KR20150110612A - Transfer film for decoration - Google Patents

Abstract

The present invention provides a decorative transfer film which satisfies molding performance during injection molding and has excellent surface protection performance. A decorative transfer film according to the present invention is a decorative transfer film comprising a support film and a decorative transferring layer formed by sequentially laminating a release layer (2), a hard coat layer (3), a primer layer (4), a decorative layer (5) And the hard coat layer (3) is formed by mixing an acrylic acrylate resin having a weight average molecular weight of 40,000 or more and 100,000 or less and containing a hydroxyl group, an ultraviolet initiator, silica particles having an average particle diameter of 10 nm or more and 100 nm or less, A non-tacky UV curable composition comprising at least a polytetrafluoroethylene powder having an average particle diameter of not less than 1 탆 and not more than 10 탆, wherein the primer layer (4) comprises an acrylic polyol resin, a polyisocyanate compound, And a two-liquid curable resin containing at least a vinyl chloride vinyl acetate copolymer resin.

Description

TRANSFER FILM FOR DECORATION

TECHNICAL FIELD The present invention relates to a decorative transfer film, and more particularly, to a molded decorative transfer film having mold transferability and excellent surface protection performance.

A method for producing a decorated molded article having a surface excellent in scratch resistance, chemical resistance, and the like, comprising the steps of: inserting a transfer film having a hard coating layer and a decorative layer into a metal mold at the time of injection molding; And simultaneously transferring the hard coat layer and the decorative layer onto a molding resin (transfer object). In recent years, the hard coat layer of the transfer film (hereinafter, also referred to as a " simultaneous decorative transfer film ") has become ultraviolet curing type mainstream rather than a thermosetting type. In addition, nowadays, a post-curing type transfer film for irradiating ultraviolet rays to the hard coating layer before the transfer is in a semi-curable state capable of being cured by ultraviolet rays and completely curing the hard coating layer becomes mainstream.

The molded decorative transfer film needs to correspond to various molding conditions (injection speed, resin temperature, pressure holding, cooling temperature, cooling time) and mold shape. As a result, there are many problems that may occur in the molded simultaneous decorative transfer film. Examples of the main defects derived from the transfer film in simultaneous molding of decorations include shot (defects), burrs, washout (pattern flow around the gate), whiteness, flow marks, cracks, and delamination.

On the other hand, the items required as the surface protection performance of the molded concurrent decorative transfer film include, for example, adhesion with a molding resin, pencil hardness, abrasion resistance (RCA abrasion), and steel wool rubbing.

There is a case where an untransferred region occurs in the transfer at the time of injection molding. The above-mentioned short (defect) refers to an area not transferred. In addition, the term refers to a portion where the transfer film is not cleanly cut off (that is, not cut as scheduled) at the boundary of the transfer region, and the transfer film is evacuated around the transfer region. The washout (pattern flow near the gate) means that the pattern printed near the gate to which the high temperature and the high pressure are applied partially disappears. In addition, the term "whitening" refers to a phenomenon in which the surface of the transferred film is whitened in white with heat during injection molding. The term "flow mark" refers to a phenomenon that remains on the surface of the transfer film or printed pattern due to the influence of the resin flow in the injection molding. Further, the crack means that the transferred film fails to follow the mold shape of the injection molding and is broken. The interlayer peeling refers to a phenomenon in which the transferred film is peeled off from the interlayer in accordance with the pressure and peeling operation during injection molding. This delamination often occurs particularly between the protective layer and the adjacent layer.

Since the demands are various, the material that can be used for the molded simultaneous decorative transfer film is not a material having particularly good properties (for example, hardness, elongation, and heat resistance), but a material having excellent balance among properties. For example, a hard material has good results in pencil hardness or steel wool rubbing, but is prone to cracking and low abrasion. On the other hand, the soft material does not cause cracks and can follow the deep drawing shape, but is prone to whitening and burrs. In addition, a material with high heat resistance can suppress washout, flow marks, whitening, but cracks tend to occur, and the deep drawing shape can not be followed. On the other hand, a material having a low heat resistance can follow the deep drawing shape without causing cracks, but is liable to cause washout, flow marks, and whitening.

As described above, the materials used in the molded decorative transfer film often have various properties and functions which are in conflict with each other. As described above, in the technical field of simultaneous decorating with many tasks, several improvements have been proposed as follows.

Generally, the physical properties of the ultraviolet ray hardening resin which is widely used as a protective layer (hard coat layer) tend to be hard and fragile, so that the hardness tends to be high but the abrasion resistance tends to be weak. Among them, in Patent Document 1, although the wear resistance is improved by crosslinking and hardening the ultraviolet ray hardening resin of the hard coat layer with the polyisocyanate compound, the film is hardly cut, and burrs tend to occur. Therefore, in Patent Document 2, the colloidal silica is placed in the hard coat layer to make the film to be transferred fragile, and to balance the countermeasure against abrasion.

However, as in Patent Documents 1 and 2, the addition of the polyisocyanate compound to the hard coat layer is a factor for inhibiting the radical polymerization of the ultraviolet curable resin, and it is understood that the steel wool rubbing and the pencil hardness are lowered. In addition, the addition of the polyisocyanate compound to the hard coat layer causes a large change in the peeling force (adhesion) when peeling between the release layer and the hard coat layer, and the peeling performance over time is not stable.

On the other hand, in the case of the post-curing type (type in which the hard coat layer is cured by irradiation with ultraviolet rays after the transfer), blocking is easy depending on the material of the hard coat layer. Therefore, blocking is prevented by incorporating silica having a particle diameter of several micrometers as an antiblocking agent in the material of the hard coat layer. However, when silica of several micrometers is put into the hard coat layer, the surface gloss may be lowered. Therefore, in Patent Document 3, it has been proposed to prevent blocking by newly forming an anti-blocking layer without putting the silica in the hard coat layer. However, forming a new anti-blocking layer leads to an increase in cost, which is undesirable.

