of the game machine could be improved.

  In addition, the initial adhesive force of the film for skin materials provided with the said adhesive layer is 4.8 N / 25mm, and the adhesive force after an adhesive force improvement process (after sticking and storing for 144 hours at room temperature) is 19.0 N / It was 25 mm.

  Since the initial adhesive strength was small, the game machine could be peeled off without being contaminated or damaged even if it was stuck. Further, since the adhesive strength after the adhesive strength improving treatment was large, peeling of the film for the skin material did not occur during use of a game machine or the like.

[Coating liquid for forming adhesive layer]
An acrylic polymer solution was made by mixing 100 parts of a polymer having a weight ratio of butyl acrylate, methyl acrylate and hydroxylethyl acrylate of 60/8/2, 40 parts of ethyl acetate and 60 parts of toluene. To this solution, 2.0 parts of blocked isocyanate ("Duranate (registered trademark) MF-K60X" manufactured by Asahi Kasei Chemical Co., Ltd.) and 3.0 parts of polyisocyanate ("Coronate L (registered trademark)" manufactured by Nippon Polyurethane Co., Ltd.) Was added and mixed uniformly to prepare a coating solution for forming an adhesive layer.

  The laminated polyester film for skin material of the present invention is excellent in the adhesiveness between the silicone rubber layer and the polyester film, its durability, heat resistant water adhesion and the like. Moreover, it adheres well to the molded body at the time of insert molding or sticking. By decorating the polyester film side of the laminated polyester film for skin material and combining it with a molded body, it has become possible to efficiently mass-produce a composite molded body to which an advanced design has been imparted. In addition, by providing the silicone rubber layer on the outermost surface, an elastic tactile sensation can be obtained, and the silicone rubber layer can relax the external force, so that the durability of the composite molded body can be improved. In addition, since the silicone rubber layer is disposed on the outermost surface and the surface shape of the silicone rubber layer is controlled by the weighting method, the slipperiness, grip and tactile properties of the silicone rubber layer surface can be changed. These functions can be imparted to the surface of the composite molded body.

  Therefore, the laminated polyester film for the skin material of the present invention is a casing, protective case, keypad, etc. for mobile phones, mobile PCs, portable game machines, portable audio devices, etc .; It is useful as a skin material for automobile interior parts such as.

Claims (14)

In a laminated polyester film for a skin material in which a silicone rubber layer is formed on one side of a polyester film having a plane orientation degree of more than 0.15 and less than 0.20,
Between the silicone rubber layer and the polyester film, a reaction product of one or more polymers selected from the group consisting of polyester, polyurethane and acrylic polymers and a crosslinking agent, or a self-crosslinking polyester is self-supporting. A heat resistant water adhesion improving layer having a thickness of 0.01 to 0.5 μm including a crosslinked one is formed,
The centerline average roughness Ra of the silicone rubber layer surface is 0.20 to 0.80 μm,
A laminated polyester film for a skin material with improved tactile sensation , characterized in that the silicone rubber layer does not peel off when hot water adhesion is evaluated by a method defined in the specification. The laminated polyester film for a skin material according to claim 1 , wherein the heat resistant water adhesion improving layer is formed on both surfaces of the polyester film. The laminated polyester film for skin material of Claim 1 or 2 with which the decorating layer is formed in the opposite side of the silicone rubber layer formation surface of the said polyester film. The laminated polyester film for a skin material according to any one of claims 1 to 3 , wherein an adhesion improving layer is formed on the surface opposite to the silicone rubber layer forming surface of the polyester film. The laminated polyester film for a skin material according to any one of claims 1 to 4 , wherein an adhesive layer is formed on a surface opposite to the silicone rubber layer forming surface of the polyester film. The laminated polyester film for a skin material according to claim 5 , wherein the adhesive layer is a double-sided adhesive sheet having a substrate sandwiched between two adhesive layers. The said double-sided adhesive sheet is a laminated polyester film for skin materials of Claim 6 in which the adhesive force of the adhesive layer equivalent to the outermost layer of the laminated polyester film for skin materials is smaller than the adhesive force of an adhesive layer inside. The laminated polyester for a skin material according to claim 7 , wherein the adhesive force of the outermost adhesive layer of the double-sided adhesive sheet is 0.05 to 12 N / 25 mm, and the adhesive force of the inner adhesive layer is 12 to 30 N / 25 mm. the film. The laminated polyester film for a skin material according to any one of claims 5 to 8 , wherein a separate film is laminated on the surface of the outermost adhesive layer. The laminated polyester film for a skin material according to any one of claims 1 to 4 is inserted into a mold so that the silicone rubber layer becomes the outermost surface of the molded body, and then the mold is closed and a resin is injected. A composite molded body with improved tactile sensation, characterized by being insert molded. A composite molded body with improved tactile sensation, characterized in that the laminated polyester film for skin material according to any one of claims 5 to 9 is adhered to the surface of the molded body with an adhesive layer. The laminated polyester film for a skin material according to any one of claims 1 to 4 , wherein the silicone rubber layer is adhered to the surface of the molded body with a separate double-sided pressure-sensitive adhesive sheet so as to be the outermost surface. A composite molded body with improved tactile feel. Each adhesive strength of the adhesive layer is different, complex molded body according to claim 1 2 is obtained by attaching a low-adhesion adhesive layer on the molded surface of the double-sided pressure-sensitive adhesive sheet. An adhesive strength 0.05~12N / 25mm of one surface of the adhesive layer of the double-sided pressure-sensitive adhesive sheet, a composite molding according to claim 1 3 adhesion of the adhesive layer on the other surface is 12~30N / 25mm body.