JP2013244650A - Laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated polyester film which is excellent in flaw recovery property and cosmetics resistance and is suitable for molding use applications.SOLUTION: A laminated film has an "A" layer on at least one side of base material film and a mass increase rate of the "A" layer when an oleic acid is applied to the surface of the "A" layer and kept at 60°C as it is for one hour is not more than 10 mass%. In addition, when a load of 0.5mN is applied for 10 seconds in microhardness gauge measurement, a maximum rate of displacement in a thickness direction of the "A" layer is 1.0 to 3.0 μm, and a rate of creep displacement in the thickness direction of the "A" layer is 0.05 to 0.5 μm. Further, when the load is set at 0mN, the residual displacement rate in the thickness direction of the "A" layer is 0.2 to 0.65 μm.

Description

  The present invention relates to a laminated film that is excellent in molding followability, scratch resistance, and adhesion to a resin substrate as a molding material, and is advantageous in terms of productivity and cost, and can be suitably used for decorative molding.

  A molding material such as decorative molding is provided with a surface hardness layer in order to prevent scratches during molding and to prevent scratches in the process of using the article after molding. However, the surface hardened layer lacks the elongation to follow the molding, so cracks occur at the time of molding, and in extreme cases, the film breaks or the surface hardened layer peels off. For example, a method of forming a surface hardness layer after molding, or molding in a semi-cured state and then completely curing by heating or actinic radiation is applied. However, since the molded article is processed three-dimensionally, it is very difficult to provide a surface hardened layer by post-processing, and when molding in a semi-cured state, depending on the molding conditions, May induce dirt. For this reason, scratch-resistant materials that follow molding are desired, and in recent years, “self-healing materials” (Patent Documents 1 and 2) that self-repair light scratches from scratch prevention due to increased hardness have attracted attention. Self-healing materials are capable of self-healing deformation in their own elastic recovery range, and two types are widely known: thermosetting type and active energy ray curable type using ultraviolet rays or electron beams.

  The thermosetting materials described in Patent Documents 1 and 2 are excellent in moldability and self-repairability.

  Further, the ultraviolet ray curable self-healing materials described in Patent Documents 3 and 4 are relatively excellent in stain resistance.

International Publication No. 2011/136042 Pamphlet Japanese Patent No. 3926461 JP 2001-2744 A Japanese Patent No. 3676260

  However, since the thermosetting materials described in Patent Documents 1 and 2 have poor stain resistance, they may cause various problems when they come into contact with fingers with cosmetics or a resin bag to which a plasticizer is added. is there. The stain resistance shown here means that the plasticizer (dioctyl phthalate, etc.) contained in the vinyl chloride sheet, cosmetics, ink components such as oil-based magic, etc. penetrate into the self-healing material and cause coloration and mottle. It is not solved only by wiping the surface.

  In addition, the ultraviolet ray curable self-healing materials described in Patent Documents 3 and 4 have poor self-healing properties, and a material that satisfies both characteristics has not yet been obtained.

  Therefore, an object of the present invention is to provide a laminated film having a self-healing layer excellent in self-healing property and stain resistance.

  The above object of the present invention has been basically achieved by the following invention. That is, the present invention is as follows.

At least one side of the base film has an A layer,
When the oleic acid is applied to the surface of the A layer and held at 60 ° C. for 1 hour, the mass increase rate of the A layer is 10% by mass or less,
The maximum displacement in the thickness direction of the A layer is 1.0 to 3.0 μm and the creep displacement in the thickness direction of the A layer is 0.05 to 0 when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement. A laminated film having a residual displacement in the thickness direction of the A layer of 0.2 to 0.65 μm when the load is 0 mN.

  The laminated film of the present invention has a surface flaw repair function (self-healing property) and has excellent stain resistance. Therefore, the laminated film of the present invention is particularly useful when a film that is easily damaged by a surface is used as a base film.

The load-indentation depth diagram when the indentation load / unloading test is performed on the laminated film of the present invention using a triangular pyramid indenter (berkovich type).

Hereinafter, the present invention will be described in more detail.

"Base film"
In the present invention, the resin constituting the base film may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, or may be a copolymer or a blend of two or more. More preferably, the resin constituting the base film is a thermoplastic resin because of good moldability.

  Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyester resins, polycarbonate resins, and polyarylate resins. Fluorine resins such as polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene-6 fluoropropylene copolymer, vinylidene fluoride resin, acrylic Resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. In particular, the thermoplastic resin is more preferably a polyester resin from the viewpoint of strength, heat resistance, and transparency.

  The polyester resin in the present invention is a general term for polymers having an ester bond as a main bond chain of the main chain, and is obtained by polycondensation of an acid component and its ester and a diol component. Specific examples include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and the like. These may be copolymerized with other dicarboxylic acids and their esters or diol components as acid components or diol components. Among these polyester resins, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable in terms of transparency, dimensional stability, heat resistance and the like.

  In addition, various additives such as an antioxidant, an antistatic agent, a crystal nucleating agent, an inorganic particle, an organic particle, a thinning agent, a heat stabilizer, a lubricant, an infrared absorber, an ultraviolet absorber, A dopant for adjusting the refractive index may be contained.

The base film may be either a single layer base film or a laminated base film.

"Polyester base film"
In this invention, when resin which comprises a base film contains 50 mass% or more and 100 mass% or less of polyester resins in 100 mass% of all the components of a base film, this base film is called polyester base film.

  In the present invention, the polyester resin constituting the polyester base film has an intrinsic viscosity of the polyester to be used (measured in o-chlorophenol at 25 ° C. according to JIS K7367 (2000)) of 0.4 to 1.2 dl / g. 0.5 to 0.8 dl / g is particularly preferable.

  The polyester base film can be any of an unstretched (unoriented) film, a uniaxially stretched (uniaxially oriented) film, and a biaxially stretched (biaxially oriented) film, but is biaxially stretched with excellent dimensional stability and heat resistance. It is preferable to use a film. The biaxially stretched film is preferably highly crystallized. In the present invention, the biaxial orientation refers to a material that exhibits a biaxial orientation pattern by wide-angle X-ray diffraction.

  The polyester base film may be a polyester film having fine cavities inside.

  The polyester base film may have a single layer structure or a laminated structure.

When the polyester base film has a laminated structure, different polyester resins, preferably a layer containing 50% by mass to 100% by mass of polyester resin C and a layer containing 50% by mass to 100% by mass of polyester resin D are laminated. Let In the present invention, when the polyester base film has a laminated structure, the different polyester resin means a polyester resin having a different molecular structure or a case where some components of the copolymer polyester resin are different.

"Laminated film with layer A"
Hereinafter, a laminated film having an A layer on at least one side of the base film will be described.
The laminated film of the present invention has an A layer on at least one side of the base film, and the mass increase rate of the A layer is 10% by mass when oleic acid is applied to the surface of the A layer and held at 60 ° C. for 1 hour. The maximum displacement amount in the thickness direction of the A layer is 1.0 to 3.0 μm and the creep displacement amount in the thickness direction of the A layer is 0 when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement. This is a laminated film having a residual displacement in the thickness direction of the A layer of 0.2 to 0.65 μm when the load is 0 mN.

  The laminated film of the present invention has an effect excellent in self-repairability and contamination resistance by having the A layer on at least one side of the base film.

  The A layer can be provided on both sides of the base film, but it depends on the use, but it is preferable that the A layer exists only on one side of the base film in consideration of cost. In many applications, the A layer is only present on one side of the base film, and the laminated film has sufficient self-healing property and stain resistance.

The resin contained in the A layer is not particularly limited, but the A layer preferably contains (1) a (poly) alkylene glycol segment and (2) a resin having a urethane bond. The resin contained in the A layer has (1) (poly) alkylene glycol segment and (2) urethane bond, and the A layer has (1) (poly) alkylene glycol segment and (2) urethane bond. In addition, the A layer may contain a plurality of resins (1) a resin having a (poly) alkylene glycol segment and (2) a resin having a urethane bond. Hereinafter, the components contained in the A layer will be described.

"(Poly) alkylene glycol segment"
In the present invention, the A layer preferably has (1) (poly) alkylene glycol segments. When the A layer has the (poly) alkylene glycol segment, self-healing property can be imparted to the A layer.

  In the present invention, the (poly) alkylene glycol segment refers to a segment represented by the following chemical formula 1.

However, n is an integer of 2-4, m is an integer of 2-11.

  Alkylene glycol is a glycol having 2 to 4 carbon atoms. Furthermore, the repeating unit number m of alkylene glycol is 2-11, Preferably it is 3-6. When the number of carbons n of the alkylene glycol exceeds 4, or when the number of repeating units m of the alkylene glycol exceeds 11, the molecular chain of the alkylene glycol becomes longer, the crosslink density of the cured product becomes lower, and its hardness becomes lower. As a result, the coating strength, scratch resistance, etc. are reduced. On the other hand, when the number of repeating units m of the alkylene glycol is less than 2, the molecular chain of the alkylene glycol is shortened, the crosslink density of the cured product is increased, and the cured product loses its flexibility. And workability is reduced.

  In addition, A layer can have a (poly) alkylene glycol segment by forming A layer using the composition containing resin containing a (poly) alkylene glycol segment.