In many cases, an ultraviolet hardening resin is used for the hard coat layer, but in this case, the hard coat layer and the decorative layer are not sufficiently brought into close contact with each other in many cases. Accordingly, in Patent Document 4, the primer layer is made of two layers of a urethane resin, a first primer layer containing an acrylic resin and a polyisocyanate compound, and a second primer layer containing an acrylic resin formed thereon, It has been proposed to maintain close contact. The primer layer needs to customize the composition for each ultraviolet curable resin used in the hard coat layer. In general, a specific primer layer is often required for a specific ultraviolet curable resin.

Japanese Patent Laid-Open No. 10-58895 Japanese Patent Application Laid-Open No. 2009-137219 Japanese Patent Application Laid-Open No. 2009-291996 Japanese Patent Laid-Open No. 5-278399

It is an object of the present invention to provide a decorative transfer film satisfying molding performance in injection molding and having excellent surface protection performance in simultaneous molding.

SUMMARY OF THE INVENTION The present invention has been extensively studied in order to solve the above problems and is achieved by the following means.

One aspect of the present invention is a decorative transfer film of the type which is cured by ultraviolet rays after transferring, wherein the decorative transfer film is provided on one surface of the support film with a releasing layer, a hard coating layer, a primer layer, , Wherein the composition of the hard coat layer is an acrylic acrylate resin having a weight average molecular weight of 40,000 or more and 100,000 or less and containing a hydroxyl group and an ultraviolet initiator and having an average particle diameter of 10 And a polytetrafluoroethylene powder having an average particle diameter in a range of 1 占 퐉 or more and 10 占 퐉 or less, wherein the composition of the primer layer is at least one selected from the group consisting of silica, An acrylic polyol resin, a polyisocyanate compound, and a vinyl chloride vinyl acetate copolymer containing a hydroxyl group That the sum of the resin to the two-liquid curing type resin including at least a decorative transfer film according to claim.

In the decorative transfer film, the content of the polytetrafluoroethylene powder contained in the hard coat layer may be set in a range of 0.1 wt% to 2 wt% with respect to the acrylic acrylate resin.

In the decorative transfer film, the content of the silica particles contained in the hard coat layer may be in the range of 10 wt% to 40 wt% with respect to the acrylic acrylate resin.

Further, in the decorative transfer film, the hard coating layer may further contain a polyisocyanate compound.

Another aspect of the present invention is to provide a decorative transfer film of the type which is cured by ultraviolet rays after the transfer, wherein the decorative transfer film is provided on one surface of the support film with a release layer, a first hard coat layer, A primer layer, a decorative printed layer, and an adhesive layer in this order, wherein the composition of the first hard coat layer is an acrylic acrylate resin having a weight average molecular weight of 40,000 or more and 100,000 or less, Silica particles having an average particle diameter within a range of 10 nm or more and 100 nm or less and polytetrafluoroethylene powder having an average particle diameter in a range of 1 μm or more and 10 μm or less, Wherein the composition of the second hard coat layer is a non-sticky ultraviolet curable composition containing no isocyanate compound, An acrylic acrylate resin containing a hydroxyl group, an ultraviolet initiator, silica particles having an average particle diameter of 10 nm or more and 100 nm or less, and a polyisocyanate compound within a range of 40,000 to 100,000 Wherein the composition of the primer layer is selected from the group consisting of an acrylic polyol resin, a polyisocyanate compound, and a vinyl chloride / vinyl acetate copolymer resin containing a hydroxyl group, wherein the composition is a non-tacky UV curable composition containing no polytetrafluoroethylene powder, Curable resin containing at least a two-component curable resin.

In the decorative transfer film, even if the thickness of the first hard coat layer is in the range of 0.5 탆 to 2.5 탆 and the thickness of the second hard coat layer is in the range of 3.0 탆 to 8.0 탆 do.

In the decorative transfer film, the content of the polytetrafluoroethylene powder contained in the first hard coat layer is preferably 0.1 wt% to 2 wt% based on the acrylic acrylate resin contained in the first hard coat layer % Or less.

In the decorative transfer film, the content of the silica particles contained in the first hard coating layer and the second hard coating layer may be controlled such that the content of the silica particles contained in the first hard coating layer and the acrylic acrylate resin To 10% by weight or more and 40% by weight or less, respectively.

According to one aspect of the present invention, it is possible to prevent short-circuiting (defects), burrs, wash-outs (pattern flow near the gate), whitening, flow marks, cracks and delamination, which are likely to occur during injection molding using a simultaneous decorative transfer film, It is possible to inexpensively provide a transfer film which can be reduced in comparison with the conventional technique and can satisfy the adhesion with the molding resin, the pencil hardness, the abrasion resistance (RCA abrasion), and the steel wool rubbing required for the surface protection performance.

1 is a cross-sectional view showing an example of a layer structure of a decorative transfer film according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view showing a layer structure of a molded product to which the decorative transfer film of Fig. 1 is transferred.
3 is a cross-sectional view showing another example of the layer structure of the decorative transfer film according to the embodiment of the present invention.
4 is a cross-sectional view showing a layer structure of a molded product to which the decorative transfer film of Fig. 3 is transferred.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same reference numerals are used for the same or similar components, and redundant description is omitted.

1 is a cross-sectional view showing an example of a layer structure of a decorative transfer film according to an embodiment of the present invention. 1, the transfer film according to the present embodiment includes a support film 1, a release layer 2, a hard coat layer 3, a primer layer 4, a decorative print layer (hereinafter simply referred to as & (Also referred to as a " layer ") 5, and an adhesive layer 6 in this order. Here, usually, the decorative layer 5 is often a plurality of layers, and a decorative material having an optical effect such as embossing or pearl pigments can also be incorporated. Fig. 2 is a cross-sectional view showing the layer structure of the molded article to which the decorative transfer film of Fig. 1 is transferred, and is a sectional view of the molded article after the decorative transfer film according to the present embodiment is transferred simultaneously with injection molding. As shown in Fig. 2, the molded product is constituted by providing an adhesive layer 6, a decorative layer 5, a primer layer 4 and a hard coat layer 3 on a molding resin 7 in this order.

