CN104884232B - Molding film - Google Patents

Abstract

It is an object of the invention to provide the flatness of the windability and molding transfer surface having concurrently in the manufacture of film and manufacturing procedure, further exterior quality is high, the molding film that mouldability is excellent.A kind of molding film, it it is the molding film using annular ethylene series resin as main constituent, have relief region at the both ends of the width of this molding film, described molding film is No yield point, and meets following (1)～the full terms of (3).(1), when being set to middle section beyond by above-mentioned relief region, surface roughness SRa of the one side in this middle section is more than 2nm below 30nm, and surface roughness SRa of another side is more than 100nm below 800nm.(2) when the height of above-mentioned relief region being set to h (μm), when the thickness of above-mentioned middle section is set to t (μm), it is less than more than 5/,100 30/100 than h/t.(3) width of above-mentioned relief region is more than 5mm below 20mm.

Description

Molding film

Technical field

The present invention relates to have concurrently the flatness of the windability and molding transfer surface in the manufacture of film and manufacturing procedure, further Exterior quality is high, the molding film that mouldability is excellent.

Background technology

In recent years, due to the raising of environmental consciousness, become in building materials, automobile component, portable phone, household electrical appliances, PC etc. In the decoration of type component, the requirement of solvent-free application, plating replacement etc. improves, and employs the importing progress of the trailing of film.

Wherein, the molding film used as carrying out printing and processing and forming, it is proposed that use biaxially oriented polyester film (with reference to patent documentation 1).Additionally, as can the molding simultaneously cosmetic sheet of deep drawing molding, it is proposed that use and poly-terephthaldehyde Acid glycol ester (following, to be sometimes referred to as PET) compares the film (reference of the low polyester of moulding stress, particularly copolymer polyester resin Patent documentation 2).Additionally, as tackling printing processing, the molding transfer foil film of coating waste water, it is proposed that at tensionless winkler foundation At least one side of polyester film is fitted with the film (with reference to patent documentation 3) of polyolefin film.Additionally, as employing cyclic polyolefin hydrocarbon system The film of resin, it is proposed that such as mold release film, decorating film (with reference to patent documentation 4 and patent documentation 5).

As the characteristic beyond the mouldability required by molding film, in the case of molding transfer foil film, to coating Decorative layer requires the exterior quality such as flatness, glossiness as the molding transfer surface of basement membrane.It is however generally that in order to realize film , there is the such undesirable condition of windability sacrifice in the manufacture and manufacturing procedure of film in the flatness on surface.As being used for disappearing Film manufacturing method except this undesirable condition, it is proposed that become important optics in the flatness on mulch film surface as molding applications In the field of purposes, it is provided with embossing concaveconvex shape, so-called processing at the both ends of film (also with the windability purpose that is improved as Be referred to as annular knurl processing, embossing processing) optical film (with reference to patent documentation 6).

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2001-347565 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2000-238070 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2004-188708 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2006-257399 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2005-162965 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2011-224934 publication

Summary of the invention

Invent problem to be solved

The film that patent documentation 1 is recorded is due to for biaxially oriented polyester film therefore excellent heat resistance, but the mouldability under low temperature Insufficient.

The film that patent documentation 2 is recorded, the solvent resistance of film is low, it is impossible to tolerance printing processing, coating waste water.

The film that patent documentation 3 is recorded, owing to employing polypropylene as polyolefin, therefore exterior quality is low, is requiring height Development difficulty in the purposes of the surface characteristic of degree.

The film that patent documentation 4 and patent documentation 5 are recorded, is not that the processability of exterior quality and then film is fully taken into account Design.

The film that patent documentation 6 is recorded, until in addition to be provided with the region of concaveconvex shape at the both ends of film, i.e. non-depressed Flower machining area, is not the windability design fully taken into account in the manufacture of film and manufacturing procedure.

Therefore, the problem of the present invention be solve above-mentioned problem of the prior art, it is provided that have concurrently film manufacture and processing work The flatness of the windability and molding transfer surface in sequence, further exterior quality is high, the molding film that mouldability is excellent.

For the method solving problem

The present invention is to solve such problem, use following methods.That is, one molding film, is with cycloolefin Resin, as the molding film of main constituent, has relief region, described molding at the both ends of the width of this molding film It is No yield point with film, and meets following (1)～the full terms of (3).

(1), when being set to middle section beyond by above-mentioned relief region, the one side in this middle section is (hereinafter referred to as A Face) surface roughness SRa be more than 2nm below 30nm, surface roughness SRa of another side (hereinafter referred to as B face) is More than 100nm below 800nm.

(2) when the height of above-mentioned relief region being set to h (μm), when the thickness of above-mentioned middle section is set to t (μm), than H/t is less than more than 5/,100 30/100.

(3) width of above-mentioned relief region is more than 5mm below 20mm.

The effect of invention

By the invention it is obtained that the windability and molding transfer surface having concurrently in the manufacture of film and manufacturing procedure is smooth Property, further exterior quality is high, the molding film that mouldability is excellent.

More specifically, owing to, in the manufacturing procedure such as the manufacture of film and coating, good windability and molding can be had concurrently The flatness of transfer surface, in vacuum forming, pressure empty molding, compressing such various forming methods, it is possible to achieve excellent Exterior quality and mouldability, therefore, it is possible to be applied to various method for processing forming, such as building materials, automotive department can be suitable for The decoration of the shaped components such as part, portable phone, household electrical appliances, PC.

Accompanying drawing explanation

Fig. 1 is for illustrating the outline side that the both ends of film width in the present invention form the method for relief region View.

Fig. 2 is the general view of Fig. 1.

Fig. 3 is the outline amplification view for illustrating relief pattern used in the present invention.

The summary sectional view of film width when Fig. 4 is to split with the dotted portion of Fig. 3.

Detailed description of the invention

The molding film of the present invention is monofilm or the stack membrane of the No yield point using annular ethylene series resin as main constituent. The present invention applies the film using annular ethylene series resin as main constituent by using as molding, thus in the decoration use of molded body In Tu, it also is able to, even for the shaped component needing deep drawing molding, the molding tracing ability that performance is excellent.

Here, so-called using annular ethylene series resin as main constituent, refer to the total of whole compositions of film is set to 100 matter Amount %, below more than annular ethylene series resin 50 mass % 100 mass %.Molding film in the present invention is more than 2 layers Stack membrane in the case of, so-called using annular ethylene series resin as main constituent, refer to the complete of whole layers by constituting stack membrane The total of portion's composition is set to 100 mass %, the annular ethylene series resin of whole layers add up to more than 50 mass % 100 mass % Below.Additionally, what is called is using annular ethylene series resin as main constituent, the total of whole compositions of film is set to 100 mass %, more It is preferably below more than annular ethylene series resin 70 mass % 100 mass %, more preferably more than 80 mass % 100 matter Amount below %, more than most preferably 90 mass % below 100 mass %.