  The resin containing a (poly) alkylene glycol segment preferably has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the end of the resin containing the (poly) alkylene glycol segment.

  When the A layer contains a resin having a (poly) alkylene glycol segment, the A layer can have self-healing properties. That is, even if the surface of the A layer is scratched, the scratch can be eliminated (self-repaired) in a short time of several seconds.

  The resin having a (poly) alkylene glycol segment is preferably a (poly) alkylene glycol (meth) acrylate having an acrylate group at the end in order to impart elasticity. The number of acrylate functional groups (or methacrylate functional groups) of the (poly) alkylene glycol (meth) acrylate is not limited, but is most preferably monofunctional from the viewpoint of self-healing properties of the cured product.

  Examples of the (poly) alkylene glycol (meth) acrylate contained in the composition used for forming the A layer include (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate, and (poly) Examples include butylene glycol (meth) acrylate. The general formula of (poly) ethylene glycol (meth) acrylate is represented by chemical formula 2, the general formula of (poly) propylene glycol (meth) acrylate is represented by chemical formula 3, and the general formula of (poly) butylene glycol (meth) acrylate is represented by chemical formula 4. Each is represented.

  Among these polyalkylene glycol (meth) acrylates, (poly) ethylene glycol (meth) acrylate, which is ethylene glycol having 2 carbon atoms of alkylene glycol, is particularly preferable. (Poly) ethylene glycol (meth) acrylate has the smallest carbon number n in Chemical Formula 1, so that a cured product obtained from the composition used to form the A layer containing (poly) ethylene glycol (meth) acrylate ( A layer) can contribute to coexistence of cosmetic resistance and scratch resistance.

  In the present invention, the resin having the (poly) alkylene glycol segment in the A layer may contain (or copolymerize) other segments and monomers in addition to the (poly) alkylene glycol segment. For example, a polydimethylsiloxane segment or a (poly) siloxane segment may be contained (or copolymerized).

  In this invention, the compound containing the isocyanate group mentioned later and the hydroxyl group of (poly) alkylene glycol (meth) acrylate are reacted, and the A layer becomes (1) ( It can have a poly) alkylene glycol segment and (2) a urethane bond. As a result, the toughness of the A layer can be improved and the self-healing property can be improved.

  In the urethanization reaction between a compound containing an isocyanate group described later and (poly) alkylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate, long-chain alcohol or the like can be blended. By blending hydroxyalkyl (meth) acrylate, the hardness of the A layer, which is a cured product, can be increased. By blending a long-chain alcohol, the surface lubricity of the A layer, which is a cured product, can be increased, and as a result, the scratch resistance can be improved. This long-chain alcohol is a compound included in the concept of the long-chain alkyl group-containing compound.

  As hydroxyalkyl (meth) acrylate compounded at the same time during the urethanization reaction between the compound containing an isocyanate group and (poly) alkylene glycol (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Examples thereof include hydroxybutyl (meth) acrylate.

  Long-chain alcohols to be blended at the same time during the urethanization reaction between the isocyanate group-containing compound and (poly) alkylene glycol (meth) acrylate include tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene mono Examples include stearate, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and glycerol monostearate. Particularly preferred long-chain alcohols include polyether-modified long-chain alcohols such as polyether-modified cetyl alcohol. This is because the use of a long-chain alcohol modified with a polyether can impart an antistatic effect to the A layer that is a cured product.

  The urethanization reaction between a compound containing an isocyanate group, which will be described later, and (poly) alkylene glycol (meth) acrylate is carried out in an organic solvent in the presence of a catalyst, a polymerization inhibitor or the like. The reaction temperature in the urethanization reaction is preferably from room temperature to 100 ° C., and the reaction time is preferably from 1 to 10 hours. When the reaction temperature is lower than normal temperature or when the reaction time is shorter than 1 hour, the progress of the reaction is slow, and the yield of the desired urethane (meth) acrylate is likely to decrease. On the other hand, when the reaction temperature exceeds 100 ° C. or when the reaction time is longer than 10 hours, a side reaction tends to occur.

  Examples of the organic solvent used in the urethanation reaction between the isocyanate group-containing compound and (poly) alkylene glycol (meth) acrylate are aromatic hydrocarbon solvents such as toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples include ketone solvents such as cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate. Examples of the catalyst include dibutyltin laurate, dibutyltin diethylhexoate, dibutyltin sulfite and the like. Examples of the polymerization inhibitor include hydroquinone monomethyl ether.

Whether the (poly) alkylene glycol segment is copolymerized or added separately, the (poly) alkylene glycol is used in 100% by mass of the total components of the composition used to form the A layer. When the amount of the segment is 5 to 50% by mass, it is preferable in terms of self-repairing property and contamination resistance. Here, 100% by mass of all the components of the composition does not include a solvent that does not participate in the reaction. The monomer component involved in the reaction is included.

"Urethane bond"
In this invention, it is preferable that resin contained in A layer has (2) urethane bond.

  In this invention, the resin contained in A layer can be made into resin which has a urethane bond by making an isocyanate group and a hydroxyl group react and producing | generating a urethane bond. By reacting an isocyanate group and a hydroxyl group to produce a urethane bond, the toughness of the A layer can be improved and the elastic recovery property (self-recovering property) can be improved.

  In addition, when a resin containing a polysiloxane segment or a resin containing a polydimethylsiloxane segment has a hydroxyl group, it is possible to generate a urethane bond between the resin and the compound containing an isocyanate group by heat or the like. It is. When the A layer is formed using a compound containing an isocyanate group, a resin containing a (poly) siloxane segment having a hydroxyl group, or a resin containing a polydimethylsiloxane segment having a hydroxyl group, the toughness and elastic recovery of the A layer (Self-repairing property) and surface slipperiness can be improved, which is preferable.

  In the present invention, the compound containing an isocyanate group refers to a resin containing an isocyanate group, and a monomer or oligomer containing an isocyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and tolylene diisocyanate. Polyisocyanates such as isocyanurate bodies, isocyanurate bodies of hexamethylene diisocyanate, burette bodies of hexamethylene isocyanate, and block bodies of the above isocyanates can be mentioned.

  As the compound containing an isocyanate group in the composition used for forming the A layer, it is possible to use an aliphatic isocyanate as compared with an alicyclic or aromatic isocyanate, and the self-healing property of the obtained A layer is improved. It is preferable because it can be increased. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. The isocyanate group-containing compound is particularly preferably an isocyanate having an isocyanurate ring from the viewpoint of heat resistance, and most preferably an isocyanurate of hexamethylene diisocyanate. By using an isocyanate having an isocyanurate ring, an A layer having both self-healing properties and heat resistance can be formed.

In the composition used to form the A layer, melamine crosslinking agents such as alkoxymethylol melamine, acid anhydride crosslinking agents such as 3-methyl-hexahydrophthalic anhydride, amine crosslinking agents such as diethylaminopropylamine, etc. Other crosslinkers can also be included. If necessary, a crosslinking catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be used to promote the urethane bond formation reaction.

"(Poly) caprolactone segment"
In this invention, it is preferable that resin contained in A layer has (3) (poly) caprolactone segment. Since the resin contained in the A layer has a (poly) caprolactone segment, the self-healing property of the A layer can be improved.

  In the present invention, the (poly) caprolactone segment refers to a segment represented by the following chemical formula 5.

  By forming the A layer using a composition containing a resin having a (poly) caprolactone segment, the resin contained in the A layer can have a (poly) caprolactone segment.

  The resin having a (poly) caprolactone segment preferably has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the end of the resin containing the (poly) caprolactone segment.

  As the resin having a (poly) caprolactone segment, (poly) caprolactone having 2 to 3 functional hydroxyl groups is particularly preferable. Specifically, (poly) caprolactone diol,

(Poly) caprolactone triol,

(Poly) caprolactone-modified hydroxyethyl (meth) acrylate

Radical polymerizable caprolactone such as can be used. The radical polymerizability is a property in which crosslinking proceeds by active energy rays, and corresponds to a compound having a (CH2 =) functional group of an acrylate group. Examples of other radical polymerizable caprolactones include (poly) caprolactone-modified hydroxypropyl (meth) acrylate, (poly) caprolactone-modified hydroxybutyl (meth) acrylate, and the like.

  In the present invention, the resin having a (poly) caprolactone segment may have (or copolymerize) other segments and monomers in addition to the (poly) caprolactone segment. For example, a polydimethylsiloxane segment or a (poly) siloxane segment may be included (or copolymerized).

In the present invention, the weight average molecular weight of the (poly) caprolactone segment in the resin having the (poly) caprolactone segment is preferably 500 to 2,500, and more preferably 1,000 to 1, 500. When the weight average molecular weight of the (poly) caprolactone segment is 500 to 2,500, the self-healing effect is further exhibited, and the scratch resistance is further improved.

"(Poly) siloxane segment"
In this invention, it is preferable that resin contained in A layer has (4) (poly) siloxane segment and / or a polydimethylsiloxane segment. In the present invention, the (poly) siloxane segment refers to a segment represented by Chemical Formula 9. In Chemical Formula 9, R ₁ and R ₂ are either OH or an alkyl group having 1 to 8 carbon atoms, and each has at least one or more in the formula.