Although not shown in the drawing, an antistatic layer may be provided on the surface of the support film 1 opposite to the release layer formation surface. By providing this antistatic layer, foreign matter adheres to the transfer film can be reduced and the yield can be improved (in other words, the incidence of defective products may be lowered). The antistatic layer may be a resin layer containing an existing antistatic agent. For example, a conductive filler such as ITO or antimony doped tin, a quaternary ammonium salt, a surfactant, a conductive polymer such as polythiophene or PEDOT, Coating layer.

Each layer of the decorative transfer film according to the present embodiment will be described below.

(Substrate film 1)

As the base film 1, for example, a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a triacetylcellulose film, a polycarbonate film, a nylon film, a cellophane film, , PET-G film can be used. The usable film thickness is within a range of 25 占 퐉 to 150 占 퐉, preferably within a range of 38 占 퐉 to 50 占 퐉.

(Releasing layer 2)

The releasing layer 2 is most preferably peelable from the hard coat layer 3, but it is preferably formed of a hardening resin because heat resistance, solvent resistance, top coatability and stretchability are also required. For this reason, for example, melamine resin, polyolefin resin, urethane resin, cellulose acetate and the like can be used as the release layer 2. Of these materials, a release layer 2 using a melamine resin is usually used in many cases. However, when a melamine resin is used for the release layer 2, a baking process at a high temperature (140 to 200 DEG C) is required, and harmful formaldehyde / RTI > Therefore, as a result of intensive studies, the inventors have found that a cured product of a long-chain alkyl group-containing acrylic resin and / or a silicone-modified acrylic resin, an acrylic polyol resin and a polyisocyanate compound is optimum as a release layer (2).

The thickness of the release layer 2 is not particularly limited, but it is optimum in the range of 0.1 탆 or more and 5 탆 or less. In addition, by containing a resin filler or an inorganic filler in the release layer 2, it is possible to make an anti-glare or to make the surface thereof matte.

(Hard coat layer 3)

The hard coat layer 3 is in a tack free state, and it is preferable that the hard coat layer 3 is formed of a crosslinkable resin by being irradiated with an ultraviolet ray or an electron beam after transferring to a transfer object. The reason for crosslinking after the transfer is that the transfer film according to the present embodiment is often used in injection molding or heat transfer, but cracking is liable to occur at the time of stretching the transferring beforehand, and thus appearance becomes poor.

As a method for realizing no tackiness before transfer, there are mainly the following three methods. The first method is a method using a polymer type acrylate or methacrylate. The second method is a method in which the liquid or semi-liquid phase ultraviolet curable resin is hardened little by using a crosslinking resin such as an isocyanate / polyol resin or an epoxy resin / amine to make it non-tacky. The third method is a method in which the hard coat layer 3 is slightly irradiated with ultraviolet rays or an electron beam to form a semi-hardened state.

In the present embodiment, the first method is used. As a reason, in the second method, the adhesion with the releasing layer 2 becomes too high, and the releasability as a transfer film becomes insufficient. In addition, the third method is a problem of variation in the intensity of the ultraviolet ray irradiator or the electron beam irradiator (specifically, variation in the intensity of the irradiated ultraviolet ray or electron beam) and reproducibility, and the process cost is also high.

In the case of using the first method, in order to prevent the resin from flowing during injection molding, it is preferable to use an acryloyl group having a weight average molecular weight of 40,000 or more and 100,000 or less and a glass transition temperature of 60 ° C or more, (Acrylic acrylate resin) containing a methacryloyl group is preferably used. In other words, it is preferable that the acrylic acrylate resin contained in the hard coat layer 3 has a weight average molecular weight of 40,000 or more and 100,000 or less and contains a hydroxyl group. When the weight-average molecular weight is less than 40,000, the tack free property is not sufficient and there is a problem in top coatability, and washout tends to occur at the time of molding. In addition, when the weight average molecular weight exceeds 100,000, the radical reactivity is lowered and the hardness at the time of crosslinking may not be increased. The optimum range of the weight average molecular weight of the acrylic acrylate resin is from 60,000 to 80,000.

Such an acrylic acrylate resin is advantageous in that it is non-tacky (when the solvent content is evaporated, stickiness is lost) as compared with an oligomer or a monomer generally used as an ultraviolet ray hardening resin, and that the hardening shrinkage is small , Since it is a polymer resin, ultraviolet curing property tends to deteriorate. Therefore, in order to compensate for the decrease in the surface hardness of the hard coat layer 3, it is necessary to add nanosilica particles to the acrylic acrylate resin. When the amount is less than 10% by weight based on the acrylic acrylate resin, the effect on hardness is not observed. On the other hand, if it exceeds 40% by weight, it tends to be too fragile and the abrasion resistance is poor. Therefore, the optimum amount of the nanosilica particles to be added is within a range of 10% by weight or more and 40% by weight or less based on the acrylic acrylate resin. The optimum range of the amount of the nano-silica particles to be added is 15 wt% or more and less than 35 wt%.

The above-mentioned weight average molecular weight is a value calculated by styrene conversion by GPC (gel permeation chromatography) measurement.

The nano-silica particles added to the hard coat layer 3 preferably have a particle diameter within a range of 10 nm to 100 nm in order to maintain transparency. Further, the nanosilica particles are preferably surface-treated with a silane coupling agent containing an acryloyl / methacryloyl group, but they may be untreated simple nanosilica particles.

When the main composition of the hard coat layer 3 is acrylic acrylate resin and nanosilica particles, the resistance of the steel wool test is excellent due to the hardness of the outermost surface, but in the abrasion resistance (especially RCA abrasion) It is easy to get results. However, by adding a polytetrafluoroethylene powder having an average particle diameter within a range of 1 占 퐉 or more and 10 占 퐉 or less to the acrylic acrylate resin within a range of 0.1 wt% or more and 2 wt% or less, the abrasion resistance can be improved have. When the average particle diameter of the polytetrafluoroethylene powder to be added is less than 1 占 퐉, the dispersibility is poor and handling is difficult. When the average particle diameter of the polytetrafluoroethylene powder to be added is more than 10 mu m, the hard coat layer 3 is hardly retained and the polytetrafluoroethylene powder tends to be easily removed. However, the hard coat layer 3 ) Is increased, so that it is not preferable. More preferably, the range of the average particle diameter of the polytetrafluoroethylene powder is from 2 탆 to 7 탆.