Additionally, the molding film of the present invention is preferably No yield point film.By making No yield point film such that it is able to suppression molding Time film stress when being stretched, also be able to, even for the shaped component needing deep drawing molding, the molding tracing ability that performance is excellent. Here, so-called No yield point film, refer to the scope that planar orientation coefficient (fn) is 0.00～0.05.In order to obtain planar orientation coefficient (fn) It is the film of 0.00～0.05, the method making tensionless winkler foundation film can be enumerated.Even if being tensionless winkler foundation film, the most sometimes led when masking Stretch, be somewhat orientated at the upper film of operating direction (hereinafter referred to as length direction), therefore to make planar orientation coefficient be 0.00～ 0.05, even if also suppression orientation is important in the case of tensionless winkler foundation.If planar orientation coefficient (fn) is more than 0.05, the most sometimes During molding, length direction is different from the mouldability of width.The scope of more preferably 0.00～0.03, more preferably The scope of 0.00～0.02.So-called planar orientation coefficient (fn), refers to by using the film length direction of mensuration, the width such as Abbe refractometer The value that degree direction, the refractive index (respectively Nx, Ny, Nz) of thickness direction are calculated by following formula.

Planar orientation coefficient: fn={ (Nx+Ny)/2}-Nz

Here, in the case of not knowing the length direction of film, width, can have largest refractive index by face Direction be set to length direction, the direction orthogonal to the longitudinal direction in face is set to width, will be to orthogonal in face Direction be set to thickness direction, obtain planar orientation coefficient (fn).Additionally, the direction of the largest refractive index in face can utilize Ah Shellfish refractometer is the refractive index in whole directions in measuring face, for example, it is possible to by utilizing measuring difference of phases device (double refraction determining Device) etc. determine that slow axis direction is obtained.

The molding film of the present invention, in order to have windability and molding transfer surface in the manufacture and manufacturing procedure of film concurrently Flatness, the preferably both ends at the width of film have relief region.Embossing as the method arranging relief region adds The formation method of concaveconvex shape of work (also referred to as annular knurl processing, embossing processing), concavo-convex shape are not particularly limited, permissible Use known method.Additionally, the two sides that concaveconvex shape can be formed at film can also be formed at one side, but in order to reduce making The cost of roller apparatus, it is desirable to only formed in one side.Such as, as the method forming concaveconvex shape, can use and will be imprinted with four ribs Marking ring (giving the treatment tube of the projection) roll-in smooth with surface of the projections such as cone, circular cone connects, and makes film pass through between these rollers Method.As marking ring, it is possible to use materials such as carbon steel, rustless steel, ceramic coating and hard chrome (following, to be sometimes referred to as HCr) coating The marking ring of matter.Marking ring is not particularly limited, and the width of ring (roller), the spacing of projection, height can select as required. Additionally, smooth roller is not particularly limited, can be as required from urethane rubber, rustless steel, ceramic coating and HCr coating Etc. material selects optimal material.Additionally, concavo-convex formation can be carried out at normal temperatures, it is also possible to carry out under heating, but from From the viewpoint of suppressing the deformation of film peripheral part along with concavo-convex formation, film abrasion dirt, carry out the most under heating.In heating Under carry out concavo-convex formation in the case of, can use will the marking ring method that carries out heating by external heater；Use internal tool The method having the marking ring of heater；The method using the smooth roller being heated；Or be passed to after film is heated in advance The method etc. of marking ring.In the case of marking ring, smooth roller are heated, in order to make the temperature around marking ring, roller equal Homogenize, preferably inside marking roller, there is thermocouple equitemperature determinator, it is possible to carry out temperature control.Above-mentioned heating-up temperature, Generally speaking the temperature range below the glass transition temperature melt point above of resin selects.But, the molding of the present invention is used Film, is main constituent in annular ethylene series resin, and in the case of there is not fusing point, heating-up temperature is preferably glass transition temperature (Tg+120 DEG C) more than (hereinafter referred to as Tg) is below, more preferably below (Tg+110) more than (Tg+30 DEG C) DEG C, optimum Elect more than (Tg+50 DEG C) (Tg+100 DEG C) as below.Heating-up temperature, less than in the case of Tg, occurs sometimes with concavo-convex formation Deformation that the physical action of film peripheral part is caused, particularly at the tucking of both sides of the edge part of film width. In the case of heating-up temperature exceedes (Tg+120 DEG C), the softening of film is excessive sometimes, and the film periphery with concavo-convex formation occurs The deformation that the heat divided is caused.Additionally, as the concaveconvex shape in relief region, be not particularly limited, such as plain weave can be enumerated Shape, diagonal shape, embossing ring-shaped etc..Now, the maximum during the height of relief region refers to multiple protrusion height.

The molding film of the present invention preferably has relief region at the both ends of the width of film.If relief region is not Being formed in inner side in the end of film, the scope that can use as the film of goods narrows the most sometimes, and cost occurs finished product Rate reduces.Here the end of the width of what is called film, refers to that each end of the width of distance film is dividing of film overall width Region within other 5%.Relief region is preferably contained in each end of the width of each film, is more preferably contained in distance film The region of the scope of each end is film overall width less than more than the 0.2% 3.5% of width.Additionally, by the embossed area of film It is set to middle section beyond territory, the height of relief region is set to h (μm), when the thickness of middle section is set to t (μm), preferably It is less than more than 5/,100 30/100 than h/t.Now, middle section refers to the relief region formed by the both ends banding at film The region of the face clipped.During than h/t less than 5/100, after forming relief region, when being wound in core as film roll, it is impossible to make The removing property of the air owing to being involved in stream is good with the balance of retentivity, and what film roll occurred rolls tightly phenomenon, as a result of which it is, As molding film described later, the flatness of the molding transfer surface sometimes defining surface roughness (SRa) is impaired, or is prone to send out Raw damage.If than h/t more than 30/100, then the intermembranous air capacity being involved in film roll becomes too much, sometimes in rolling step Occur complications, curling staggered, or fold occurs.Additionally, relief region is formed at the both ends of the width of film, relief region Width be preferably more than 5mm below 20mm.More preferably more than 7mm below 15mm.It addition, the width of so-called relief region, Refer in each relief region that the both ends banding of the width of film is formed, the film width from multiple protuberances The end of the end side of the width of the film of the protuberance that outermost is formed is to the protuberance that inner side is formed of film width The scope of end of middle section side.When the width of relief region is less than 5mm, what film roll occurred sometimes rolls tightly phenomenon, or is prone to Damage.If the width of relief region is more than 20mm, in the rolling step of film, the most sometimes there is film on fold, or cost The scope that can use narrow.Additionally, relief region can have the place being partially interrupted on film length direction, but It is preferably formed into continuous print banding.

The formation of relief region can be carried out in the operation of film manufacture, and maybe can also be cut into by film by cutting machine need to After the goods width wanted, length, carry out in the Special process for concavo-convex formation.Drop in order to Shi Mo manufacturing process simplifies Low manufacturing cost, can intermediate in film manufacturing process rolling step, cut in operation, previously described quarter is set Print ring and smooth roller carry out concavo-convex processing, it is also possible to replace smooth roller and arrange marking on film conveying roller in these operations Roller carries out concavo-convex processing.

About the thickness t of the middle section in the molding film of the present invention, the i.e. thickness of film, from production stability, molding From the viewpoint of property, workability, more than preferably 50 μm below 200 μm.More than more preferably 75 μm 150 μm.If it is central The thickness t in region is thinner than 50 μm, and the rigidity of film, production stability reduce the most sometimes, or is prone to during molding introduce fold etc..This Outward, if the thickness t of middle section is more than 200 μm, operability, mouldability reduce the most sometimes, or cost of material uprises.Additionally, From the viewpoint of mouldability, processability, the uneven thickness of the molding film of the present invention is preferably less than 10%.By making thickness It is not less than 10%, such that it is able to molding equably, can suppress further to be coated with, be laminated, print, evaporation etc. adds man-hour Uneven.The method that uneven thickness is less than 10% making the molding film of the present invention is not particularly limited, and can enumerate and such as will water Casting temperature carries out high temperature until the method for nonadherent degree, the method making casting position be front casting, makes the mould of mouth die The method etc. that interlabial gap narrows.Uneven thickness more preferably less than 8%, most preferably less than 5%.