  In order for the resin contained in the A layer to have a (poly) siloxane segment and / or a polydimethylsiloxane segment, the composition used to form the A layer can include a resin having a (poly) siloxane segment. It becomes.

  In the present invention, a partially hydrolyzed product of a silane compound containing a hydrolyzable silyl group, an organosilica sol, or a composition obtained by adding a hydrolyzable silane compound having a radical polymer to the organosilica sol has a polysiloxane segment. It can be used as a resin.

  Resins having (poly) siloxane segments are tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyl Completely or partially hydrolyzed silane compounds having hydrolyzable silyl groups such as trialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, organosilica sol dispersed in organic solvent, hydrolyzable silyl on the surface of organosilica sol The thing etc. which added the hydrolysis silane compound of group can be illustrated.

  In the present invention, the resin having a (poly) siloxane segment may contain (copolymerize) other segments in addition to the (poly) siloxane segment. For example, a monomer component having a (poly) alkylene glycol segment, a (poly) caprolactone segment, and a polydimethylsiloxane segment may be contained (copolymerized).

  In the present invention, as the resin having a (poly) siloxane segment, a monomer having a hydroxyl group that reacts with an isocyanate group is preferably copolymerized. When a monomer having a hydroxyl group that reacts with an isocyanate group is copolymerized with a resin having a (poly) siloxane segment, the toughness of the resulting A layer is improved.

  When the resin having a (poly) siloxane segment is a copolymer containing a hydroxyl group, a composition comprising a resin having a (poly) siloxane segment containing a hydroxyl group (copolymer) and a compound containing an isocyanate group When the A layer is formed by use, the A layer containing a resin having a (poly) siloxane segment and a urethane bond can be efficiently formed.

Whether the (poly) siloxane segment is copolymerized or added separately, the (poly) siloxane segment is 100% by mass of the total component of the composition used to form the A layer. The content of 1 to 20% by mass is preferable from the viewpoint of the self-healing property, contamination resistance, weather resistance, and heat resistance of the obtained A layer. 100% by mass of the total components of the composition does not include a solvent that does not participate in the reaction. The monomer component involved in the reaction is included.

"Polydimethylsiloxane segment"
In the present invention, the polydimethylsiloxane segment refers to a segment represented by Chemical Formula 10.

  If the resin contained in the A layer has a polydimethylsiloxane segment, the polydimethylsiloxane segment is coordinated to the surface of the A layer. When the polydimethylsiloxane segment is coordinated on the surface of the A layer, the lubricity of the surface of the A layer is improved, and the frictional resistance can be reduced. As a result, scratchability can be suppressed.

  In order for the resin contained in the A layer to have a (poly) siloxane segment and / or a polydimethylsiloxane segment, the composition used to form the A layer can include a resin having a polydimethylsiloxane segment. It is. In the present invention, as the resin having a polydimethylsiloxane segment, it is preferable to use a copolymer obtained by copolymerizing a vinyl monomer with a polydimethylsiloxane segment.

  For the purpose of improving the toughness of the A layer, the resin having a polydimethylsiloxane segment is preferably copolymerized with a monomer having a hydroxyl group that reacts with an isocyanate group. In the case where the resin having a polydimethylsiloxane segment is a copolymer having a hydroxyl group, a layer A using a composition comprising a resin having a hydroxyl group-containing polydimethylsiloxane segment (copolymer) and a compound containing an isocyanate group When A is formed, the A layer having a polydimethylsiloxane segment and a urethane bond can be efficiently formed.

  When the resin having a polydimethylsiloxane segment is a copolymer with a vinyl monomer, it may be any of a block copolymer, a graft copolymer, and a random copolymer. When the resin having a polydimethylsiloxane segment is a copolymer with a vinyl monomer, this is referred to as a polydimethylsiloxane copolymer. Polydimethylsiloxane copolymers can be produced by the living polymerization method, polymer initiator method, polymer chain transfer method, etc., but considering the productivity, the polymer initiator method, polymer chain transfer method can be used. It is preferable to use it.

  When the polymer initiator method is used, it can be copolymerized with other vinyl monomers using a polymer azo radical polymerization initiator represented by Chemical Formula 11. In addition, a two-stage polymerization is carried out by synthesizing a prepolymer in which a peroxide group is introduced into the side chain by copolymerizing a peroxy monomer and polydimethylsiloxane having an unsaturated group at a low temperature, and then copolymerizing the prepolymer with a vinyl monomer. Can also be done.

When the polymer chain transfer method is used, for example, HS-CH ₂ COOH or HS-CH ₂ CH ₂ COOH is added to the silicone oil represented by Chemical Formula 12 to form a compound having an SH group, and then the SH group A block copolymer can be synthesized by copolymerizing the silicone compound and vinyl monomer using chain transfer.

  In order to synthesize a polydimethylsiloxane-based graft copolymer, for example, a graft copolymer can be easily obtained by copolymerizing a compound represented by Chemical Formula 13, that is, a methacrylic ester of polydimethylsiloxane and a vinyl monomer. .

  Examples of vinyl monomers used in the copolymer with polydimethylsiloxane include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n -Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride , Vinyl fluoride, vinylidene fluoride, glycidyl acrylate Glycidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminoethyl Examples thereof include methacrylate, N, N-diethylaminoethyl methacrylate, diaceton acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and allyl alcohol.

  Polydimethylsiloxane copolymers include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ethanol, isopropyl alcohol, etc. It is preferable that the alcoholic solvent is produced by a solution polymerization method alone or in a mixed solvent.

  If necessary, a polymerization initiator such as benzoyl peroxide or azobisisobutylnitrile is used in combination. The polymerization reaction is preferably performed at 50 to 150 ° C. for 3 to 12 hours.

  The amount of the polydimethylsiloxane segment in the polydimethylsiloxane copolymer in the present invention is 1 to 30 in 100% by mass of all components of the polydimethylsiloxane copolymer in terms of the lubricity and stain resistance of the A layer. It is preferable that it is mass%. The weight average molecular weight of the polydimethylsiloxane segment is preferably 1,000 to 30,000.

  Whether the polydimethylsiloxane segment is copolymerized or added separately, the dimethylsiloxane segment is 1 to 20 in 100% by mass of the total components of the composition used to form the A layer. When the content is% by mass, it is preferable in terms of self-repairing property, contamination resistance, weather resistance, and heat resistance. 100% by mass of the total components of the composition does not include a solvent that does not participate in the reaction. The monomer component involved in the reaction is included.

  In the present invention, when a resin having a polydimethylsiloxane segment is used as the composition used for forming the A layer, other segments may be included (copolymerized) in addition to the polydimethylsiloxane segment. good. For example, (poly) alkylene glycol segment, (poly) caprolactone segment, and (poly) siloxane segment may be present (copolymerized).

  The composition used to form the A layer includes a copolymer of (poly) alkylene glycol segment and polydimethylsiloxane segment, a copolymer of (poly) alkylene glycol segment and (poly) siloxane segment, (poly) Copolymer of alkylene glycol segment, polydimethylsiloxane segment and (poly) siloxane segment, copolymer of (poly) caprolactone segment and polydimethylsiloxane segment, copolymer of (poly) caprolactone segment and (poly) siloxane segment It is possible to use a polymer, a copolymer of a (poly) caprolactone segment, a polydimethylsiloxane segment, and a (poly) siloxane segment. The A layer obtained using such a composition can contain a resin having a (poly) alkylene glycol segment or a (poly) caprolactone segment, a polydimethylsiloxane segment, and / or a (poly) siloxane segment.

A polydimethylsiloxane copolymer in a composition used to form an A layer comprising a resin having a (poly) alkylene glycol segment or a (poly) caprolactone segment, a (poly) siloxane segment and a polydimethylsiloxane segment; In the reaction of (poly) alkylene glycol or (poly) caprolactone and (poly) siloxane, (poly) alkylene glycol segment or (poly) caprolactone segment and polysiloxane segment are appropriately added during the synthesis of the polydimethylsiloxane copolymer. Can be copolymerized.

"Other additives"
The composition used for forming the A layer preferably contains an initiator, a curing agent, and a catalyst. Initiators and catalysts are used to promote curing of the A layer. As the initiator, those capable of initiating or accelerating polymerization, condensation or cross-linking reaction of the coating composition by anion, cation, radical reaction or the like are preferable.

  Various initiators, curing agents and catalysts can be used. In addition, the initiator, the curing agent, and the catalyst may be used alone, or a plurality of initiators, curing agents, and catalysts may be used at the same time. Furthermore, you may use together an acidic catalyst, a thermal-polymerization initiator, and a photoinitiator. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, amine compounds, and the like. As the photopolymerization initiator, an alkylphenone compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone type compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2.2-dimethoxy-1.2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropane-1-o 1- [4- (2-ethoxy) - phenyl] -2-hydroxy-2-methyl-1-like.

Further, a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, etc. may be added to the composition used for forming the A layer as long as the effect of the present invention is not impaired. Thereby, A layer can contain a leveling agent, a ultraviolet absorber, a lubricant, an antistatic agent, etc. Examples of the leveling agent include an acrylic copolymer or a silicone-based or fluorine-based leveling agent. Specific examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, oxalic anilide-based, triazine-based and hindered amine-based ultraviolet absorbers. Examples of the antistatic agent include metal salts such as lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt and calcium salt.