If the addition amount of the polytetrafluoroethylene powder is less than 0.1% by weight based on the acrylic acrylate resin, the effect of abrasion resistance is insufficient, and if it exceeds 2% by weight, scattering property is caused and transparency is lowered. Therefore, the preferable range of the amount of the polytetrafluoroethylene powder to be added is 0.1 wt% or more and 2 wt% or less. And more preferably in the range of 0.2 wt% or more and 1 wt% or less.

The total thickness of the hard coat layer 3, the primer layer 4, and the adhesive layer 6 from the hard coat layer 3 to the adhesive layer 6, except for the release layer 2, It is preferable to coat and print in-line the decorative layer 5 and the adhesive layer 6, but since the hard coat layer 3 to which the polytetrafluoroethylene powder is added has a high effect of preventing the blocking, the hard coat layer 3 ) Can be rolled after coating and temporarily stored.

Also, by adding a metallic soap such as polyethylene wax or zinc stearate to the hard coat layer 3, the wear resistance of the hard coat layer 3 can be improved. However, the above-mentioned addition of the metal soap does not show a remarkable effect unless it is added at least 10 times as much as the addition amount of the polytetrafluoroethylene powder. However, since the particle diameter is relatively large, the hardness of the hard coat layer 3 It is liable to cause deterioration and transparency deterioration, which is not suitable.

By adding a small amount of a polyisocyanate compound to the hard coat layer 3 and crosslinking it, it is possible to improve the toughness of the film and reduce the peeling of the foil (peeling off the foil during the production process). However, depending on the amount of the polyisocyanate compound to be added, it may cause peeling failure, burrs and shorts, pencil hardness and steel wool rubbing. Therefore, the amount of the polyisocyanate compound to be added is preferably 5% by weight or less based on the acrylic acrylate resin.

Next, Fig. 3 and Fig. 4 will be described. 3 is a cross-sectional view showing another example of the layer structure of the decorative transfer film according to the embodiment of the present invention. 3, the transfer film according to the present embodiment includes a support film 1, a release layer 2, a first hard coat layer 8, a second hard coat layer 9, a primer layer 4, A decorative layer 5, and an adhesive layer 6 in this order. 4 is a cross-sectional view showing the layer structure of the molded article to which the decorative transfer film of Fig. 3 is transferred, and is a sectional view of the molded article to which the decorative transfer film according to this embodiment is transferred. 4, the molded product has an adhesive layer 6, a decorative layer 5, a primer layer 4, a second hard coat layer 9, a first hard coat layer 8, In this order.

The decorative transfer film shown in Fig. 3 differs from the decorative transfer film shown in Fig. 1 in that the first hard coat layer 8 and the second hard coat layer 9 are provided. Therefore, the first hard coat layer 8 and the second hard coat layer 9 will be described below.

The first hard coat layer 8 contains an acryl acrylate resin having a weight average molecular weight of 40,000 or more and 100,000 or less and containing a hydroxyl group, an ultraviolet ray initiator, and an inorganic filler having an average particle diameter of 10 nm or more and 100 nm or less Silica particles and at least a polytetrafluoroethylene powder having an average particle diameter in a range of 1 占 퐉 or more and 10 占 퐉 or less and further contains no polyisocyanate compound.

The second hard coat layer 9 has a weight average molecular weight in the range of 40,000 or more and 100,000 or less and contains an acrylate acrylate resin containing a hydroxyl group and an ultraviolet ray initiator and an ultraviolet ray initiator having an average particle diameter of 10 nm or more and 100 nm or less Free ultraviolet curable composition which contains at least silica particles in a range of from 0.1 to 10 parts by weight and a polyisocyanate compound and further contains no polytetrafluoroethylene powder.

As described above, the hard coating layer of the present embodiment may include two or more layers. In this case, as described above, it is preferable that the first hard coat layer 8 adjacent to the release layer 2 contains polytetrafluoroethylene powder and does not contain a polyisocyanate compound. It is also preferable that the second hard coat layer 9 adjacent to the first hard coat layer 8 contains no polytetrafluoroethylene powder and also contains a polyisocyanate compound. It is for three reasons.

The first reason is as follows.

The nanosilica particles contained in the hard coat layer tend to be liable to be distributed on the surface opposite to the release layer 2 (that is, the atmosphere surface) when the coating liquid for the hard coating layer is applied and dried on the release layer 2. As a result, the nanosilica particle component is less on the side that becomes the outermost surface after the transfer, and consequently, the steel wool resistance and the pencil hardness are not increased. Therefore, by dividing the hard coat layer into two or more layers and making the first hard coat layer 8, which is the outermost layer, as thin as possible, the influence of the unevenization of the nano-silica particles can be reduced.

The second reason is as follows.

In order to improve the adhesion between the hard coat layer and the primer layer 4, it is preferable to add a polyisocyanate compound to the hard coat layer. However, if a polyisocyanate compound is added to the hard coat layer in contact with the release layer 2, Layer) may change with time, or peeling failure may occur at the time of transfer. Further, addition of a polyisocyanate compound to the first hard coat layer 8, which becomes the outermost surface after transfer, tends to result in lowering of the radical reactivity of the ultraviolet ray hardening resin and lowering of the surface hardness (particularly the steel wool resistance). Therefore, the hard coat layer (8), which is in contact with the release layer (2), is added to the second hard coat layer (9) on the primer layer (4) side without adding the polyisocyanate compound, This can be achieved by transferring the film to the balance.

The third reason is as follows.

When the primer layer (4) is overlaid on the hard coat layer containing the polytetrafluoroethylene powder, the coating liquid for the primer layer may be splashed or the interlayer adhesion may be insufficient. Therefore, polyfluoroethylene powder is added to the first hard coat layer 8 to set the second hard coat layer 9 that does not include the polyfluoroethylene powder to have a larger application amount than the first hard coat layer 8 Thereby preventing cratering of the coating liquid for the primer layer and improving adhesion.