The molding film of the present invention, in order to have windability and molding transfer surface in the manufacture and manufacturing procedure of film concurrently Flatness, in the middle section beyond the relief region that the both ends of the width of film are arranged, to shaped component applying The face of decoration side, i.e. surface roughness SRa of molding transfer surface (hereinafter referred to as A face) is preferably more than 2nm below 30nm. If the flatness that SRa more than 30nm, then puts on the decorative cover on film is insufficient, the most decorated shaped component Appearance impaired.Considering from the appearance of decorative cover, the lower limit of SRa is the smaller the better, but as industrially becoming The roughness of the film that product rate manufactures well, for more than 2nm.Surface roughness SRa in A face is preferably more than 2nm below 20nm, More preferably more than 2nm below 10nm.Additionally, the face contrary with the A face that film applies decoration side is (hereinafter referred to as B Face) surface roughness SRa be preferably more than 100nm below 800nm.If surface roughness SRa in B face is more than 800nm, then By film roll around and when making film roll, the core part of film roll is affected by rolling tightly, and the embossing in the B face that surface roughness is big occurs The phenomenon that the produced strain in portion applies to the smooth A face as opposing face as compression stress is (hereinafter referred to as ripping up the back (back attack)), as a result of which it is, the flatness in A face is impaired sometimes, on A face, there is fluctuating shape as ripping up the back deformation Irregular.Further, by there occurs that the irregular A face of fluctuating shape is applied with the molding transfer foil of decorative layer, after molding transfer Shaped component generation bad order.Additionally, in the case of surface roughness SRa in B face is less than 100nm, the system of molding film When making and to apply the sliding adding film in man-hour of decorative layer impaired, there is fold during the winding of therefore film, rupture, sometimes can not get The film roll of good package formation.Surface roughness SRa in B face is preferably more than 200nm below 700nm, more preferably More than 300nm below 500nm.

In the molding film of the present invention, in order to make surface roughness SRa in A face be more than 2nm below 30nm, such as, have Utilize the method etc. that the sheet-shaped molten polymer extruded from T-shaped die head is cooled and solidified by the casting roll with smooth surface.Casting The smooth surface of roller is transferred to the film after casting, and the surface smoothness of the film of casting roll contact surface side improves.

In the above-mentioned methods, the arithmetic average roughness obtained according to JIS B 0601:2001 mensuration on casting roll surface Ra is preferably below 50nm, more preferably below 40nm, more preferably below 20nm.Additionally, the arithmetic average of casting roll The lower limit of roughness Ra is not particularly limited, but if it is considered that the volume of film is windability, the most preferably more than 2nm.About casting roll Surface roughness, as long as obtaining desired surface roughness i.e. by suitably selecting from known grinding method Can, but more it is advantageously controlled superficiality for precision, preferably through polishing grinding step after grinding.Additionally, water as mensuration The method of the surface roughness of casting roll, can enumerate: make triacetyl cellulose etc. crimp with roll surface after being dissolved in organic solvent, is dried And make the sample transferred with roller surface configuration as replicate sample, the method measuring the surface roughness of this replicate sample；Right The method etc. that roller surface is directly measured with surface roughness meter.Additionally, transfer more strongly as the flatness making casting roll In film, make the method that surface smoothness improves, it is possible to use following method: use wire electrode to apply to make film closely sealed by electrostatic Method in casting roll；By the method being sealed at roller with air knife, air chamber injection air；By by casting roll and niproll A pair chill roll constituted clamps the sheet-shaped molten polymer extruded from T-shaped die head, then makes it be sealed at casting roll one While carry out the method etc. drawn.

On the other hand, in order to make the scope that surface roughness SRa is more than 100nm below 800nm of side, B face, have following Method: add particle in film raw material and surface is carried out roughened method；Make when being shaped on casting roll by film to gather Surface is carried out roughened method by compound crystallization；Clamp at a pair chill roll by being made up of casting roll and niproll The sheet-shaped molten polymer extruded from T-shaped die head, then makes it be sealed at casting roll and carries out in the method drawn, will The surface of niproll is pre-machined into the surface roughness of appropriateness, then is transferred to the method etc. of face.

As the manufacture method of the molding film of the present invention, the such viewpoint of controlling from the surface roughness of film is examined Consider, be preferably and clamp from T-shaped mould at a pair chill roll by being made up of the casting roll forming A face and the niproll forming B face The sheet-shaped molten polymer of head extrusion, then makes it be sealed at casting roll and carries out in the method drawn, by niproll Surface the surface roughness of appropriateness, then the method that be transferred to face are pre-machined into.Casting roll during manufacture film and niproll The material used is not particularly limited, and is preferably metal material, the opposing party in the case of wanting to form even surface (A face) Face, wants surface breakdown becomes the face (B face) of embossing shape be preferably elastomeric material to improve windability.

It addition, the characteristic aspect of the molding film as the present invention, the annular ethylene series resin in the present invention, the most not Material is lubricated containing as the particle etc. that film surface is carried out roughened method.It is said that in general, by adding particle in the feed It is known for making the roughened method giving sliding in film surface, but has the table of film occurring to be caused by coming off of particle The worry of planar defect, it is therefore desirable for without.Particularly in the case of molding applications, by the stretched film when molding, thus The particle on film surface comes off and forms the probability height of surface defect, therefore without particle preferably.

The molding film of the present invention preferably has A layer and the stack membrane of B layer, and preferably this A layer is with cyclic olefin copolymerization tree Fat (hereinafter referred to as COC) is as main constituent, and this B layer is using cyclic olefin resin (hereinafter referred to as COP) as main constituent.

In the case of the stack membrane with A layer and B layer, the B layer of this film, A layer, B layer are the most directly stacked, at A layer In, preferably with cyclic olefin copolymer resins described later (following, to be sometimes referred to as COC) as main constituent.The present invention finds pass through Using COC as main constituent in A layer, it is possible to obtain the mouldability of excellence, the appearance of molded body.Here so-called in A layer Using COC as main constituent, refer to that the total of the whole compositions by the A layer of film is set to 100 mass %, containing COC 50 mass % with Below upper 100 mass %.Whole one-tenth of A layer are more preferably divided into 100 mass % by the stack membrane in the present invention, comprise COC More than 70 mass % mode below 100 mass %, more preferably comprises below more than COC 80 mass % 100 mass % Mode, particularly preferably comprise the mode of below more than COC 90 mass % 100 mass %.

Additionally, this film preferably in B layer with cyclic olefin resin described later (following, be sometimes referred to as COP) as main constituent. The present invention finds by B layer using COP as main constituent, thus such as maintain by A layer obtain as molding applications Excellent mouldability, the appearance of molded body, obtain the molding film of the resistance to tearing with excellence simultaneously.

Here, in B layer, so-called using COP as main constituent, refer to that the total of the whole compositions by the B layer of film is set to 100 Quality %, below more than COP 50 mass % 100 mass %.Stack membrane in the present invention is more preferably by whole one-tenth of B layer It is divided into 100 mass %, containing the mode below more than COP 70 mass % 100 mass %, more preferably contains 80 matter Mode below amount more than % 100 mass %, particularly preferably containing the mode below more than 90 mass % 100 mass %.