“Performance of layer A”
In the laminated film of the present invention, it is important that the mass increase rate of the A layer is 10.0% by mass or less when oleic acid is applied to the surface of the A layer and held at 60 ° C. for 1 hour.

  In particular, the mass increase rate of the A layer under the above-described conditions is more preferably 0.3% by mass or more and 5.0% by mass or less, and further preferably 0.3% by mass or more and 3.0% by mass or less. When the rate of mass increase due to oleic acid in the A layer is 10.0% by mass or less, the contamination resistance is good, and when it is 3.0% by mass or less, problems due to the contamination hardly occur. The lower the rate of increase in mass due to oleic acid in layer A, the better, but if the resin contained in layer A has a (poly) alkylene glycol segment, the rate of increase in mass due to oleic acid should be less than 0.3% by mass. Therefore, the lower limit is considered to be about 0.3% by mass. Contamination resistance refers to the resistance to discoloration of the surface and the occurrence of mottled spots when in contact with creams, oil-based magic, and PVC sheets.

In order to control the mass increase rate of the A layer to 10.0% by mass or less when oleic acid is applied to the surface of the A layer and kept at 60 ° C. for 1 hour, the A layer is (1) (poly) alkylene glycol. It is possible to use a segment and (2) a layer containing a resin having a urethane bond.

The laminated film of the present invention has a maximum displacement amount of 1.0 to 3.0 μm in the thickness direction of the A layer when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement, and the thickness direction of the A layer is It is important that the creep displacement amount is 0.05 to 0.5 μm, and the residual displacement amount in the thickness direction of the A layer is 0.2 to 0.65 μm when the load is 0 mN.

  The maximum displacement in the thickness direction of the A layer is more preferably 1.0 to 1.7 μm. If the maximum displacement amount in the thickness direction of the A layer is larger than 3.0, the self-healing of the A layer is incomplete, and if the maximum displacement amount in the thickness direction of the A layer is smaller than 1.0, Visibility deteriorates. Further, if the creep displacement amount in the thickness direction of the A layer is in the range of 0.05 to 0.3 μm, self-repair occurs instantaneously, which is important. When the creep displacement amount in the thickness direction of the A layer is in the range of 0.05 to 0.5 μm, the visibility of self-healing of the A layer is high, which is preferable in terms of design. Moreover, it is more preferable that the residual displacement in the thickness direction of the A layer is 0.4 to 0.6 μm. If the residual displacement amount in the thickness direction of the A layer is larger than 0.65 μm, visible scratches remain even after the self-repair of the A layer, and the appearance is deteriorated. From the viewpoint of the self-healing property of the A layer, the smaller the residual displacement, the better. However, since the self-healing material generally undergoes plastic deformation, the lower limit of the residual displacement is considered to be about 0.2 μm.

  The maximum displacement amount in the thickness direction of the A layer is 1.0 to 3.0 μm, the creep displacement amount in the thickness direction of the A layer is 0.05 to 0.5 μm, and the remaining displacement amount in the thickness direction of the A layer is By being 0.2 to 0.65 μm, excellent self-repairing properties are exhibited.

  In the laminated film of the present invention, the mass increase rate of the A layer is 10% by mass or less when oleic acid is applied to the surface of the A layer and held at 60 ° C. for 1 hour, and a 0.5 mN load is applied in the microhardness meter measurement. When applied for 10 seconds, the maximum displacement in the thickness direction of the A layer is 1.0 to 3.0 μm, the creep displacement in the thickness direction of the A layer is 0.05 to 0.5 μm, and the load is 0 mN. When the amount of residual displacement in the thickness direction of the A layer is 0.2 to 0.65 μm, both cosmetic resistance and self-repairing properties are achieved.

In addition, when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement, the maximum displacement amount in the thickness direction of the A layer is 1.0 to 3.0 μm, and the creep displacement amount in the thickness direction of the A layer is 0.05. In order to set the residual displacement in the thickness direction of the A layer to 0.2 to 0.65 μm when the load is 0 mN, the A layer is composed of (1) (poly) alkylene glycol segments, and ( 2) It is possible to use a layer containing a resin having a urethane bond.

In general, self-healing materials elastically recover minor scratches by the soft segment component contained acting as a cushion, so increasing the soft segment component can improve self-healing properties. It becomes possible. Specifically, by increasing the (1) (poly) alkylene glycol segment and (3) (poly) caprolactone segment in the A layer, the maximum displacement, creep displacement, and remaining displacement in microhardness meter measurement are changed. And can achieve excellent self-healing properties.

  However, if a method for improving the self-healing property of the A layer by such an improved method is adopted, the ratio of the free volume of the molecules constituting the A layer increases, so that oils and chemicals are likely to penetrate between the molecules. The cosmetic resistance of the A layer deteriorates. On the other hand, by reducing the (1) (poly) alkylene glycol segment and (3) (poly) caprolactone segment in the A layer, the cosmetic resistance of the A layer is improved, but the self-repairing property is deteriorated. For this reason, since self-restoration and cosmetic resistance are contradictory properties, it is very difficult to achieve both.

In order to achieve both the self-repairing property and the cosmetic resistance property, an A layer containing urethane (meth) acrylate B having excellent self-repairing property and urethane (meth) acrylate C having excellent cosmetic resistance is formed. Therefore, it is important that the composition used for this purpose is cured with active energy rays such as ultraviolet rays and electron beams.

"Urethane (meth) acrylate B"
Urethane (meth) acrylate B with excellent self-healing properties is a layer obtained by curing a mixture of urethane (meth) acrylate B and a photoinitiator to a thickness of 30 μm with ultraviolet light from a high-pressure mercury lamp with an illuminance of 400 mW / cm ² (hereinafter referred to as “urethane (meth) acrylate B”). , Means a urethane (meth) acrylate having a physical property of the following range.

  When the oleic acid is applied to the surface of the B layer and held at 60 ° C. for 1 hour, the mass increase rate of the B layer is 45% by mass or less, and a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement. The maximum displacement amount in the thickness direction of the B layer is 1.0 to 3.0 μm, and the creep displacement amount in the thickness direction of the B layer is 0.4 to 0.7 μm.

When the oleic acid is applied to the surface of the B layer and held at 60 ° C. for 1 hour, the mass increase rate of the B layer is 45% by mass or less, and a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement. In order to form a B layer in which the maximum displacement in the thickness direction of the B layer is 1.0 to 3.0 μm and the creep displacement in the thickness direction of the B layer is 0.4 to 0.7 μm, the B layer is formed. It is preferable that the urethane (meth) acrylate B in the composition used for the purpose has at least (2) a urethane bond.

"Urethane (meth) acrylate C"
Urethane (meth) acrylate C with excellent cosmetic resistance is a layer obtained by curing a mixture of urethane (meth) acrylate C and a photoinitiator to a thickness of 30 μm with ultraviolet light from a high-pressure mercury lamp with an illuminance of 400 mW / cm ² (hereinafter referred to as “urethane (meth) acrylate C”). , C (layer) means urethane (meth) acrylate having the following range.

  When the oleic acid is applied to the surface of the C layer and kept at 60 ° C. for 1 hour, the mass increase rate of the C layer is 5.0% by mass or less, and a 0.5 mN load is applied for 10 seconds in the microhardness measurement. The maximum displacement amount in the thickness direction of the C layer is 0.2 to 3.0 μm, and the creep displacement amount in the thickness direction of the C layer is 0.02 to 0.35 μm.

When oleic acid is applied to the surface of the C layer and held at 60 ° C. for 1 hour, the mass increase rate of the C layer is 5.0% by mass or less, and when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement, In order to form a C layer in which the maximum displacement in the thickness direction of the C layer is 0.2 to 3.0 μm and the creep displacement in the thickness direction of the C layer is 0.02 to 0.35 μm, the C layer is formed. It is preferable that the urethane (meth) acrylate C in the composition to be used has at least (2) a urethane bond.

Further, the content ratio of urethane (meth) acrylate B and urethane (meth) acrylate C in the composition used to form the A layer (mass of urethane (meth) acrylate B / mass of urethane (meth) acrylate C) When the composition used for forming the A layer is cured within the range of 70/30 to 30/70, oleic acid is applied to the surface of the obtained A layer and held at 60 ° C. for 1 hour. The mass increase rate of the A layer is 10.0% by mass or less, and the maximum displacement in the thickness direction of the A layer is 1.0 to 3.0 μm when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement. A laminated film in which the creep displacement amount in the thickness direction of the A layer is 0.05 to 0.5 μm and the residual displacement amount in the thickness direction of the A layer is 0.2 to 0.65 μm when the load is 0 mN. Get Bets can be, it is possible to achieve both anti-makeup resistance and self-healing. In the composition used to form the A layer, the content ratio of urethane (meth) acrylate B and urethane (meth) acrylate C (mass of urethane (meth) acrylate B / mass of urethane (meth) acrylate C) is If it deviates from 70/30 to 30/70, it becomes difficult to achieve both self-repairing properties and cosmetic resistance properties.

  Here, the urethane (meth) acrylate B and the urethane (meth) acrylate C are not particularly limited as long as the urethane (meth) acrylate has a (poly) alkylene glycol segment or a (poly) caprolactone segment in one of them.