Here, the content of the polytetrafluoroethylene powder contained in the first hard coat layer 8 is set within the range of 0.1 wt% to 2 wt% with respect to the acrylic acrylate resin contained in the first hard coat layer 8 .

The content of the silica particles contained in the first hard coat layer 8 and the second hard coat layer 9 is preferably such that the content of the silica particles contained in the first hard coat layer 8 and the second hard coat layer 9 It is preferable that the amount of each component is in the range of 10 wt% or more and 40 wt% or less.

The thickness of the first hard coat layer 8 is preferably in the range of 0.5 m to 2.5 m and the thickness of the second hard coat layer 9 is preferably in the range of 3.0 m to 8.0 m.

When the thickness of the first hard coat layer 8 is less than 0.5 탆, it is difficult to maintain the polytetrafluoroethylene powder, and there is a risk that the guide roll and the nip roll of the coating and spreading apparatus are dirty. In addition, when the thickness of the first hard coat layer 8 is more than 2.5 mu m, the effect of the anti-misalignment of the nano-silica particles is low.

When the thickness of the second hard coat layer 9 is less than 3.0 탆, the entire layer thickness as the hard coat layer including the first hard coat layer 8 is thin, and hardness as a hard coat layer can not be sufficiently exhibited due to oxygen inhibition or the like. In addition, the effect of preventing the coating liquid for primer layer from cratering is also reduced. When the second hard coat layer 9 is more than 8.0 mu m, not only the cost is increased but also the toughness becomes too strong and burrs tend to occur, which is not preferable.

Since the first hard coat layer 8 has a thin layer thickness, the amount of the nanosilica particles can be increased and the transparency is slightly lower than that in the case of forming the hard coat layer in one layer. However, It is possible to add nano-alumina particles having a high molecular weight.

The acrylic acrylate resin is a polymer having radical reactivity obtained by further pendanting a (meth) acryloyl group to a (meth) acrylic copolymer containing a copolymer of various (meth) acryloyl monomers, Meth) acryloyl monomers, various physical properties of the coating film can be exhibited. Generally, oligomers such as urethane acrylate, epoxy acrylate and polyester acrylate used in ultraviolet ray hardening resins have a weight average molecular weight of several hundred to several thousands, whereas acryl acrylate resins have several thousand to several hundred thousand, It has other properties such as no adhesion when cured.

Examples of the monomer component constituting the acrylic acrylate resin include mono / multifunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone, (Meth) acrylate, hexanediol (meth) acrylate, diethylene glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, neopentyl glycol (meth) acrylate, and the like.

Herein, the polyisocyanate compound is a polyisocyanate compound which is obtained by reacting toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene isocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) Quot; refers to a prepolymer.

The ultraviolet ray initiator is an initiator that generates a radical by ultraviolet rays. In the present embodiment, examples thereof include benzophenone, diethylthioxanthone, benzyldimethylketal, 2-hydroxy-2-methyl- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, acylphosphine oxide, and the like. The ultraviolet initiator is not particularly limited in use but may be selected depending on the wavelength of the irradiation light of the ultraviolet irradiation device used for curing the hard coat layer 3. [ The amount of the ultraviolet initiator to be added varies depending on the kind of the ultraviolet initiator, but it is preferably within a range of 1 wt% or more and 10 wt% or less with respect to the acryl acrylate resin.

(Primer layer 4)

The primer layer 4 is a layer for maintaining the adhesion between the hard coat layer 3 (or the second hard coat layer 9) and the decorative layer 5. As a result of intensive studies, , A hydroxyl group-containing vinyl chloride-vinyl acetate copolymer resin, and a polyisocyanate compound. More specifically, the primer layer 4 is a two-component curable resin containing at least a resin containing an acrylic polyol resin, a polyisocyanate compound, and a hydroxyl group-containing vinyl chloride-vinyl acetate copolymer resin. Further, by adding an extender pigment such as silica, barium sulfate, or calcium carbonate to the primer layer 4, the adherence of the coating solution for decorative layer is improved. In addition, since it is possible to reduce the number of burrs, it is optimal to add the above-mentioned extender pigment to the acrylic polyol resin in the range of 5 wt% or more and 20 wt% or less.

When the glass transition temperature of the acrylic polyol resin is less than 50 캜, burrs tend to occur. When the glass transition temperature exceeds 90 캜, adhesion of the acrylic polyol resin to the hard coat layer 3 tends to become difficult. For this reason, it is preferable that the acrylic polyol resin used in the present embodiment has a glass transition temperature in the range of 50 占 폚 to 90 占 폚.

The vinyl chloride vinyl acetate copolymer resin can be reacted with the polyisocyanate compound by using a vinyl alcohol vinyl chloride or vinyl chloride vinyl acetate copolymer resin modified with hydroxyalkyl acrylate, and the adhesion is improved. It is preferable that the hydroxyl group-containing vinyl chloride vinyl acetate copolymer resin is blended in the primer layer 4 within the range of 10 wt% or more and 60 wt% or less with respect to the acrylic polyol resin. Although the thickness of the primer layer 4 is not particularly limited, it is optimum in the range of 0.5 m or more and 4 m or less.

(Decorative layer 5)

The decorative layer 5 has no particular difference in material compared with the above-mentioned respective layers. As decorative techniques that can be employed in forming the decorative layer 5, there are a decorative printing technique such as a general printing using a colored coating liquid, a special printing such as pearl, fluorescence, mirror, retroreflection, magnetic printing, An embossing process for forming various lens effects or holograms), and a thin film forming technique in which aluminum, silver, chromium, titanium oxide, zinc sulfide or the like is formed by vacuum evaporation or sputtering.

The decorative layer 5 is generally formed of two or more layers and is formed of, for example, a black pattern printed layer / white backing layer, perl layer / black printed layer, red pattern printed layer / mirror ink layer, navy pattern / embossed layer / (For example, in order to improve the quality of printing defects and functional separation (in this case, adhesion and burr compatibility), such as the case of considering designability as well as the case of black solid printing layer (containing hardening agent) / black solid printing layer / black solid printing layer , It is selected according to various demands.

