JPH08216598A - Transfer sheet - Google Patents

Abstract

PURPOSE: To provide a transfer sheet capable of transfer forming on a transfer medium a surface protective layer having not only excellent superficial physical properties such as wear resistance, anti-abrasion property, solvent resistance or the like, but also weatherability. CONSTITUTION: At least rigid coating layer 3 and adhesive layer 4 are successively laminated in turn on the base body sheet 2, and each layer is transferred on the transfer medium as a transfer layer 6, then, the constitution is made such that, as the base body sheet 2 is separated, the rigid coating layer 3 appears on the surface side and the rigid coating layer 3 being transferred on the transfer medium becomes a superficial protective layer, in addition, the rigid coating layer 3 is formed of crosslinking resin, and both layers of the rigid coating layer 3 and adhesive layer 4 are incorporated with a ultraviolet absorber.

Description

Detailed Description of the Invention

[0001]

The present invention relates to wear resistance, scratch resistance,
The present invention relates to a transfer sheet capable of transferring and forming a surface protective layer excellent in weather resistance as well as surface properties such as solvent resistance on a transfer target.

[0002]

2. Description of the Related Art Heretofore, transfer sheets have been known for transferring and forming decorative layers, surface protective layers, etc. on various products for the purpose of decorating various products and protecting their surfaces. In order to impart abrasion resistance, scratch resistance, solvent resistance, etc. to the layer to be the surface protective layer that is transferred to the transfer target in the transfer sheet used for such purpose, ionization of ultraviolet rays, electron beams, etc. It has been proposed to form the layer using an ionizing radiation-curable resin that forms a cured film having a three-dimensional cross-linking structure when irradiated with radiation (Japanese Patent Publication No. Sho 6).
1-3327, JP-B 64-1114, JP-B 64-1115, etc.).

[0003]

However, although the surface protective layer formed of the ionizing radiation-curable resin exhibits the above-mentioned physical properties, it has insufficient weather resistance and is particularly suitable for outdoor use. The protective layer transferred and formed on the product to be provided was discolored, cracked, deteriorated, etc. with the passage of time, and the physical properties of the resin were deteriorated, which also became a factor of impairing the aesthetic appearance of the product to be transferred. .

On the other hand, it has been proposed to add an ultraviolet absorber to the protective layer to improve the weather resistance of the protective layer itself and also the transferred material (Japanese Patent Laid-Open No. 56-53086). When an ultraviolet absorber in an amount capable of obtaining sufficient weather resistance is added to the above-mentioned ionizing radiation-curable resin, the crosslinking reaction is inhibited by the absorber and the crosslinking density of the resin is lowered, resulting in a protective layer. It is difficult to impart desired physical properties, and it is difficult to improve wear resistance and weather resistance at the same time.

Further, when the protective layer to which the ultraviolet absorber is added is exposed to sunlight, the ultraviolet absorber in the protective layer bleeds (exudes) on the surface of the protective layer due to heating over time due to exposure to sunlight or the like. Not only does the surface whiten, but if the UV absorber near the surface of the protective layer flows out due to rain or dew, the amount of UV absorber contained in the protective layer will naturally decrease, so even if the UV absorber is added, it will be weather resistant. The result was contrary to expectations, such as the fact that it did not improve.

The present invention has been made in order to solve the above problems and provides a surface protective layer having not only surface properties such as abrasion resistance, scratch resistance and solvent resistance but also excellent weather resistance. It is an object of the present invention to provide a transfer sheet that can be transferred and formed on a transfer target.

[0007]

The transfer sheet of the present invention is a transfer sheet in which at least a hard coating layer and an adhesive layer are sequentially laminated on a base sheet having releasability, and the transfer sheet comprises a crosslinkable resin. The hard coating layer is formed, and an ultraviolet absorber is added to both the hard coating layer and the adhesive layer.

In the present invention, as a UV absorber added to the hard coating layer, a reactive UV absorber having a functional group in the molecule that chemically bonds with the resin forming the hard coating layer is used to form an adhesive layer. As the ultraviolet absorber to be added, it is preferable to use a non-reactive ultraviolet absorber having no functional group chemically bonded to the resin forming the adhesive layer.