  Further, when the oleic acid is applied to the surface of the A layer and held at 60 ° C. for 1 hour, the mass increase rate of the A layer is 3.0% by weight or less, and a 0.5 mN load is applied for 10 seconds in the microhardness measurement. The maximum displacement amount in the thickness direction of the A layer is 1.0 to 1.7 μm, the creep displacement amount in the thickness direction of the A layer is 0.3 to 0.5 μm, and the residual displacement in the thickness direction of the A layer In order to make the amount 0.4 to 0.6 μm, the urethane (meth) acrylate B in the composition used for forming the A layer has at least a (poly) caprolactone segment, and urethane (meta) It is preferred that acrylate C has at least a (poly) alkylene glycol segment. Moreover, it can achieve by making the physical property of B layer and C layer into the following range.

  (Physical properties of layer B) When the oleic acid is applied to the surface of layer B and kept at 60 ° C. for 1 hour, the rate of mass increase of layer B is 5.0% by mass or less, and a 0.5 mN load is 10 in the microhardness meter measurement. The maximum displacement in the thickness direction of the B layer when applied for 1 second is 1.0 to 3.0 μm, and the creep displacement in the thickness direction of the B layer is 0.4 to 0.5 μm.

  When the oleic acid is applied to the surface of the B layer and held at 60 ° C. for 1 hour, the mass increase rate of the B layer is 5.0% by mass or less, and when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement, In order to form the B layer in which the maximum displacement amount in the thickness direction of the B layer is 1.0 to 3.0 μm and the creep displacement amount in the thickness direction of the B layer is 0.4 to 0.5 μm, It is important that the urethane (meth) acrylate B in the composition used to form has at least (3) (poly) caprolactone segments and (2) urethane bonds.

  (Physical properties of the C layer) When the oleic acid is applied to the surface of the C layer and kept at 60 ° C. for 1 hour, the mass increase rate of the C layer is 3.0% by mass or less, and a 0.5 mN load is 10 in the microhardness meter measurement. The maximum displacement amount in the thickness direction of the C layer when applied for 2 seconds is 0.8 to 3.0 μm, and the creep displacement amount in the thickness direction of the C layer is 0.05 to 0.35 μm.

When oleic acid is applied to the surface of the C layer and kept at 60 ° C. for 1 hour, the mass increase rate of the C layer is 3.0% by mass or less, and when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement, In order to form a C layer in which the maximum displacement in the thickness direction of the C layer is 0.8 to 3.0 μm and the creep displacement in the thickness direction of the C layer is 0.05 to 0.35 μm, the C layer is formed. It is important that the urethane (meth) acrylate C in the composition to be used has at least (1) (poly) alkylene glycol segment and (2) urethane bond.

Furthermore, A layer obtained by hardening the composition used in order to form A layer which mixed the content ratio of urethane (meth) acrylate B and urethane (meth) acrylate C as 70 / 30-30-70. When the surface layer is coated with oleic acid and kept at 60 ° C. for 1 hour, the mass increase rate of the A layer is 3.0% by weight or less, and when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement, The maximum displacement in the thickness direction of the A layer is 1.0 to 1.7 μm, the creep displacement in the thickness direction of the A layer is 0.3 to 0.5 μm, and the thickness of the A layer when the load is 0 mN. A laminated film having a residual displacement in the direction of 0.4 to 0.6 μm can be obtained, and is excellent in cosmetic resistance and self-repairing properties.

  The composition used to form layer A contains urethane (meth) acrylate B and urethane (meth) acrylate C, the urethane (meth) acrylate B has a (poly) caprolactone segment, and the urethane (meth) acrylate When C has a (poly) alkylene glycol (meth) segment, an A layer superior in self-restoring property and cosmetic resistance can be obtained. This is because the (poly) alkylene glycol segment with excellent cosmetic resistance is unevenly distributed on the surface due to the difference between surface tension and intermolecular force, and the (poly) caprolactone segment with excellent self-healing properties is unevenly distributed in the inner layer. Is considered to be more prominent.

In particular, the mass m of the (1) (poly) alkylene glycol segment in the resin contained in the A layer and the mass n of the (3) (poly) caprolactone segment in the resin contained in the A layer are 0.3 n ≦ m ≦ 10n is preferably satisfied, 0.3n ≦ m ≦ 5n is more preferable, and 0.65n ≦ m ≦ 1.20n is more preferable. The mass m of the (1) (poly) alkylene glycol segment in the resin contained in the A layer and the mass n of the (3) (poly) caprolactone segment in the resin contained in the A layer satisfy 0.3n ≦ m ≦ 10n. When satisfied, the uneven distribution of each segment during the above-mentioned curing occurs more remarkably, and it is possible to obtain a layer A having further excellent self-repairing properties and cosmetic resistance. The mass m of the (1) (poly) alkylene glycol segment in the resin contained in the A layer and the mass n of the (3) (poly) caprolactone segment in the resin contained in the A layer satisfy 0.3n ≦ m ≦ 10n. When not satisfy | filling, the dispersibility of each segment at the time of the above-mentioned hardening will go up, and uneven distribution will become weak.

(A layer thickness)
In the laminated film of the present invention, the thickness of the A layer is preferably 10 to 30 μm in order to obtain a laminated film with good self-restoring property and cosmetic resistance. By setting the thickness of the A layer to 10 to 30 μm, a laminated film having a self-healing effect and having good cosmetic resistance can be obtained. More preferably, by setting the thickness of the A layer to 10 to 20 μm, the mass increase rate of the A layer when oleic acid is applied to the surface of the A layer is reduced, and cosmetic resistance is improved.

(Dynamic friction coefficient of layer A)
In the laminated film of the present invention, the dynamic friction coefficient (μk) of the A layer is preferably 0.10 to 0.45, and more preferably 0.10 to 0.30. When the coefficient of dynamic friction (μk) is 0.10 to 0.45, the touch feeling when touched is excellent. In addition, when the coefficient of dynamic friction (μk) is 0.10 to 0.30, not only is the touch feeling excellent, but also the resistance to the object is reduced, so that a more excellent scratch resistance is obtained. The dynamic friction coefficient (μk) of the A layer is preferably as low as possible, but the lower limit is considered to be about 0.10.

In order to reduce the dynamic friction coefficient of the A layer to 0.10 to 0.45, the resin having the (poly) siloxane segment and the resin having the polydimethylsiloxane segment in the A layer constitute the A layer. It is preferable that it is 1-5 mass% in 100 mass% of all the components.

(Break elongation and particles of layer A)
The breaking elongation of the A layer of the laminated film of the present invention is preferably 30 to 80%, and more preferably 50 to 80%. When the breaking elongation of the A layer is 30 to 80%, the molding followability is excellent, so that it can be used for decorative molding. The higher the breaking elongation of the A layer, the better the mold following ability. However, when the breaking elongation of the A layer is higher than 80%, the resin constituting the A layer has high flexibility and maintains cosmetic resistance. It becomes difficult.

  In order to set the breaking elongation of the A layer to 30 to 80%, the A layer preferably contains particles. When the A layer contains particles, when the A layer is stretched, fine breaks (cavities) that cannot be seen from the particle are generated. Due to this fine break (cavity), the A layer is flexible, and the elongation at break is better than when no particles are contained. As the extension of the A layer is further continued, the above-described fine breakage (cavity) is eventually connected, and finally the A layer becomes a visible breakage. The particles contained in the A layer preferably have an average particle size of 0.3 μm or less. If the average particle size of the particles contained in the A layer is larger than 0.3 μm, the transparency of the A layer is impaired, which is not preferable. Moreover, it is preferable that content of particle | grains is 0.05-2 mass% in all the components 100 mass% of the composition used in order to form A layer. Here, 100% by mass of all the components of the composition used for forming the A layer does not include a solvent that does not participate in the reaction, but includes a monomer component that participates in the reaction. If the content of the particles in the composition used to form the A layer is less than 0.05% by mass, secondary aggregation tends to occur, and if it exceeds 2% by mass, the surface of the A layer becomes rough and the transparency is lost. This is not preferable.

Particles contained in layer A are silica particles such as dry silica and wet silica, metals such as titanium oxide, zirconium oxide, zinc oxide, tin oxide, cerium oxide, antimony oxide, indium tin mixed oxide and antimony tin mixed oxide. Examples thereof include organic particles such as oxide particles, acrylic and styrene, and various commercial products using an organic solvent as a dispersion medium can also be used. The shape of the particles is preferably spherical or beaded, but is not particularly limited thereto. In particular, it is preferable to employ silica particles because the obtained laminated film has low transparency and good dispersibility when mixed in a coating agent.

“Method of forming layer A”
The layer A of the laminated film of the present invention can be produced, for example, through a laminating step, a heating step, and an energy ray irradiation step described later in this order.

(Lamination process)
As for the lamination of the A layer on the base film, for example, a method of applying the composition used for forming the A layer to at least one side of the base film can be mentioned. As the coating method, a known coating method such as a gravure coating method, a micro gravure coating method, a die coating method, a reverse coating method, a knife coating method, or a bar coating method can be applied.