(Adhesive layer 6)

As the adhesive layer 6, known heat sealable adhesives or pressure sensitive adhesives can be used. Examples of the adhesive layer 6 include a vinyl acetate resin, an ethylene vinyl acetate copolymer resin, a vinyl chloride acetate resin, an acrylic resin, a butyral resin, an epoxy resin, a polyester resin, a polyurethane resin, an acrylic pressure sensitive adhesive, a rubber pressure sensitive adhesive, , Urethane-based pressure-sensitive adhesives, and the like. Further, the thickness of the adhesive layer 6 is most preferably in the range of 0.5 占 퐉 to 10 占 퐉.

As a method of forming each layer in the present embodiment, a conventional coating / printing method can be employed. Examples of the method of forming each layer in the present embodiment include direct gravure, gravure reverse, microgravure, roll coating, curtain coating, die coating, spray coating, Mayer coating, comma coating, screen printing, . Drying conditions of the coating liquid vary depending on the solvent used, but drying is usually sufficient by drying for 2 to 60 seconds under an environment of 80 to 150 ° C. However, depending on the thickness of the coating liquid and the type of coating liquid, it may be necessary to perform additional drying for several tens of seconds at 120 to 180 DEG C in order to reduce the residual solvent and accelerate the two-liquid curing reaction.

The transfer film of the present embodiment is obtained by applying each layer of the release layer 2, the hard coat layer 3, the primer layer 4, the decorative layer 5 and the adhesive layer 6 including the above composition to the application / By the method described above.

The thus-produced transfer film of the present embodiment can be transferred to the surface of a molded article by injection molding by inserting it into a mold at the time of injection molding. The peeling interface is the interface between the release layer 2 and the hard coat layer 3 (or the second hard coat layer 9). After the transfer, the hard coat layer 3 (or the second hard coat layer 9) is cured by irradiation with a high-pressure mercury lamp or a metal halide lamp at an exposure dose of about 500 to 1500 mJ / cm 2. By doing so, it is possible to obtain a molded article satisfying various physical properties (steel wool test, pencil hardness, etc.).

Next, the present invention will be described more specifically by way of examples.

≪ Example 1 >

On the biaxially stretched polyester film (G440E50 manufactured by Mitsubishi Jushi Co., Ltd.) having a thickness of 50 占 퐉, the coating solution for releasing layer prescribed as described below was applied and dried to a thickness of 0.4 占 퐉 after drying by microgravure method. Thereafter, aging was performed for 5 days under an environment of 50 캜 to form a release layer (2).

· Application liquid for release layer

Acrylic polyol manufactured by Toei Kasei LC # 6560 ... 100 parts by weight

Silicone-modified acrylic resin for healing production FS730 ... 20 parts by weight

Nippon Polyurethane Manufacturing Isocyanate Compound Coronate L ... 20 parts by weight

Subsequently, the following hard coating layer coating liquid was applied as a hard coating layer 3 so as to have a thickness of 5.0 mu m after drying by the microgravure method and dried. Thereafter, this film was wound. This film was stored for 30 days under an environment of 40 DEG C, but no blocking occurred.

· Coating liquid for hard coating layer

DIC manufactured non-stick UV-curable resin (containing ultraviolet polymerization initiator) solid content 30%

RC29-117 ... 100 parts by weight

Manufactured by Nissan Chemical Industries, Ltd. (particle diameter: 10 to 20 nm) MEK dispersion (solid content: 30%)

                                                             ... 20 parts by weight

Polyfluoroethylene powder L173J (particle diameter 7 占 퐉, solid content 100%) manufactured by Asahi Glass Co., Ltd. ... 0.3 parts by weight

Subsequently, as a coating liquid for a primer layer, a coating liquid for a primer layer prescribed as described below was applied to the film so that the film thickness after drying by the direct gravure method was 1.0 占 퐉.

· Coating liquid for primer layer

Acrylic polyol manufactured by Toei Kasei YB # 7004 ... 100 parts by weight

Hydroxyalkyl acrylate-modified vinyl chloride-vinyl acetate copolymer resin Solvain TA2 manufactured by Nisshin Kagaku Co., Ltd. 10 parts by weight

Nippon Polyurethane Manufacturing Isocyanate Compound Coronate L ... 20 parts by weight

Subsequently, the adhesive layer 6 was coated with a coating solution for a decorative layer, and the adhesive layer 6 (K539HP adhesive varnish manufactured by Toy ink) was applied by a gravure method so as to have a thickness of 1 mu m, .

Subsequently, the decorated transfer film was set inside the mold of the injection molding machine, and injection molding was carried out with a polycarbonate ABS alloy resin. Thus, a molded product obtained by transferring the transfer film of this example was obtained.

≪ Example 2 >

On the biaxially stretched polyester film (G440E50 manufactured by Mitsubishi Jushi Co., Ltd.) having a thickness of 50 占 퐉, the coating solution for releasing layer prescribed as described below was applied and dried to a thickness of 0.4 占 퐉 after drying by microgravure method. Thereafter, aging was performed for 5 days under an environment of 50 캜 to form a release layer (2).

· Application liquid for release layer

Acrylic polyol manufactured by Toei Kasei LC # 6560 ... 100 parts by weight

Silicone-modified acrylic resin for healing production FS730 ... 20 parts by weight

Nippon Polyurethane Manufacturing Isocyanate Compound Coronate L ... 20 parts by weight

Subsequently, as the first hard coat layer 8, the following coating liquid for the first hard coat layer was applied and dried to a thickness of 1.0 mu m after drying by the microgravure method. Thereafter, the coating liquid for the second hard coating layer was applied and dried to a thickness of 2.0 mu m after drying by the microgravure method. Thereafter, this film was wound. The film was stored for 30 days in an environment of 40 DEG C, but no blocking occurred.