Further, in the present invention, it is preferable that spherical particles having a hardness higher than that of the resin forming the hard coating layer are dispersed in the hard coating layer.

[0010]

Embodiments of the present invention will now be described in detail with reference to the drawings. 1 is a sectional view showing an example of the transfer sheet 1 of the present invention.

The transfer sheet 1 of the present invention is a transfer sheet in which at least a hard coating layer 3 and an adhesive layer 4 are sequentially laminated on a base sheet 2, and each of the above layers is used as a transfer layer 6 as a transfer target. The hard coating layer 3 appears on the front surface side when the base sheet 2 is peeled off after being transferred, and the hard coating layer 3 transferred to the transfer target serves as the surface protective layer.

In the transfer sheet 1 of the present invention having the above-mentioned constitution as a basic constitution, a decorative property is given between the hard coating layer 3 and the adhesive layer 4 laminated on the base sheet 2 as shown in the figure. For the purpose, a decorative layer 5 such as a pattern print layer or a solid print layer can be provided if necessary.

These layers are gravure-printed, offset gravure-printed, silk-screen-printed, offset-printed, using an ink in which a pigment or the like is dispersed in a known binder.
Known printing means such as electrostatic printing and jet printing,
It can be formed by transfer means, partial vapor deposition, gross matte printing, or the like. The print pattern of the pattern print layer or the solid print layer may be appropriately selected from patterns such as lattices, polka dots and the like, abstract patterns, patterns of natural products such as stones and woods, letters, symbols and the like as desired.

A material having releasability from the hard coating layer 3 is used as the base sheet 2, and a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, polyethylene,
Polyolefin resin such as polypropylene and polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polytetrafluoroethylene resin such as ethylene-tetrafluoroethylene copolymer, polyamide such as nylon 6 and nylon 66, Polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinyl polymers such as vinylon, cellulose triacetate, cellulosic resin such as cellophane, Acrylic resins such as methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate, and polybutyl acrylate, and synthetic resins such as polystyrene, polycarbonate, polyarylate, and polyimide, and, if necessary, melamine resin, silicone , H The release agent is added to an acrylic resin, a fiber material, or the like, which is formed into a sheet by adding a release agent such as base resin or paraffin, or paper such as high-quality paper, thin paper, glassine paper, and sulfuric acid paper. Forming coating films of paints added to known vehicles such as vinyl resins and vinyl resins,
Examples thereof include melamine-based resins, silicones, fluorine-based resins, paraffin and other releasable resins formed by a film such as extrusion coating.

The thickness of the base sheet 2 is appropriately selected according to the intended use, and a thickness of about 4 to 100 μm is usually used.
The preferred thickness is 12-75 μm. If the thickness of the base sheet 2 is less than 12 μm, inconveniences such as breakage and wrinkles are likely to occur during the production of the transfer sheet 1 or during transfer. Further, when the thickness of the base sheet 2 exceeds 75 μm, not only is it disadvantageous in terms of cost, but also the disadvantage that heat during transfer is difficult to be transferred easily occurs. Especially, when transfer is performed by the injection molding simultaneous transfer method. However, the sheet may not be stretched, which may hinder the transfer.

In the transfer sheet 1 of the present invention, the hard coating layer 3 is formed of a crosslinkable resin, and the hard coating layer 3 and the adhesive layer 4 both have an ultraviolet absorber. Has been added.

The crosslinkable resin for forming the hard coating layer 3 has abrasion resistance, scratch resistance, water resistance, chemical resistance, high heat resistance, acid resistance, etc., which can be sufficiently used for outdoor use. It is not particularly limited as long as it has physical properties, and thermosetting resins, room temperature curable resins, two-component reaction curable resins, and the like, conventionally known resins used as crosslinkable resins can be used, The curing reaction is not hindered by the added ultraviolet absorber, and the workability is good because the curing speed is fast and a high crosslink density can be obtained in a short time of several seconds or less, and moreover, flexibility, flexibility and hardness. It is preferable to use an electron beam curable resin because it is easy to control the physical properties of the resin. The details of the electron beam curable resin preferably used in the present invention will be described later.