So-called cyclic olefin resin (COP) in the present invention, refers to only make " repetitive that main chain contains cyclic olefin " The resin of the mode being polymerized, the so-called cyclic olefin copolymer resins (COC) in the present invention, is to instigate that " main chain contains ring-type alkene The repetitive of hydrocarbon " and at least two or more repetition list of " not contained the repetitive that the alkene of cyclic olefin is formed by main chain " The resin (sometimes the repetitive containing cyclic olefin being referred to as cyclic olefin monomers) of the mode that unit has been polymerized.

As constitute COP, COC cyclic olefin, can enumerate cyclobutane, cyclopentenes, cycloheptene, cyclo-octene, cyclopentadiene, 1，3-cyclohexadiene such monocyclic alkene,

Bicyclo-[2,2,1] hept-2-ene", 5-methyl-bicyclo-[2,2,1] hept-2-ene", 5,5-dimethyl-bicyclo-[2,2,1] Hept-2-ene", 5-ethyl-bicyclo-[2,2,1] hept-2-ene", 5-butyl-bicyclo-[2,2,1] hept-2-ene", 5-octyl group-bicyclo-[2,2, 1] hept-2-ene", 5-octadecyl-bicyclo-[2,2,1] hept-2-ene", 5-methylene-bicyclo-[2,2,1] hept-2-ene", 5-vinyl- The such two ring type alkene of bicyclo-[2,2,1] hept-2-ene", 5-acrylic-bicyclo-[2,2,1] hept-2-ene",

Three rings [4,3,0,12.5] decyl-3,7-diene, three rings [4,3,0,12.5] decyl-3-alkene, three rings [4,3,0,12.5] 11 carbon-3,7-diene or three rings [4,3,0,12.5] 11 carbon-3,8-diene or as their partial hydrogenation thing (or ring penta The addition product of diene and cyclohexene) three rings [4,3,0,12.5] 11 carbon-3-alkene；5-cyclopenta-bicyclo-[2,2,1] hept-2- Alkene, 5-cyclohexyl-bicyclo-[2,2,1] hept-2-ene", 5-cyclohexenyl group bicyclo-[2,2,1] hept-2-ene", 5-phenyl-bicyclo-[2,2, 1] hept-2-ene" such three-ring type alkene,

Fourth Ring [4,4,0,12.5,17.10] 12 carbon-3-alkene, 8-methyl Fourth Ring [4,4,0,12.5,17.10] 12 carbon- 3-alkene, 8-ethyltetracyclo [4,4,0,12.5,17.10] 12 carbon-3-alkene, 8-methylene Fourth Ring [4,4,0,12.5,17.10] ten Two carbon-3-alkene, 8-ethylidene Fourth Ring [4,4,0,12.5,17.10] 12 carbon-3-alkene, 8-vinyl Fourth Ring [4,4,0,12.5, 17.10] 12 carbon-3-alkene, 8-acrylic-Fourth Ring [4,4,0,12.5,17.10] the 12 such four ring type alkene of carbon-3-alkene,

8-cyclopenta-Fourth Ring [4,4,0,12.5,17.10] 12 carbon-3-alkene, 8-cyclohexyl-Fourth Ring [4,4,0,12.5, 17.10] 12 carbon-3-alkene, 8-cyclohexenyl group-Fourth Ring [4,4,12.5,17.10] 12 carbon-3-alkene, 8-phenyl-cyclopenta-four Ring [4,4,0,12.5,17.10] 12 carbon-3-alkene, Fourth Ring [7,4,13.6,01.9,02.7] 14 carbon-4,9,11,13-four Alkene, Fourth Ring [8,4,14.7,01.10,03.8] 15 carbon-5,10,12,14-tetraene, five rings [6,6,13.6,02.7,09.14]- 4-hexadecene, five rings [6,5,1,13.6,02.7,09.13]-4-15 carbene, five rings [7,4,0,02.7,13.6, 110.13]-4-15 carbene, seven rings [8,7,0,12.9,14.7,111.17,03.8,012.16]-5-eicosylene, seven rings The polycycle alkene etc. such as [8,7,0,12.9,03.8,14.7,012.17,113.16]-14-such tetramer of eicosylene.

These ring type alkene can individually use or two or more is applied in combination.

Wherein, from the viewpoint of productivity, superficiality, as the cyclic olefin of composition COP and COC, it is preferably used two Three rings of the carbon numbers 10 such as ring [2,2,1] hept-2-ene" (hereinafter referred to as norborene), three rings [4,3,0,12.5] decyl-3-alkene The Fourth Ring of the carbon numbers 12 such as formula alkene (hereinafter referred to as tricyclo decene), Fourth Ring [4,4,0,12.5,17.10] 12 carbon-3-alkene Formula alkene (hereinafter referred to as tetracyclododecane), cyclopentadiene or 1，3-cyclohexadiene.

As the manufacture method of COP, the known method such as addition polymerization or ring-opening polymerisation of cyclic olefin monomers can be enumerated, can Enumerate such as, after making norborene, tricyclo decene, tetracyclododecane and their derivant ring-opening metathesis polymerization, carry out hydrogen The method changed；Make the method that norborene and its derivant carry out addition polymerization；Cyclopentadiene, cyclohexadiene is made to carry out 1,2-, 1,4- The method etc. hydrogenated is carried out after addition polymerization.

From the viewpoint of productivity, superficiality, mouldability, the COP in the present invention for make norborene, tricyclo decene, Resin obtained by hydrogenating after tetracyclododecane and their derivant ring-opening metathesis polymerization is most preferred mode.

As " not contained the repetitive that the alkene of cyclic olefin is formed by main chain " of the COC in the present invention, Ke Yiwei Side chain contains the mode of cyclic olefin, side chain does not contains any one of mode of cyclic olefin, but from productivity, the viewpoint of cost Consider, do not contain preferably as side chain cyclic olefin mode, so-called chain olefin.As preferred chain olefin, can lift Go out ethylene, propylene, 1-butylene, 1-amylene, 1-hexene, 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4- Methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-bis- Ten carbenes etc..Wherein, from the viewpoint of productivity, cost, can particularly preferably use ethylene.

As the manufacture method of COC, the known methods such as the cyclic olefin monomers addition polymerization with chain olefin monomer can be enumerated, Can enumerate such as, make norborene and derivant thereof and ethylene carry out the method etc. of addition copolymerization.

COC in the present invention, " repetitive that main chain contains cyclic olefin " with " do not contained cyclic olefin by main chain The repetitive that alkene is formed " quality ratio be preferably " repetitive that main chain contains cyclic olefin "/" do not contained by main chain The repetitive that the alkene of cyclic olefin is formed "=60/40～85/15, more preferably 65/35～80/20." master in COC Chain contains the repetitive of cyclic olefin " ratio less than in the case of 60 mass %, glass transition temperature is low sometimes, heat-resisting Property is insufficient.Additionally, the ratio of the repetitive of cyclic olefin " main chain contain " in COC is more than the situation of 85 mass % Under, mouldability, resistance to tearing are insufficient sometimes.

From the viewpoint of productivity, superficiality, mouldability, the COC in the present invention is the copolymerization of norborene and ethylene Thing is most preferred mode.