The coating liquid for the first hard coating layer

DIC manufactured non-stick UV-curable resin (containing ultraviolet polymerization initiator) solid content 30%

RC29-117 ... 100 parts by weight

Manufactured by Nissan Chemical Industries, Ltd. (particle diameter: 10 to 20 nm) MEK dispersion (solid content: 30%)

                                                             ... 20 parts by weight

Polyfluoroethylene powder L173J (particle diameter 7 占 퐉, solid content 100%) manufactured by Asahi Glass Co., Ltd. ... 0.3 parts by weight

The coating liquid for the second hard coating layer

DIC manufactured non-stick UV-curable resin (containing ultraviolet polymerization initiator) solid content 30%

RC29-117 ... 100 parts by weight

Manufactured by Nissan Chemical Industries, Ltd. (particle diameter: 10 to 20 nm) MEK dispersion (solid content: 30%)

                                                             ... 20 parts by weight

Nippon Polyurethane Manufacturing Isocyanate Compound Coronate HL ... 5 parts by weight

Subsequently, as a coating liquid for a primer layer, a coating liquid for a primer layer prescribed as described below was applied to the film so that the film thickness after drying by the direct gravure method was 1.0 占 퐉.

· Coating liquid for primer layer

Acrylic polyol manufactured by Toei Kasei YB # 7004 ... 100 parts by weight

Hydroxyalkyl acrylate-modified vinyl chloride-vinyl acetate copolymer resin Solvain TA2 manufactured by Nisshin Kagaku Co., Ltd. 10 parts by weight

Fuji Silica Manufactured Silica Fo ... 2 parts by weight

Nippon Polyurethane Manufacturing Isocyanate Compound Coronate L ... 20 parts by weight

Subsequently, the adhesive layer 6 was coated with a coating solution for a decorative layer, and the adhesive layer 6 (K539HP adhesive varnish manufactured by Toy ink) was applied by a gravure method so as to have a thickness of 1 mu m, .

Subsequently, the decorated transfer film was set inside the mold of the injection molding machine, and injection molding was carried out with a polycarbonate ABS alloy resin. Thus, a molded product obtained by transferring the transfer film of this example was obtained.

≪ Comparative Example 1 &

On the biaxially stretched polyester film (G440E50, manufactured by Mitsubishi Jushi Co., Ltd.) having a thickness of 50 占 퐉, the coating solution for releasing layer prescribed as described below was applied and dried to a thickness of 0.2 占 퐉 after drying by microgravure method. Thereafter, aging was performed for 5 days under an environment of 50 캜 to form a release layer (2).

· Application liquid for release layer

Acrylic polyol manufactured by Toei Kasei LC # 6560 ... 100 parts by weight

Silicone-modified acrylic resin for healing production FS730 ... 20 parts by weight

Nippon Polyurethane Manufacturing Isocyanate Compound Coronate L ... 20 parts by weight

Subsequently, as a hard coat layer 3, the following coating liquid for a hard coat layer was applied and dried to a thickness of 6.0 mu m after drying by a microgravure method. Thereafter, this film was wound. The film was stored for 30 days under an environment of 40 캜, resulting in blocking and unusable.

· Coating liquid for hard coating layer

DIC manufactured non-stick UV-curable resin (containing ultraviolet polymerization initiator) solid content 30%

RC29-117 ... 100 parts by weight

Manufactured by Nissan Chemical Industries, Ltd. (particle diameter: 10 to 20 nm) MEK dispersion (solid content: 30%)

                                                             ... 30 parts by weight

Nippon Polyurethane Manufacturing Isocyanate Compound Coronate HL ... 10 parts by weight

Subsequently, as a coating liquid for a primer layer, a coating liquid for a primer layer prescribed as described below was applied to the film so that the film thickness after drying by the direct gravure method was 1.0 占 퐉.

· Coating liquid for primer layer

Acrylic polyol manufactured by Toei Kasei YB # 7004 ... 100 parts by weight

Hydroxyalkyl acrylate-modified vinyl chloride-vinyl acetate copolymer resin Solvain TA2 manufactured by Nisshin Kagaku Co., Ltd. 10 parts by weight

Fuji Silica Manufactured Silica Fo ... 2 parts by weight

Nippon Polyurethane Manufacturing Isocyanate Compound Coronate L ... 20 parts by weight

Subsequently, the adhesive layer 6 was coated with a coating solution for a decorative layer, and the adhesive layer 6 (K539HP adhesive varnish manufactured by Toy ink) was applied by a gravure method so as to have a thickness of 1 mu m, .

Subsequently, the decorated transfer film was set inside the mold of the injection molding machine, and injection molding was carried out with a polycarbonate ABS alloy resin. Thus, a molded article obtained by transferring the transfer film of this comparative example was obtained.

≪ Comparative Example 2 &

On the biaxially stretched polyester film (G440E50 manufactured by Mitsubishi Jushi Co., Ltd.) having a thickness of 50 占 퐉, the coating solution for releasing layer prescribed as described below was applied and dried to a thickness of 0.6 占 퐉 after drying by microgravure method. Thereafter, aging was performed for 5 days under an environment of 50 캜 to form a release layer (2).

· Application liquid for release layer

Acrylic polyol manufactured by Toei Kasei LC # 6560 ... 100 parts by weight

Silicone-modified acrylic resin for healing production FS730 ... 20 parts by weight

Nippon Polyurethane Manufacturing Isocyanate Compound Coronate L ... 20 parts by weight

Subsequently, as a hard coat layer 3, the following coating liquid for a hard coat layer was applied and dried to a thickness of 6.0 mu m after drying by a microgravure method. Thereafter, this film was wound.

· Coating liquid for hard coating layer

DIC manufactured non-stick UV-curable resin (containing ultraviolet polymerization initiator) solid content 30%

RC29-117 ... 100 parts by weight

Manufactured by Nissan Chemical Industries, Ltd. (particle diameter: 10 to 20 nm) MEK dispersion (solid content: 30%)

                                                             ... 20 parts by weight

Subsequently, an acrylic polyol / isocyanate coating liquid (V425 anchor manufactured by Toy ink) was applied as a primer layer 4 to the film so as to have a thickness of 2 mu m after dried by the gravure method. Then, the adhesive layer 6 was coated with a coating solution for a decorative layer, and the adhesive layer 6 (K539HP adhesive varnish manufactured by Toyoko Ink) was coated by a gravure method so as to have a thickness of 1 mu m, .