The hard coating layer 3 is preferably formed on the base sheet 2 with a film thickness of 1 to 200 μm, and is preferably a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, Coating using a coating composition using a crosslinkable resin as a binder such as a wheeler coat, a dip coat, a solid coat by a silk screen coat, a wire bar coat, a flow coat, a comma coat, a pouring coat, a brush coat, and a spray coat. can do.

When the film thickness of the hard coating layer 3 is less than 1 μm when it is formed by coating, an amount of the ultraviolet absorber necessary to obtain a sufficient effect is added to the hard coating layer 3. If this is the case, the amount of the ultraviolet absorber added will increase relative to the amount of the crosslinkable resin used, and the hard coating layer 3 will be inferior in abrasion resistance and the like and desired physical properties cannot be obtained. Further, particularly when a radical polymerization type coating material is used, there is a disadvantage that the hardness of the coating film becomes insufficient due to the inhibition of curing due to the penetration of oxygen in the air. Further, the film thickness of the hard coating layer 3 is 200 μm.
If it exceeds m, inconveniences such as occurrence of burrs and deterioration of flexibility will occur. The more preferable film thickness of the hard coating layer 3 is 2 to 30 μm. With such a film thickness, the hard coating layer 3 can be easily coated with a general-purpose machine such as a gravure coater or a roll coater and with good productivity. Can be formed.

The adhesive layer 4 is made of a thermoplastic resin such as an acrylic resin, a vinyl chloride-vinyl acetate copolymer, a thermoplastic polyurethane resin, or a thermosetting resin such as a two-component curable polyurethane having a blocked isocyanate as a curing agent. 3 to 20 μm using a resin and the same coating means as the hard coating layer 3.
The coating is formed to a thickness of.

The ultraviolet absorbers to be added to both the hard coating layer 3 and the adhesive layer 4 are conventionally known ultraviolet absorbers such as benzotriazole type and salicylate type.
Examples include organic UV absorbers such as benzophenone-based, cyanoacrylate-based, substituted acrylonitrile-based, and nickel chelate-based UV absorbers, or inorganic-based UV absorbers composed of fine particles such as zinc oxide, titanium oxide, and cerium oxide having a particle size of 0.2 μm or less. However, considering the ultraviolet absorbing performance, the surface properties of the hard coating layer 3 after addition, the price, etc., a benzotriazole type is preferable. Further, in order to prevent the deterioration of the ultraviolet absorbent, the hard coating layer 3 and the adhesive layer 4 include a hindered amine light stabilizer (HALS), a phenol heat stabilizer, an antioxidant, etc. It is preferably added in addition to the ultraviolet absorber.

When the decorative layer 5 is provided between the hard coating layer 3 and the adhesive layer 4, an ultraviolet absorber, a hindered amine light stabilizer (HALS), or a phenolic resin is also provided in the decorative layer 5. It is also possible to add heat stabilizers, antioxidants, etc.,
The transfer sheet 1 of the present invention also includes such a sheet.

In the present invention, the hard coating layer 3 is made of a crosslinkable resin, and the hard coating layer 3 and the adhesive layer 4 are used.
It is particularly important that an ultraviolet absorber is added to both layers.
Here, the ultraviolet light attenuation reaching the surface of the transferred material is proportional to the total amount δ of the ultraviolet absorbents in the thickness direction per unit area contained in the transfer layer if the type of the added ultraviolet absorbents is the same, When the addition concentration of the ultraviolet absorber per volume is d and the total film thickness of the layer containing the ultraviolet absorber in the transfer layer is t, the total amount δ of the ultraviolet absorber can be represented by the following formula 1.