From the viewpoint of making film good with the adaptation of film in time making film, COC, the COP in the present invention can contain Polar group.As polar group, can enumerate such as, carboxyl, anhydride group, epoxy radicals, amide groups, ester group, hydroxyl etc., as make COC, COP contains the method for polar group, can enumerate unsaturated compound grafting and/or the method etc. of copolymerization making to have polar group.Make For having the unsaturated compound of polar group, (methyl) acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, (methyl) can be enumerated Glycidyl acrylate, (methyl) acrylic acid alkyl (carbon number 1～10) ester, maleic acid alkyl (carbon number 1～10) Ester, (methyl) acrylamide, (methyl) 2-Hydroxy ethyl acrylate etc..

As long as the molding film of the present invention meet make in A layer COC become main constituent with in B layer, make COP become main become Point, then A layer, B layer each layer in, can be only made up of COC or COP as main constituent, it is also possible to containing other olefin-based Resin, in addition can be containing the resin beyond olefin-based resin.

As the olefin-based resin beyond COC, COP, it is possible to use such as, Low Density Polyethylene, medium density polyethylene, height Ethene-alpha-olefin copolymer obtained by the polymerization of density polyethylene, linear low density polyethylene (LLDPE), use metalloscene catalyst is such The such various polypropylene of various polyethylene-based resins, polypropylene, ethylene-propylene copolymer, ene-propylene-butene copolymer It it is the polyolefin-based resins such as resin, methylpentene polymer.In addition it is also possible to use by ethylene, propylene, butene-1, amylene-1, Polymer that the 'alpha '-olefin monomers such as 4-methylpentene-1, hexene-1, octene-1 is formed, the block formed by this 'alpha '-olefin monomers are altogether Polymers etc..Wherein, from the compatibility of COC and/or COP from the viewpoint of, as the olefin-based resin beyond COC, COP, excellent Choosing uses various polyethylene-based resins, various polypropylene-based resin.

The molding film of the present invention is by containing polyethylene-based resin, polypropylene-based resin, such that it is able to reduce extrusion work Shear stress in sequence, it is possible to the generation of the foreign body that suppression is caused by crosslinking, also is able to suppress COC, COP distinctive crisp further Property, the most preferably.

On the other hand, if polyethylene-based resin, polypropylene-based resin is many containing quantitative change, self-preservation reduces the most sometimes, Or the appearance of stack membrane, the transparency reduce, or molded body appearance reduces.From appearance, processability, tear-resistant From the viewpoint of property, self-preservation, the total content of polyethylene-based resin and/or polypropylene-based resin is relative to film entirety 100 Quality %, more than preferably 1 mass % below 40 mass %, more preferably below more than 1 mass % 30 mass %, optimum Elect below more than 1 mass % 20 mass % as.It is here, so-called that " total of polyethylene-based resin and/or polypropylene-based resin contains Amount ", refer in the case of containing both polyethylene-based resin or polypropylene-based resin, both total content.And this In the case of bright molding film is the stack membrane of more than 2 layers, so-called relative to overall 100 mass % of film, polyethylene-based resin And/or the total content of polypropylene-based resin is below more than 1 mass % 40 mass %, be using the total quality of each layer as " film is overall " is treated, and treats judge as the polyethylene-based resin of each layer, the total content of polypropylene-based resin in addition.

Additionally, in polyethylene-based resin, polypropylene-based resin, examine from the viewpoint of the compatibility with annular ethylene series resin Consider, polyethylene-based resin is preferably used, more preferably uses high density polyethylene (HDPE), linear low density polyethylene (LLDPE), most preferably with line Type polyethylene.

It addition, the so-called polyethylene-based resin in the present invention, refer to, in polymer 100 mass %, derive from ethylene The polymer adding up to below more than 50 mass % 100 mass % of composition.Additionally, the polypropylene-based tree of what is called in the present invention Fat, refers in polymer 100 mass %, derive from propylene composition add up to below more than 50 mass % 100 mass % Polymer.

About the A layer (COC) of the stack membrane of the molding film constituting the present invention, from adding the dimensional stability in man-hour, molding From the viewpoint of property, glass transition temperature is preferably more than 70 DEG C less than 140 DEG C.If the glass transition temperature of A layer is little In 70 DEG C, the most sometimes it is being coated with, is being laminated, printing, is being deposited with in such manufacturing procedure, the change in size of the molding film of the present invention Suppression becomes insufficient, and the flatness etc. of the film after processing becomes insufficient.If additionally, the glass transition temperature of A layer surpasses Crossing 140 DEG C, the mouldability of the molding film of the present invention becomes insufficient the most sometimes.

Further for having high-dimensional stability and mouldability concurrently, the glass transition temperature of A layer be more preferably 80 DEG C with Upper less than 130 DEG C, particularly preferably more than 90 DEG C less than 120 DEG C.It addition, the glass transition temperature at A layer exists multiple In the case of, use the glass transition temperature of high temperature side.

In order to make the glass transition temperature of A layer be more than 70 DEG C less than 140 DEG C, such as, using norborneol as COC In the case of the copolymer of alkene and ethylene, by making the content of the norborene in A layer increase such that it is able to adjust vitrification and turn Temperature.Further, 2 kinds of COC that the content of norborene is different are blended, it is also possible to adjust the glass transition temperature of A layer.

About the B layer (COP) of the stack membrane of the molding film constituting the present invention, from adding the dimensional stability in man-hour, molding From the viewpoint of property, glass transition temperature is preferably more than 70 DEG C less than 140 DEG C.If the glass transition temperature of B layer is little In 70 DEG C, the most sometimes it is being coated with, is being laminated, printing, is being deposited with in such manufacturing procedure, the dimensionally stable of the molding film of the present invention Property becomes insufficient.If additionally, the glass transition temperature of B layer is more than 140 DEG C, the one-tenth of the molding film of the present invention the most sometimes Type becomes insufficient.

Further for having high-dimensional stability and mouldability concurrently, the glass transition temperature of B layer be more preferably 80 DEG C with Upper less than 130 DEG C, particularly preferably more than 90 DEG C less than 120 DEG C.It addition, the glass transition temperature at B layer exists multiple In the case of, use the glass transition temperature of high temperature side.

Such as, as COP, norborene, tricyclo decene, tetracyclododecane and their derivant open loop are made In the case of resin obtained by hydrogenating after metathesis polymerization, in order to make the glass transition temperature of B layer become more than 70 DEG C 140 Below DEG C, by making the cyclic olefin (norborene, tricyclo decene, tetracyclododecane and their derivant) carrying out being polymerized Molecule quantitative change big, or increase number of rings and become upright and outspoken structure such that it is able to adjust glass transition temperature.Further, mix 2 kinds of COP that mixed glass transition temperature is different, it is also possible to adjust the glass transition temperature of film.It addition, in the molding of the present invention In the case of being stack membrane with film, in order to have dimensional stability and mouldability concurrently, the glass transition temperature of preferably B layer is A layer Glass transition temperature more than.By becoming such composition, such that it is able to remain dimensionally-stable in B layer the most dividually Property and the function of high release property, keep the function of mouldability in A layer.

In the case of the molding film of the present invention is stack membrane, preferably there is A layer and B layer.By having A layer, B layer, Respectively become the important document of regulation, such that it is able to realize excellent exterior quality and mouldability.Additionally, from the transparency, self-preservation, From the viewpoint of appearance, (aggregate thickness of B layer/film gross thickness (the thickness t) of=middle section) is preferably 0.2 to lamination ratio ～0.7.The lamination ratio of film can pass through scanning electron microscope, transmission electron microscope, optical microscope etc. and observe film Cross section be measured.Additionally, constitute about lamination, from the viewpoint of operability (curling suppression), with A layer, the 2 of B layer Layer is constituted to be compared, preferably B layer, A layer, 3 layers of composition of B layer, particularly preferably becomes B layer, A layer, B layer direct lamination successively and forms 3 layers of composition.