Subsequently, the decorated transfer film was set inside the mold of the injection molding machine, and injection molding was carried out with a polycarbonate ABS alloy resin. Thus, a molded article obtained by transferring the transfer film of this comparative example was obtained.

Ultraviolet rays of an exposure dose of 1000 mJ / cm 2 were irradiated to the molded articles obtained in Examples 1, 2, and 1 and Comparative Example 2 with a high-pressure mercury lamp of 120 W / cm to form the hard coat layer 3 (or the second hard coat layer 9) was fully cured. Next, evaluation items and evaluation criteria of these molded products are shown below.

(Bur)

○: There is no burr.

?: There are burrs of less than 5 mm.

X: There is burr of 5 mm or more.

(short)

○: There is no shot at all.

?: There is a shot of less than 5 mm.

X: There is a shot of 5 mm or more.

(crack)

○: There is no crack.

X: There is a crack.

(Wash out)

○: There is no washout at all.

?: There is a washout of less than 1 mm.

×: There is a washout of 1 mm or more.

(Flow mark)

○: Flow trace can not be confirmed.

X: Flow marks can be confirmed.

(all sorts of flowers)

○: There is no roughness on the surface.

X: There is roughness on the surface.

(Interlayer delamination)

○: No peeling.

X: In peeling.

(Adhesion test)

This test is based on the adhesion crosscut method of JIS K5600-5-6.

○: No peeling at all.

B: The peeled state is 2 or less.

X: Peeled state is 3 or more.

(Pencil hardness test)

This test conforms to JIS K5600-5-4.

(Steel woolling)

The surface of the steel wool # 0000 after the reciprocating rubbing five times at a load of 500 g / cm 2 at a speed of 30 mm / sec was observed with naked eyes and evaluated as follows.

○: Almost no scratches are seen.

?: No more than 20 scratches.

X: Appears as whitened scattered surface.

(RCA wear test)

This test conforms to the test of ASTM F2357-04.

After a 200-count test in a continuous test with a load of 175 g, the sample was observed with naked eyes and evaluated as follows.

○: Almost no scratches are seen.

△: It was shaved but not exposed to the base.

X: The lower surface is exposed.

Table 1 shows the evaluation results of each example and each comparative example.

From the results shown in Table 1, it can be seen that Examples 1 and 2, which are examples of the embodiments of the present invention, exhibit balanced performance in each evaluation item.

The transfer film obtained by the present invention can be used for surface protection and decoration of housings, panel members, etc. used for home appliances, home appliances, office equipment, automobile parts and the like.

1: Support film
2:
3: hard coat layer
4: Primer layer
5: decorative floor
6: Adhesive layer
7: Molded resin
8: First hard coating layer
9: Second hard coating layer

Claims (8)

In the decorative transfer film of the type which is cured by ultraviolet rays after transferring,
The decorative transfer film is formed by laminating a releasing layer, a hard coating layer, a primer layer, a decorative printing layer, and an adhesive layer on one surface of a supporting film in this order,
Wherein the composition of the hard coat layer is an acrylic acrylate resin having a weight average molecular weight of 40,000 or more and 100,000 or less and containing a hydroxyl group and an ultraviolet initiator and silica particles having an average particle diameter of 10 nm or more and 100 nm or less And a polytetrafluoroethylene powder having an average particle diameter in a range of 1 占 퐉 to 10 占 퐉,
Wherein the composition of the primer layer is a two-component curing resin comprising at least an acrylic polyol resin, a polyisocyanate compound and a vinyl chloride vinyl acetate copolymer resin containing a hydroxyl group. The method according to claim 1,
Wherein the content of the polytetrafluoroethylene powder contained in the hard coat layer is in the range of 0.1 wt% to 2 wt% with respect to the acrylic acrylate resin. 3. The method according to claim 1 or 2,
Wherein the content of the silica particles contained in the hard coat layer is in the range of 10 wt% to 40 wt% with respect to the acrylic acrylate resin. 4. The method according to any one of claims 1 to 3,
Wherein the hard coat layer further comprises a polyisocyanate compound. In the decorative transfer film of the type which is cured by ultraviolet rays after transferring,
The decorative transfer film is formed by laminating a release layer, a first hard coat layer, a second hard coat layer, a primer layer, a decorative print layer, and an adhesive layer on one surface of a support film in this order,
Wherein the composition of the first hard coat layer is selected from the group consisting of an acryl acrylate resin having a weight average molecular weight of 40,000 or more and 100,000 or less and containing a hydroxyl group and an ultraviolet ray initiator and having an average particle diameter of 10 nm or more and 100 nm or less Silica particles and at least a polytetrafluoroethylene powder having an average particle diameter in a range of 1 占 퐉 or more and 10 占 퐉 or less and further containing no polyisocyanate compound as an ultraviolet-
Wherein the composition of the second hard coat layer is selected from the group consisting of an acryl acrylate resin having a weight average molecular weight of 40,000 or more and 100,000 or less and containing a hydroxyl group and an ultraviolet ray initiator and having an average particle diameter of 10 nm or more and 100 nm or less A non-sticky ultraviolet-curable composition containing at least silica particles and a polyisocyanate compound and free of polytetrafluoroethylene powder,
Wherein the composition of the primer layer is a two-component curing resin comprising at least an acrylic polyol resin, a polyisocyanate compound and a vinyl chloride vinyl acetate copolymer resin containing a hydroxyl group. 6. The method of claim 5,
The thickness of the first hard coat layer is set within a range of 0.5 탆 to 2.5 탆,
Wherein the thickness of the second hard coat layer is in the range of 3.0 占 퐉 to 8.0 占 퐉. The method according to claim 5 or 6,
Wherein the content of the polytetrafluoroethylene powder contained in the first hard coat layer is in the range of 0.1 wt% to 2 wt% with respect to the acrylic acrylate resin contained in the first hard coat layer Decorative transfer film. 8. The method according to any one of claims 5 to 7,
Wherein the content of the silica particles contained in the first hard coating layer and the second hard coating layer is 10 wt% or more and 40 wt% or less relative to the acrylic acrylate resin contained in the first hard coating layer and the second hard coating layer, Of the total thickness of the decorative transfer film.

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