(Heating process)
The solvent in the layer can be volatilized by heating. The heating method in the heating step is preferably performed with hot air from the viewpoint of heating efficiency, and a known hot air dryer or a hot air furnace capable of continuous conveyance such as roll conveyance or floating can be applied. The heating temperature in the heating step is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, whereby the solvent is sufficiently volatilized. Further, considering the generation of wrinkles due to heat shrinkage of the base film, the heating temperature is preferably 180 ° C. or lower, but in order to improve the adhesion to the base film, the heating is performed at a temperature of 120 ° C. or higher. It is preferable.

  The heating time is 1 minute or longer, preferably 2 minutes or longer, more preferably 3 minutes or longer. From the viewpoint of maintaining productivity, dimensional stability of the base film, and transparency, the heating time is desirably 5 minutes or less.

(Energy beam irradiation process)
By irradiating the energy beam, the composition used for forming the A layer can be cured. Curing with energy rays is preferably electron beams (EB rays) or ultraviolet rays (UV rays) from the viewpoint of versatility. Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. Case of UV cured using a high pressure mercury lamp is a discharge lamp type, illuminance of ultraviolet rays is 100 mW / cm ² or more 3,000 mW / cm ² or less. In order to achieve both self-healing property and contamination resistance, the illuminance of ultraviolet rays is preferably 200 mW / cm ² or more and 1,000 mW / cm ² or less. Here, the ultraviolet illuminance is the irradiation intensity received per unit area, and varies depending on the lamp output, the emission spectrum efficiency, the diameter of the light emitting bulb, the design of the reflecting mirror, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

Preferred uses of the laminated film of the present invention are decorative molding applications applied to housings such as personal computers and mobile phones, and screen protection applications such as touch panels and antireflection plates. The laminated film of the present invention can be formed into a molded body by applying a molding method such as injection molding, pressure molding, vacuum molding, thermoforming, press molding or the like. Especially, it can apply especially suitably for the use heated at 80 to 180 degreeC at the time of shaping | molding.

[Characteristic measurement method and effect evaluation method]
The characteristic measurement method and effect evaluation method in the present invention are as follows.

(1) Thickness of A layer The cross section of a laminated film is obtained by freezing and cutting with a diamond knife of a microtome (manufactured by Nippon Microtome, RMS-50). The obtained cross section was expanded to a range of magnification of 100 to 300 times with an optical microscope, and the layer thickness of the A layer was measured from an image photograph in which a clear interface between the base film and the A layer was seen. In addition, the measurement was made into the average value of 3 samples.

(2) The mass increase rate laminated film by the oleic acid of A layer was cut out to 200 mm x 200 mm length, and the mass of this laminated film was set to A. It fixed to the bakelite board and oleic acid was apply | coated to 100 mm x 100 mm length of the A layer side. When applying, a plastic enclosure was made to prevent oleic acid from flowing out. This was stored in an oven heated to 60 ° C. for 1 hour. After storage, the laminate film was wiped off using a Hize gauze until it became transparent, and stored under an atmosphere of 23 ° C. for 24 hours. The mass of the film measured after this was set to B. The mass increase rate by oleic acid at this time was calculated | required from the following formulas. Each measurement was performed three times, and the average value was adopted.
(BA) / (100 × t × d) × 100
t: Layer A thickness (cm)
d: Specific gravity of layer A (g / cm ³ )
(3) A slice of layer A was cut out of the layer A specific gravity laminated film with a single-edged knife and measured according to a density gradient tube method (JISK7112 JIS handbook (1999 edition)) using a sodium bromide aqueous solution as a medium. At this time, the measurement was performed with n number 5, and the average value was adopted.

(4) Apply 1g of “High Vacuum Grease” manufactured by Toray Dow Corning to a smooth metal plate (die steel: SKD-11) with maximum displacement, creep displacement, and residual displacement in the thickness direction of layer A Then, the base film side of the laminated film was affixed to the coated portion, and the filter paper was sandwiched between the surfaces and pressed with a hand press machine so that air was not bitten. An indentation load / unloading test was performed on a static sample obtained by such a method using a triangular pyramid indenter (berkovich type), and a weight-indentation depth diagram (see FIG. 1) was obtained. .

From this diagram, the amount of displacement in the thickness direction (maximum displacement amount) from when a 0.5 mN load is applied for 10 seconds to when it is unloaded, and the thickness direction when holding for 10 seconds after reaching 0.5 mN. A displacement amount (creep displacement amount) and a displacement amount in the thickness direction (residual displacement amount) when the load was 0 mN after being held for 10 seconds were obtained. Each measurement was performed three times, and the average value was adopted.
Apparatus: Dynamic ultra micro hardness tester “DUH-201” (manufactured by Shimadzu Corporation)
Working indenter: Diamond triangular pyramid indenter (berkovich type, 115 ° ridge angle)
Measurement mode: 2
Maximum load: 0.5mN
Holding time when 10 mN load is reached: 10 second load speed, unload speed: 0.1422 mN / sec
(5) Applying 0.5 g of Katrix Co., Ltd. ATRIX “Hand Cream A” (NO413) to a sample cut into a 5 cm square cosmetic resistant product and leaving it in an atmosphere at a temperature of 60 ° C. and a relative humidity of 95% for 6 hours Then, it is left for 30 minutes in an atmosphere of 25 ° C. and 65% relative humidity, and the surface is wiped clean with gauze. After standing for 24 hours in an atmosphere at a temperature of 25 ° C. and a relative humidity of 65%, the surface state was observed and a determination was made according to the following criteria.
○ (excellent): No vitiligo occurred.
● (Good): Almost no vitiligo occurs.
Δ (possible): Vitiligo occurs, but cleans if wiped off.
X (impossible): Vitiligo occurs. Even after wiping, it occurs again after being left for 24 hours in an atmosphere at a temperature of 25 ° C. and a relative humidity of 65%.

(6) Self-healing property of layer A The state of recovery of scratches when the surface of layer A was scratched horizontally with a brass brush (manufactured by TRUSCO) under a load of 500 g was visually determined according to the following criteria.
◎ (excellent): All wounds recover within 3 seconds.
○ (good): All wounds recover within 4 to 10 seconds.
● (possible): All wounds recover within 11 to 30 seconds.
X (Not possible): Others (All wounds take 31 seconds or longer to recover, there are scratches that do not recover, or there are no scratches, etc.)
(7) A dynamic friction coefficient of layer A 23 ° C., 60% (relative humidity) atmosphere, using a hemispherical polyacetal resin touch pen (made of stylus) with a radius of 0.8 mm R at the tip shape, load 200 g, speed 100 mm The dynamic friction coefficient (μk) when the sheet member surface was moved at / sec was measured with a surface property measuring machine (trade name “Tribogear”, type “14FW”) manufactured by Shinto Kagaku Co., Ltd. Each measurement was performed three times, and the average value was adopted.
<Measurement conditions>
・ Measurement length: 100mm
・ Output machine: Automatic detection by computer ・ Load converter capacity: 2000g
・ Sampling speed: 2ms
Coefficient of dynamic friction: Calculated from the average load of the last 20 mm in the measurement length of 100 mm (8) Breaking elongation laminated film of layer A is cut into 10 mm width x 200 mm length, gripped with a chuck in the longitudinal direction and Instron type The sample was stretched at a pulling speed of 100 mm / min with a tensile testing machine (Ultrasonic Material Testing Machine Model 5848 manufactured by Instron). The measurement atmosphere at this time is 23 ° C. and 65 RH%. When the sample is stretched, the sample being stretched is observed, and is stopped when a crack is visually observed (the elongation at the time of stopping is adjusted to be an integer of 5). The samples to be measured from the next were sequentially sampled with the elongation decreased by 5% from the elongation at the time of stopping, and finally the elongation was such that no cracks were visually observed.

  Cut out the thin film cross section of the cracked portion of the sample collected, observe the A layer at a magnification such that the thickness of the observed A layer is 30 mm or more on the observation screen of the transmission electron microscope, and the average thickness of the A layer When cracks of 50% or more have occurred, cracks are present (layer A is broken), and the elongation value of the sample having the lowest elongation among the samples with cracks is defined as the fracture elongation. .

  Then, the same measurement was performed three times in total, and the average value of the breaking elongations was taken as the breaking elongation of the A layer.

(9) About the sample which cut out the cross section of the laminated film using the average particle diameter microtome in A layer, it calculated | required by electron microscope observation. That is, using a transmission electron microscope H-7100FA type (manufactured by Hitachi, Ltd.), the cross section of the film was magnified 20,000 times at an acceleration voltage of 75 kV, a cross-sectional photograph was taken, and the layer configuration and each layer thickness were measured. did. In some cases, in order to obtain high contrast, a staining technique using a known RuO ₄ or OsO ₄ may be used.

"material"
(Raw material 1)
50 parts by mass of toluene, 50 parts by mass of isocyanurate modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Takeda Pharmaceutical Co., Ltd.), 90 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate (Placcel FA2D manufactured by Daicel Chemical Industries, Ltd.) , 0.02 part by mass of dibutyltin laurate and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a urethane acrylate mixture having a solid content of 50% by mass.