In the case of the molding film of the present invention is monofilm, same with the A layer (COC) of above-mentioned stack membrane or B layer (COP) Sample ground, from the viewpoint of adding the dimensional stability in man-hour, mouldability, glass transition temperature is preferably more than 70 DEG C 140 DEG C Below.

The molding film of the present invention can contain antioxidant, antistatic additive, fire retardant, thermally-stabilised the most in right amount The coloring agent such as agent, UV absorbent, plasticizer, cohesiveness imparting agent, defoamer, pigment or dyestuff.

The molding film of the present invention is high due to exterior quality, and mouldability is excellent, therefore even for needing deep drawing molding Shaped component also is able to the molding tracing ability that performance is excellent, in molding trailing, is particularly preferably used as molding transfer foil Basement membrane.By the transfer surface side lamination decorative layer of the molding film in the present invention, with molding simultaneously to molded body (transfer printing body) Transfer, thus the molding film of the present invention and decorative layer can be easily peeled off, it is possible to obtain what appearance was excellent has dress The shaped component of decorations layer.As the composition of molding transfer foil, it is not particularly limited, is preferably on the molding film of the present invention folded The composition of layer decorative layer.Here, decorative layer is for additional coloring, floral designs, wood grain style, metallic, pearly-lustre style Layer Deng decoration.The marresistance of shaped component after transfer, against weather, from the viewpoint of design, preferably further Stacked laminated transparent layer.In such a situation it is preferred that clear layer is stacked on molding film side.But, although the molding film of the present invention is originally Body has a release property, but the situation insufficient with the release property of clear layer at the material phasic property due to molding film and clear layer Under, as long as known release layer raw material to be coated the molding film of the present invention.

The molding transfer foil of the present invention, as long as at least one side stacked laminated transparent layer successively of molding film, decorative layer and Adhesive linkage and must.From the viewpoint of the adaptation of molded body (transfer printing body) and decorative layer after transfer, preferably lamination Adhesive linkage.In such a situation it is preferred that adhesive linkage is stacked on molded body (transfer printing body) side.

As the optimal way of molding transfer foil, molding film/(release layer)/clear layer/decoration of the present invention can be enumerated The such composition of layer/adhesive linkage.Here so-called clear layer, refers to be positioned at the layer on the top layer of shaped component, is to turn for additional The marresistance of the shaped component after print, against weather, the layer of design.Additionally, so-called decorative layer here, refer to for adding The layer of the decoration such as coloring, floral designs, wood grain style, metallic, pearly-lustre style.

As long as the resin used as clear layer is high transparent resin, it is not particularly limited, from the viewpoint of marresistance Consider, thermosetting resin, light-cured resin or uv curing resin are preferably used.As thermosetting resin, preferably make With such as thermoset acrylic resins, phenoxy resin, epoxy resin etc., as light-cured resin or ultra-violet solidified Resin, is preferably used such as urethane acrylate resin, polyester acrylate resin, unsaturated polyester resin, organic Si acrylate resin, Epocryl etc..These resins can mixed light polymerization initiator, solidification as required Agent, curing accelerator, binding agent, surface conditioner, pigment, plasticizer, UV absorbent, ultraviolet reflection agent, light are stable Agent etc..Additionally, the resin used in clear layer can be copolymer, furthermore, it is possible to be the mixture of two or more resin.It addition, In the case of using light-cured resin or ultraviolet curable resin, examine from the viewpoint of the good forming ability making molding transfer foil Consider, carry out cured the most after shaping.

Additionally, from the viewpoint of marresistance, design, the thickness of clear layer is preferably 10～100 μm, the most excellent Elect 15～80 μm, most preferably 20～60 μm as.

As the forming method of clear layer, can enumerate be directly coated at molding film and formed method, be temporarily forming in Carrier film makes its method etc. transferred.In the case of needing the baking temperature after making clear layer be formed to be high temperature, it is preferably used It is made to be temporarily forming in carrier film, then so that it is the method for transfer.As the forming method of clear layer, except roller finishing, brush Beyond hair finishing, injection finishing, dipping coating method, can enumerate and employ gravure coater, die coating machine, comma coating Machine, rod coater, the method for scraper type coating machine.

As the forming method of decorative layer, be not particularly limited, can by being such as coated with, printing, metal evaporation etc. comes Formed.In the case of being coated, it is possible to use the rubbing methods such as gravure coating process, rolling method, comma rubbing method.Additionally, In the case of printing, it is possible to use the print processes such as lithography, woodburytype, screen painting method.As now institute The resin used, is preferably used polyester based resin, polyolefin-based resins, acrylic resin, carbamate system resin, fluorine system Resin, polyvinyl acetate system resin, vinyl chloride vinyl acetate copolymer system resin, vinyl-vinyl acetate copolymer system Resin etc..As the coloring agent used, it is not particularly limited, it is considered to dispersibility etc., from dyestuff, inorganic pigment, organic pigment Suitably select in Deng.

As the thickness of the decorative layer formed by coating, printing, the tone retentivity after molding, the sight of design Point considers, preferably 10～100 μm, more preferably 15～80 μm, most preferably 20～60 μm.

As the raw material of the adhesive linkage arranged for the purpose of giving cementability to molded body (transfer printing body), can make With thermosensitive type or pressure sensitive.The resin-formed body of molding by injection moulding etc. is being used as molded body (transfer printing body) In the case of, the adhesive linkage of the molding transfer foil being transferred to them can design according to the material of the resin-formed body as object The material of adhesive linkage.Such as, in the case of resin-formed body is acrylic resin, acrylic resin is preferably used, gathers Phenylate/polystyrene resin, polycarbonate-based resin, styrene copolymerized system resin, be polystyrene at resin-formed body In the case of being resin, it is preferably used, with these resins, there is the acrylic resin of affinity, polystyrene resin, polyamides Amine system resin etc..Additionally, in the case of resin-formed body is polypropylene-based resin, be preferably used chlorinated polyolefin hydrocarbon system resin, Ethlyene dichloride-vinyl acetate copolymer system resin, thermoprene, coumarone indene system resin.

As the forming method of adhesive linkage, it is not particularly limited, it is possible to use such as rolling method, gravure coating process, comma The rubbing methods such as rubbing method, additionally, the such as print process such as intaglio printing, screen painting.As using the molding that make use of the present invention Carry out the molded body (transfer printing body) decorated with the molding transfer foil of film, be not particularly limited, it is possible to use such as, polypropylene, Such resin, the hardwares such as acrylic acid series, polystyrene, polyacrylonitrile/styrene, polyacrylonitrile/Butadiene/Styrene Deng.

The molding film of the present invention due to the windability excellence in the manufacture and manufacturing procedure of film, the therefore conveying shape of film State is good, it is possible to obtain the film roll that package formation is good.Here, so-called film roll, refer to be wound in the molding film of the present invention Material obtained by the core formed by paper, plastics etc..Specifically, be wound when film manufactures machine winding goods (or Middle) volume, be processed into cutting machine after masking need the goods of width roll up, the goods that implement various coating in manufacturing procedure are rolled up Deng.

Embodiment

Hereinafter, according to embodiment, the present invention is described, but the present invention is not limited by these embodiments.It addition, each characteristic is led to Cross following method to be measured.