(Raw material 2)
50 parts by mass of toluene, biuret-modified type of hexamethylene diisocyanate (Duranate 24A-90CX, manufactured by Asahi Kasei Corporation, nonvolatile content: 90% by mass, isocyanate content: 21.2% by mass), (poly) caprolactone-modified hydroxy 80 parts by mass of ethyl acrylate (Placcel FA5 manufactured by Daicel Chemical Industries, Ltd.), 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 82 parts by mass of toluene was added to obtain urethane acrylate having a solid content of 50% by mass. The number of repeating caprolactone units per acrylate monomer residue in this urethane acrylate is 2.

(Raw material 3)
50 parts by mass of toluene, 25 parts by mass of isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Takeda Pharmaceutical Co., Ltd.), (poly) caprolactone-modified hydroxyethyl acrylate (Placcel FA10 manufactured by Daicel Chemical Industries, Ltd.) 162.8 Part by mass, 0.02 part by mass of dibutyltin laurate and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 137.8 parts of toluene was added to obtain urethane acrylate having a solid content of 50% by mass. In addition, the repeating number of the caprolactone unit per acrylate monomer residue in this urethane acrylate is 10.

(Raw material 4)
50 parts by mass of toluene, 50 parts by mass of isocyanurate modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Takeda Pharmaceutical Co., Ltd.), 114 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate (Placcel FA3 manufactured by Daicel Chemical Industries, Ltd.) Then, 0.02 part by mass of dibutyltin laurate and 0.02 part by mass of hydroquinone monomethyl ether were added and held at 70 ° C. for 3 hours. Thereafter, 118.2 parts by mass of toluene was added to obtain urethane acrylate having a solid content of 50% by mass. The number of repeating caprolactone units per acrylate monomer residue in this urethane acrylate is 3.

(Raw material 5)
100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanatohexanoate (LDI manufactured by Kyowa Hakko Kogyo Co., Ltd.) and 119 parts by mass of polycarbonate diol (Plaxel CD-210HL manufactured by Daicel Chemical Industries, Ltd.) are mixed and heated to 40 ° C. The temperature was raised to and maintained for 8 hours. Then, 28 parts by mass of 2-hydroxyethyl acrylate (Kyoeisha Chemical Co., Ltd. light ester HOA), 5 parts by mass of dipentaerystol hexaacrylate (Made by Toagosei Co., Ltd.) and 0.02 parts by mass of hydroquinone monomethyl ether were added. After maintaining at 70 ° C. for 30 minutes, 0.02 part by mass of dibutyltin laurate was added and maintained at 80 ° C. for 6 hours. Finally, 97 parts by mass of toluene was added to obtain a urethane acrylate having a solid content of 50% by mass.

(Raw material 6)
Hexamethylene diisocyanate modified isocyanurate (Takenate D-170N, Takeda Pharmaceutical Co., Ltd., isocyanate group content: 20.9% by mass), 50 parts by mass, polyethylene glycol monoacrylate (Nippon Yushi Blenmer AE-90, hydroxyl value: 332) (MgKOH / g)) 42 parts by mass, 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were charged. And it reacted by hold | maintaining at 70 degreeC for 5 hours. After completion of the reaction, 92 parts by mass of methyl ethyl ketone (MEK) was added to the reaction solution to obtain a urethane acrylate having a solid content of 50% by mass.

(Raw materials 7-9)
Urethane acrylate (raw material 6) was the same as raw material 6 except that polyethylene glycol monoacrylate was changed to 53 parts by weight of BLEMMER AE-150 (hydroxyl value: 264 (mgKOH / g)) and MEK of the reaction solution to 102 parts by weight. Raw material 7) was obtained.

  Further, urethane acrylate (raw material 8) was used in the same manner as in raw material 6 except that polyethylene glycol monoacrylate was changed to 68 parts by mass of BLEMMER AE-200 (hydroxyl value: 205 (mgKOH / g)) and MEK of the reaction solution to 118 parts by mass. )

  Further, urethane acrylate (raw material 9) was changed in the same manner as in raw material 6 except that polyethylene glycol monoacrylate was changed to 142 parts by mass of Bremer AE-400 (hydroxyl value: 98 (mg KOH / g)) and MEK of the reaction liquid was changed to 192 parts by mass. )

(Raw material 10)
50 parts by mass of toluene, 50 parts by mass of isocyanurate modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Takeda Pharmaceutical Co., Ltd.), 70 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate (Placcel FA5 manufactured by Daicel Chemical Industries, Ltd.) Polydimethylsiloxane (X-22-160AS manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts by mass Dibutyltin laurate 0.02 parts by mass and hydroquinone monomethyl ether 0.02 parts by mass were mixed and held at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a urethane acrylate mixture having a solid content of 50% by mass.

(Raw material 11)
<Synthesis of polysiloxane (a)>
In a 500 ml flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, 106 parts by mass of ethanol, 270 parts by mass of methyltrimethoxysilane, 23 parts by mass of γ-methacryloxypropylmethyldimethoxysilane, 100 parts by mass of deionized water, 1 part by mass of hydrochloric acid 1 part by mass and 0.1 part by mass of hydroquinone monomethyl ether were charged and reacted at 80 ° C. for 3 hours to synthesize polysiloxane (a). This was adjusted to 50 mass% with methyl isobutyl ketone.

<Synthesis of polydimethylsiloxane block copolymer (a)>
Using the same apparatus as the synthesis of polysiloxane (a), 50 parts by mass of toluene and 50 parts by mass of methyl isobutyl ketone, 20 parts by mass of a polydimethylsiloxane polymer polymerization initiator (WPS Pure Chemicals, VPS-0501) Parts, 18 parts by weight of methyl methacrylate, 38 parts by weight of butyl methacrylate, 23 parts by weight of 2-hydroxyethyl methacrylate, 1 part by weight of methacrylic acid and 0.5 parts by weight of 1-thioglycerin are reacted at 180 ° C. for 8 hours. Thus, a polydimethylsiloxane block copolymer (a) was obtained. The obtained block copolymer had a solid content of 50% by mass.

(Raw material 12)
50 parts by mass of toluene, 34 parts by mass of hexamethylene diisocyanate isocyanurate modified type (Takenate D-170N manufactured by Takeda Pharmaceutical Co., Ltd.), 57 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate (Daicel Chemical Industries, Ltd. Plaxel FA10) , 57 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Placcel FA3 manufactured by Daicel Chemical Industries, Ltd.), 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. . Thereafter, 137.8 parts by mass of toluene was added to obtain a urethane acrylate having a solid content of 50% by mass.

(Raw material 13)
50 parts by mass of 1,3-bisisocyanatomethylcyclohexane, 100 parts by mass of hydroxyalkyl acrylate, 0.05 parts by mass of dibutyltin laurate and 2 parts by mass of hydroquinone were added and held at 70 ° C. for 3 hours. Thereafter, aging was carried out at 85 ° C. for 2 hours to obtain urethane acrylate.

(Raw material 14)
It was obtained by dissolving 50 parts by mass of urethane acrylate (Sin Nakamura Chemical U5201) at 80 ° C. in 50 parts of MEK.

"Example"
Example 1
50 parts by mass of raw material 1 which is urethane (meth) acrylate B, 50 parts by mass of raw material 2 which is urethane (meth) acrylate C, 10 parts by mass of monohydroxyethyl acrylate phthalate (M-5400 manufactured by Toagosei Co., Ltd.), 10 parts by mass of toluene and 3 parts by mass of a photoinitiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) were mixed to prepare a radically polymerizable composition having a solid content of 50% by mass.

(Example 2)
70 parts by mass of raw material 3 which is urethane (meth) acrylate B, 30 parts by mass of raw material 4 which is urethane (meth) acrylate C, and 3 parts by mass of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) A radically polymerizable composition having a content of 50% by mass was prepared.

(Example 3)
30 parts by mass of raw material 5 which is urethane (meth) acrylate B, 70 parts by mass of raw material 4 which is urethane (meth) acrylate C, and 3 parts by mass of a photoinitiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) are mixed to form a solid A radically polymerizable composition having a content of 50% by mass was prepared.

Example 4
50 parts by mass of raw material 1 which is urethane (meth) acrylate B, 50 parts by mass of raw material 6 which is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) are mixed. 50 mass% of radically polymerizable composition was obtained.

  Further, the ratio of the mass m of the (1) (poly) alkylene glycol segment and the mass n of the (3) (poly) caprolactone segment in this radical polymerizable composition is m = 0.46 n.

(Example 5)
50 parts by mass of raw material 1 which is urethane (meth) acrylate B, 50 parts by mass of raw material 7 which is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) are mixed. 50 mass% of radically polymerizable composition was obtained.

  Further, the ratio of the mass m of the (1) (poly) alkylene glycol segment and the mass n of the (3) (poly) caprolactone segment in this radical polymerizable composition is m = 0.67 n.

(Example 6)
50 parts by mass of raw material 1 which is urethane (meth) acrylate B, 50 parts by mass of raw material 8 which is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) are mixed. 50 mass% of radically polymerizable composition was obtained.

  The ratio of the mass m of the (1) (poly) alkylene glycol segment to the mass n of the (3) (poly) caprolactone segment in this radical polymerizable composition is m = 0.88n.

(Example 7)
50 parts by mass of raw material 1 which is urethane (meth) acrylate B, 50 parts by mass of raw material 9 which is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) are mixed. 50 mass% of radically polymerizable composition was obtained.