(1) surface roughness SRa

Surface roughness SRa of film, based on the surface roughness Ra according to JIS B 0601:2001, uses little slope to study Made 3-dimensional surface roughness meter ETB-30HK, measures under the following conditions with contact pin type.

Contact pilotage point diameter: 2 μm, contact pilotage increases the weight of: 10mg, measured length: 1mm, conveying spacing: 50 μm,

Mensuration bar number: 40, cutoff: 0.25mm

Under these conditions, it is thus achieved that (x, time y), SRa is drawn roughness curve f by following formula (several 1).

[several 1]

$SRa=\frac{1}{S_M}{{\∫}_0}^{Lx}{{\∫}_0}^{Ly}\left\{f(x,y)\right\}\mathrm{dx},dy$ Several 1

S_M=Lx × Ly

Wherein, 1x；Measured length=1mm, 1y=(conveying spacing) × (measuring bar number)=2mm, S=1x × 1y

(2) glass transition temperature

Use differential scanning calorimetry (DSC) (セ イ U electronics industry system, RDC220), according to JIS K7121:1987, JIS K 7122:1987 is measured and resolves.

Film 5mg (in the case of carrying out the evaluation of certain layer of film, cut take the layer being measured be 5mg) is used as Sample, read based on 20 DEG C/min in time being warming up to 300 DEG C for 25 DEG C by vitreousness to the specific heat of the transformation of rubbery state Change, obtains the prolongation straight line apart from each baseline and is in equidistant straight line and glass on the longitudinal axis (axle of display hot line) direction The intermediate point glass transition temperature of the point of the curve intersection of the stepped changing unit of glass transition, is set to glass transition temperature Degree.It addition, glass transition temperature exist multiple in the case of, use high temperature side glass transition temperature.

(3) film thickness (the thickness t) of=middle section

Use the digital micrometer μM ate M-of ソ ニ プ レ シ ジ ョ Application テ Network ノ ロ ジ Co., Ltd. 30, to measure 10 points at equal intervals on the width of film (=middle section), obtain their meansigma methods as measurement result.

(4) thickness of relief region

Use the digital micrometer μM ate M-of ソ ニ プ レ シ ジ ョ Application テ Network ノ ロ ジ Co., Ltd. 30, for the thickness of relief region at the both ends of film, in the scope of film length direction 1m with every each 10 surveys in side at equal intervals Fixed 20 points, obtain their meansigma methods as measurement result.

(5) the height h of relief region

The measurement result of thickness of above-mentioned (4) relief region is set with the difference of the measurement result of the thickness t of (3) middle section Height h for relief region.

(6) layer thickness of film

When measuring the layer thickness of each layer of stack membrane, use ラ イ カ マ イ Network ロ シ ス テ system ズ (strain) metal microstructure processed Mirror LeicaDMLM, shoots transmission radiograph to the cross section of film under conditions of multiplying power 100 times.Then by the photo shot, to folded Each layer of tunic respectively measures at arbitrary 5, is averaged value and is set to the layer thickness of each layer.

(7) width of relief region

Use metal scale, for the width of relief region at the both ends of film, each 5 mensuration 10 points in every side, ask Go out its meansigma methods as measured value.

(8) windability

Observe in rolling step when film manufactures, the feed status of film and be wound the surface of film roll obtained by machine winding State, windability according to following benchmark evaluation.

The feed status of A: film is good especially, film roll obtained by winding do not observe the most completely fold, damage, cave in, Convex deformation etc..

The feed status of B: film is good, film roll obtained by winding be visually barely perceivable fold, damage, cave in, convex Deformation etc..

The feed status of C: film is good, but film roll obtained by winding is visually observed the pleat of level no problem in practicality Wrinkle, damage, cave in, convex deformation etc..

The feed status of D: film is poor, film roll obtained by winding be visually observed significant fold, damage, cave in, convex becomes Shape etc.

(9) flatness of molding transfer surface

The film cutting into 10cm × 10cm size is pasted on black base stock, then covers with fluorescent lamp to observe sample Surface (side, A face) state, is evaluated according to following benchmark.

A: lustrous surface is the highest, does not observes irregular the most completely.

B: lustrous surface is high, is visually barely perceivable irregular.

C: the fluctuating shape being visually observed surface some is irregular, but be practical no problem level.

D: be visually observed surface significantly fluctuating shape irregular.

(10) mouldability

The size that film cuts out 200mm × 300mm in arbitrary position is used as sample.Use spreader at the table of sample Face (side, A face) coating ultraviolet hardening acrylic resin (BASF ジ ャ パ Application society's system " LAROMER " (registered trade mark) LR8983), carry out 10 minutes being dried at 80 DEG C, form the clear layer of coating thickness 50 μm.Additionally, use spreader at clear layer The silver ink of upper coating acrylic acid series/carbamate system, carries out 10 minutes being dried at 80 DEG C, it is thus achieved that coating thickness 30 μm Decorative layer.Use spreader to coat Japan ケ ミ カ Le 892L on decorative layer further, carry out 10 minutes doing at 80 DEG C Dry, form the adhesive linkage of coating thickness 20 μm, it is thus achieved that molding transfer foil.For the molding transfer foil of gained, use charity true The Three-dimensional vacuum heating-forming machine (NGF-0406-T TOM engineering method) of empty Co., Ltd., carries out the temperature heating to become 120 DEG C Degree, carries out vacuum/pressure empty molding (pressure along polypropylene rounding column resin die (basal diameter 150mm) being heated to 50 DEG C Empty: 0.2MPa), it is thus achieved that the shaped component of molding film/clear layer/decorative layer/adhesive linkage/polypropylene resin die.Close In the shaped component of gained, according to following benchmark evaluation along mould can (deep-draw be compared: forming height/end with the state of molding Face diameter).As long as being any one of S, A, B, C, it is simply that qualified level.

S: can be with deep-draw than more than 1.0 molding.

A: can with deep-draw than 0.9 less than 1.0 molding.

B: can with deep-draw than 0.8 less than 0.9 molding.

C: can with deep-draw than 0.7 less than 0.8 molding.

D: the deep-draw shape than 0.7 can not be shaped to.

(11) appearance of molded body

Utilize die coating machine to coat common prosperity society chemistry UF-TCI-1 in the side, A face of film roll, carry out 10 minutes being dried at 80 DEG C, Form the clear layer of coating thickness 50 μm.Then, same die coating machine is used to coat acrylic acid series/carbamate on clear layer The silver ink of system, carries out 10 minutes being dried at 80 DEG C, forms the decorative layer of coating thickness 30 μm.Spreader is used to exist further Coating Japan ケ ミ カ Le 892L on decorative layer, carries out 10 minutes being dried at 80 DEG C, forms the adhesive linkage of coating thickness 20 μm, Produce molding transfer foil volume.Roll up from the molding transfer foil of gained and cut out with the size of 200mm × 300mm in arbitrary position Film, operation carries out the empty molding of vacuum/pressure in the same manner as (10), it is thus achieved that molding film/clear layer/decorative layer/adhesive linkage/poly-third The shaped component of alkene resin die.The shaped component of gained is become 2,000mJ/cm with exposure rate²Mode irradiate purple Outside line and make varnish solidify.Observe the local transfer article (clear layer/decorative layer/adhesive linkage/polypropylene having peeled off molding film Resin die processed) surface, according to following benchmark evaluation appearance.

S: lustrous surface is the highest, the profile of fluorescent lamp is clearly mirrored.

A: lustrous surface is high, and the profile of fluorescent lamp is the most clearly mirrored.

B: surface observation is irregular to the fluctuating shape of part, but in addition as A, the profile of fluorescent lamp is the most clearly Mirror.

C: surface observation is irregular to fluctuating shape, and the profile of fluorescent lamp is slightly hazy unclear, but is practical no problem Level.

D: seen from surface, significant fluctuating shape is irregular, and the profile of fluorescent lamp is hardly visible.

(12) overall merit

Overall merit is carried out according to following benchmark.

AA: in each assessment item, B and C and D are 0, the situation of all A (or S)

BB: in each assessment item, C and D are 0, but B has the situation of more than 1

CC: in each assessment item, D are 0, but C has the situation of more than 1

DD: in each assessment item, D has the situation of more than 1

(cyclic olefin copolymer resins A (COC-A))

(ice drops in ethylene-norbornene based copolymer to employ Port リ プ ラ ス チ ッ Network ス society's system " TOPAS 8007F-04 " Sheet alkene content ratio 65 mass %).

(cyclic olefin copolymer resins B (COC-B))

(ice drops in ethylene-norbornene based copolymer to employ Port リ プ ラ ス チ ッ Network ス society's system " TOPAS 6013F-04 " Sheet alkene content ratio 76 mass %).

(cyclic olefin resin C (COP-C))

Employing Japan ゼ オ Application society's system " ZEONOR 1060R " (makes cyclic olefin and/or its derivant ring-opening metathesis gather Make after conjunction its hydrogenate obtained by resin).

(polyethylene-based resin D (PE-D))

Employ プ ラ イ system Port リ マ society's system " エ ボ リ ュ SP2540 ".

(embodiment 1)

Being constituted with 3 layers of B layer/A layer/B layer, the composition making each layer is as shown in table 1, is respectively fed to single axle extruding machine (L/D =28), for A layer side, B layer side, it is all to melt respectively in supply unit temperature 240 DEG C, its later temperature 250 DEG C so that it is logical Cross the leaf disk filter of filtering accuracy 30 μm, then in the feed block that the top of die head is arranged, carry out lamination to become B layer/A Layer/B layer (laminated thickness is than reference table), is then expelled to temperature to lamellar by T-shaped die head (die lip gap: 0.4mm) and controls into The casting roll (surface roughness 0.2s) of the minute surface of 50 DEG C controls into the rubber rollers (surface roughness Ra 0.4 μm) of 40 DEG C with temperature Between, clamp with this roller, then, control into after film cools down by the mirror roller of 25 DEG C by temperature, rolling step makes film pass through crimping Have between the roller of warmed-up marking ring and smooth roller, form banding in the longitudinal direction at the both ends of the width of film and extend The relief region of plain weave shape, by cutting the edge, both sides of intermediate coat in the air, then by the film of film thickness 100 μm It is wound with up-coiler, it is thus achieved that width 1,000mm, the molding film of the present invention of length 500m.The film being achieved in that and The characteristic of molding transfer foil, the evaluation result that use this film and make are as shown in table 1, windability, the flatness of molding transfer surface, Mouldability, molded body appearance the best.

(embodiment 2,3)

With composition same as in Example 1, change the surface roughness of the rubber rollers of clamping, film be filmed, it is thus achieved that This film and use this film and the molding transfer foil made.A face in middle section and surface roughness SRa in B face such as table 1 institute Showing, evaluation result is the best.

(embodiment 4～8)

With composition same as in Example 1, change the thickness t (embodiment 4,5) of middle section, the height h of relief region, recessed The width of convex domain, is filmed film, it is thus achieved that this film and use this film and the molding transfer foil made.Their characteristic, Evaluation result is as shown in table 1,2, the most well.

(embodiment 9,10)

The composition making each layer is as shown in table 2, and embodiment 10 is monofilm, and in addition, operation obtains similarly to Example 1 Obtained the molding film of the present invention and used this molding film and the molding transfer foil made.Their characteristic, evaluation result are such as Shown in table 2, the most well.

(comparative example 1,2)

With composition same as in Example 1, change the surface roughness of the rubber rollers of clamping, film be filmed, it is thus achieved that This film and use this film and the molding transfer foil made.A face in middle section and surface roughness SRa in B face such as table 3 institute Showing, windability difference in comparative example 1, in comparative example 2, the flatness of molding transfer surface and the appearance of molded body are poor, overall merit For DD.

(comparative example 3,4)

With composition same as in Example 1, change the height h of relief region, the width of relief region, film be filmed, The molding transfer foil obtaining this film and this film of use and make.As shown in table 3, comparative example 3,4 windability the poorest, comprehensively comment Valency is CC.

(comparative example 5)

With composition same as in Example 1, do not form relief region at the both ends of the width of film, by film system Film, it is thus achieved that this film and use this film and the molding transfer foil made.As shown in table 3, windability, molding transfer surface is smooth Property, molded body appearance poor, overall merit is DD.

[table 1]

[table 2]

[table 3]

Industry utilizability

The molding film of the present invention has the flatness of the windability and molding transfer surface in the manufacture of film and manufacturing procedure concurrently, In vacuum forming, pressure empty molding, compressing such various forming methods, it is possible to achieve excellent exterior quality and molding Property, therefore can be suitable for the decoration of the shaped components such as such as building materials, automobile component, portable phone, household electrical appliances, PC.

The explanation of symbol

1: film

2: marking ring (gives the treatment tube of projection)

3: smooth roller (opposed roll)

4: film direct of travel

5: film roll

6: marking part

7: relief pattern

8: film length direction

9: film end

10: the cross section (example) of the relief region of film width.

Claims (9)

1. a molding film, is the molding film using annular ethylene series resin as main constituent, at the width of this molding film The both ends in direction have relief region, and described molding film is No yield point, and meet following (1)～the full terms of (3),

(1) when being set to middle section beyond by described relief region, the surface roughness in the i.e. A of the one side in this middle section face SRa is more than 2nm below 30nm, and surface roughness SRa in another side i.e. B face is more than 100nm below 800nm,

(2) when the height of described relief region is set to h, when the thickness of described middle section is set to t, than h/t be 5/100 with Upper less than 30/100, wherein the unit of h and t is all μm,

(3) width of described relief region is more than 5mm below 20mm.

Molding film the most according to claim 1, the thickness t of described middle section is below more than 50 μm 200 μm.

Molding film the most according to claim 1 and 2, described molding film is to have A layer and the stack membrane of B layer,

This A layer using cyclic olefin copolymer resins i.e. COC as main constituent,

This B layer is using cyclic olefin resin i.e. COP as main constituent.

Molding film the most according to claim 3, in described stack membrane, direct lamination B layer, A layer, B layer successively.

Molding film the most according to claim 3, in described stack membrane, the glass transition temperature of A layer is more than 70 DEG C Less than 140 DEG C.

Molding film the most according to claim 3, in described stack membrane, the glass transition temperature of B layer is more than 70 DEG C Less than 140 DEG C, the glass transition temperature of B layer is more than the glass transition temperature of A layer.

Molding film the most according to claim 1 and 2, described molding film is monofilm, and the vitrification of this monofilm turns Temperature is more than 70 DEG C less than 140 DEG C.

8. a film roll, it is to be wound in the molding film described in any one of claim 1～7 in obtained by core.

9. a molding transfer foil, it is to fold successively at least one side of the molding film described in any one of claim 1～7 Obtained by layer clear layer, decorative layer and adhesive linkage.