  The ratio of the mass m of the (1) (poly) alkylene glycol segment and the mass n of the (3) (poly) caprolactone segment in the radical polymerizable composition is m = 1.6n.

(Example 8)
50 parts by mass of raw material 10 that is urethane (meth) acrylate B, 50 parts by mass of raw material 7 that is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba-Geigy Corporation) 50 mass% of radically polymerizable composition was obtained.

  The ratio of the mass m of the (1) (poly) alkylene glycol segment to the mass n of the (3) (poly) caprolactone segment in the radical polymerizable composition is m = 0.65n.

Example 9
47 parts by mass of raw material 1 which is urethane (meth) acrylate B, 47 parts by mass of raw material 7 which is urethane (meth) acrylate C, MEK dispersion of silica particles (manufactured by JGC Catalysts & Chemicals: Spherica slurry 120, average particle diameter) 5 parts by mass of 120 nm, SiO concentration of 5% by mass) and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy) were blended to obtain a radical polymerizable composition having a solid content of 100% by mass.

  Further, the ratio of the mass m of the (1) (poly) alkylene glycol segment and the mass n of the (3) (poly) caprolactone segment in this radical polymerizable composition is m = 0.67 n.

(Example 10)
20 parts by mass of raw material 1 that is urethane (meth) acrylate B, 80 parts by mass of raw material 8 that is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy Co., Ltd.) 50 mass% of radically polymerizable composition was obtained.

  The ratio of the mass m of the (1) (poly) alkylene glycol segment and the mass n of the (3) (poly) caprolactone segment in this radical polymerizable composition is m = 3.5n.

(Example 11)
100 parts by mass of raw material 7 which is urethane (meth) acrylate C and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) were blended to obtain a radical polymerizable composition having a solid content of 50% by mass.

(Example 12)
100 parts by mass of raw material 8 being urethane (meth) acrylate C and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) were blended to obtain a radical polymerizable composition having a solid content of 50% by mass.

(Example 13)
20 parts by mass of raw material 1 which is urethane (meth) acrylate B, 80 parts by mass of raw material 9 which is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) 50 mass% of radically polymerizable composition was obtained.

  Further, the ratio of the mass m of the (1) (poly) alkylene glycol segment and the mass n of the (3) (poly) caprolactone segment in this radical polymerizable composition is m = 6.3n.

(Example 14)
10 parts by mass of raw material 1 which is urethane (meth) acrylate B, 90 parts by mass of raw material 9 which is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) are mixed. 50 mass% of radically polymerizable composition was obtained.

  The ratio of the mass m of the (1) (poly) alkylene glycol segment to the mass n of the (3) (poly) caprolactone segment in this radical polymerizable composition is m = 14n.

"Comparative example"
(Comparative Example 1)
Polydimethylsiloxane block copolymer (a) 75 parts by mass, polysiloxane (a) 10 parts by mass and (poly) caprolactone triol having a hydroxyl group (Placcel 308, manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight 850) 15 parts by mass Parts were mixed (mixed) to obtain a raw material 11. 100 parts by mass of raw material 11 and 25 parts by mass of hexamethylene diisocyanate isocyanurate (Takeda Pharmaceutical Co., Ltd., Takenate D-170N) were added, diluted with methyl ethyl ketone, and a solid content of 40% by mass. A curable composition was obtained.

(Comparative Example 2)
100 parts by mass of raw material 1 which is urethane (meth) acrylate B and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) were blended to obtain a radical polymerizable composition having a solid content of 50% by mass.

(Comparative Example 3)
100 parts by mass of raw material 3 which is urethane (meth) acrylate B and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) were blended to obtain a radical polymerizable composition having a solid content of 50% by mass.

(Comparative Example 4)
100 parts by mass of raw material 12 which is urethane (meth) acrylate B and 3 parts by mass of a photoinitiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) were mixed to prepare a radical polymerizable composition having a solid content of 50% by mass.

(Comparative Example 5)
50 parts by mass of raw material 3 that is urethane (meth) acrylate B, 50 parts by mass of raw material 1 that is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) are mixed. 50 mass% of radically polymerizable composition was obtained.

(Comparative Example 6)
80 parts by mass of raw material 5 which is urethane (meth) acrylate B, 20 parts by mass of raw material 4 which is urethane (meth) acrylate C, 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) A 20 mass% radically polymerizable composition was obtained.

(Comparative Example 7)
50 parts by mass of raw material 5 which is urethane (meth) acrylate B, 50 parts by mass of raw material 3 which is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) 50 mass% of radically polymerizable composition was obtained.

(Comparative Example 8)
100 parts by mass of raw material 13 which is urethane (meth) acrylate B and 3 parts by mass of a photoinitiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) were mixed to prepare a radical polymerizable composition having a solid content of 50% by mass.

(Comparative Example 9)
100 parts by mass of raw material 14 which is urethane (meth) acrylate B and 3 parts by mass of a photoinitiator (Irgacure 184 manufactured by Ciba Specialty Chemicals) were mixed to prepare a radically polymerizable composition having a solid content of 50% by mass.
(Comparative Example 10)
50 parts by mass of raw material 5 which is urethane (meth) acrylate B, 50 parts by mass of raw material 14 which is urethane (meth) acrylate C, and 3 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Geigy Co., Ltd.) 50 mass% of radically polymerizable composition was obtained.

“Formation of B and C layers”
3 parts by weight of a photoinitiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) is mixed with 100 parts by weight of each composition of raw materials 1 to 10 and raw materials 12 to 14, and a radical polymerizable composition having a solid content of 50% by weight is mixed. Prepared. This composition was coated on a 100 μm thick polyester base film (“Lumirror” U46, manufactured by Toray Industries, Inc.) with a bar coater so that the layer thickness after drying was 30 μm. It is passed through a drying oven at 80 ° C. for 1 minute, and then cured while moving at a conveyor speed of 4 m / min in an ultraviolet (UV) drying oven with a high-pressure mercury lamp with an output of 400 mW / cm 2 to obtain a laminated film. It was. The obtained results are shown in Tables 1 and 2.

“Formation of layer formed from composition of raw material 11”
The composition of the raw material 11 was coated with a bar coater on a 100 μm thick polyester base film (“Lumirror” U46, manufactured by Toray Industries, Inc.) so that the film thickness of the layer after the aging process was 30 μm. After the application, it was heated with a hot air dryer at 160 ° C. for 2 minutes (heating step). Thereafter, heating (aging) was performed at 40 ° C. for 2 days (aging process) to obtain a laminated film. The obtained results are shown in Table 3.

"Formation of layer A"
3 parts by weight of a photoinitiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) is mixed with 100 parts by weight of each composition of Examples 1 to 14 and Comparative Examples 2 to 10, and a radical polymerizable composition having a solid content of 50% by weight. A product was prepared. This composition was coated on a 100 μm thick polyester base film (“Lumirror” U46, manufactured by Toray Industries, Inc.) with a bar coater so that the layer thickness after drying was 30 μm. It is passed through a drying oven at 80 ° C. for 1 minute, and then cured while moving at a conveyor speed of 4 m / min in an ultraviolet (UV) drying oven with a high-pressure mercury lamp with an output of 400 mW / cm 2 to obtain a laminated film. It was. The results obtained are shown in Tables 4 and 5.

Comparative Example 1
The composition of Comparative Example 1 was coated with a bar coater on a 100 μm thick polyester base film (“Lumirror” U46, manufactured by Toray Industries, Inc.) so that the layer thickness after the aging step was 30 μm. . After the application, it was heated with a hot air dryer at 160 ° C. for 2 minutes (heating step). Thereafter, heating (aging) was performed at 40 ° C. for 2 days (aging process) to obtain a laminated film. The results obtained are shown in Table 5.

Claims (8)

At least one side of the base film has an A layer,
When the oleic acid is applied to the surface of the A layer and held at 60 ° C. for 1 hour, the mass increase rate of the A layer is 10% by mass or less,
The maximum displacement in the thickness direction of the A layer is 1.0 to 3.0 μm and the creep displacement in the thickness direction of the A layer is 0.05 to 0 when a 0.5 mN load is applied for 10 seconds in the microhardness meter measurement. A laminated film having a residual displacement in the thickness direction of the A layer of 0.2 to 0.65 μm when the load is 0 mN.   The laminated film according to claim 1, wherein the resin contained in the A layer has (1) a (poly) alkylene glycol segment and (2) a urethane bond.   The laminated film according to claim 2, wherein the resin contained in the A layer has (3) (poly) caprolactone segments. The mass m of the (1) (poly) alkylene glycol segment in the resin contained in the A layer and the mass n of the (3) (poly) caprolactone segment in the resin contained in the A layer satisfy the following formula: 3. The laminated film according to 3.
0.3n ≦ m ≦ 10n   The laminated film according to any one of claims 1 to 4, wherein the elongation at break of the A layer is 30 to 80%.   The laminated film according to any one of claims 1 to 5, wherein the A layer contains particles.   The laminated film according to claim 1, wherein the dynamic friction coefficient (μk) of the A layer is 0.10 to 0.45.   The laminated film according to any one of claims 1 to 7, wherein the resin contained in the A layer has (4) a (poly) siloxane segment and / or a polydimethylsiloxane segment.

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