[0024]

[Equation 1] δ = dt ... [1]

In order to increase the total amount of ultraviolet rays absorbed in the transfer layer and reduce the deterioration of the body to be transferred and the transfer layer due to ultraviolet rays (increase the weather resistance), the larger the total amount δ of the ultraviolet absorbers, the more preferable. As can be seen from the above formula [1], if the total amount δ of the ultraviolet absorbers is increased when the film thickness t is small, the concentration d of the ultraviolet absorbers becomes too large, which causes the problem of the coating film as described above. Further, if the concentration d is set to such a level that problems such as inhibition of curing of the coating film do not occur, then the total amount δ becomes small this time, and the ultraviolet absorbing ability becomes insufficient. On the other hand, if the film thickness t is large, a sufficient total amount δ of the ultraviolet absorber can be obtained even with a low concentration d of the ultraviolet absorber which does not cause the above problems in the coating film. When only the thickness of 3 is increased, the transfer sheet becomes hard and lacks flexibility, and cracks are likely to occur at the time of transfer or at the time of printing formation of the decorative layer 5, and foil breakage also becomes poor. Further, there is a problem that curling and distortion of the transfer sheet may occur due to curing shrinkage of the hard coating layer 3, which is not realistic.

However, the layer to which the ultraviolet absorber is added is changed from only the hard coating layer 3 to the adhesive layer 4, and further to the decorative layer 5.
By increasing the thickness to, it is possible to increase the total film thickness t of the layer containing the ultraviolet absorber without increasing the thickness of each layer. Then, it becomes possible to sufficiently increase the total amount δ of the ultraviolet absorbers without increasing the addition concentration d of the ultraviolet absorbers. For example, if the thickness of the hard coating layer 3 and the thickness of the adhesive layer 4 are the same, the addition of the ultraviolet absorber to both layers will result in the above [1 ] The film thickness t in the equation is doubled. Therefore, even if the addition concentration d of the ultraviolet absorber in each layer is lowered to 70%, the total amount δ of the ultraviolet absorbers, that is, the ultraviolet absorbing ability is 14%.
It will be 0% and increase.

Therefore, by adding an ultraviolet absorber to both the hard coating layer 3 and the adhesive layer 4 (and also to the decorative layer 5 if necessary), only the hard coating layer 3 can be obtained. Compared with the case where a required amount of ultraviolet absorber is added, the same ultraviolet absorption performance can be obtained with a smaller addition concentration, and the reduction of the crosslink density of the crosslinkable resin forming the hard coating layer 3 can be suppressed to make it hard. A hard coating layer transferred to a transfer target as a transfer layer 6 while maintaining surface properties such as abrasion resistance, scratch resistance, water resistance, chemical resistance, high heat resistance, and acid resistance of the coating layer 3. Even when the adhesive layer 3 and the adhesive layer 4 are exposed to sunlight (ultraviolet ray), these layers do not cause inconveniences such as discoloration, cracks, deterioration, etc., and can have excellent weather resistance. Moreover, the hard coating layer 3 having a three-dimensional crosslinked structure cured with a sufficient crosslink density can suppress the bleeding of the ultraviolet absorber to the surface as much as possible.

The amount of the ultraviolet absorber added to the hard coating layer 3 or the adhesive layer 4 depends on the required weather resistance, the kind of resin forming these layers and the ultraviolet absorbing performance of the ultraviolet absorber added. And the total amount δ per unit area of the ultraviolet absorber added to all layers to which the ultraviolet absorber is added according to the above formula [1] It is sufficient to obtain sufficient weather resistance, for example, when an acrylate resin is used, a benzotriazole-based UV absorber is used, and weather resistance is required to withstand 2000 hours of sunshine weatherometer irradiation. When the layer thickness is about 5 μm, it is preferable to adjust the coating composition for forming each layer so that the coating composition is 5 to 20 parts by weight with respect to 100 parts by weight of the crosslinkable resin after curing. In the same case as above, when the layer thickness is about 50 μm, the addition amount is preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the crosslinkable resin after curing. If the amount of the ultraviolet absorber added is less than the above range, sufficient weather resistance cannot be obtained. On the other hand, when the amount is more than the above range, the surface properties of the hard coating layer 3 are inferior, the ultraviolet absorber impairs the adhesiveness, and the like. This makes it difficult to suppress the bleeding of the ultraviolet absorbent.

Further, in the present invention, as the ultraviolet absorber added to the hard coating layer 3, a reactive ultraviolet absorber having a functional group in the molecule that chemically bonds with the resin forming the hard coating layer 3 is used. As such a reactive ultraviolet absorber, a radical polymerizable double bond such as a vinyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, or the like in the organic ultraviolet absorber as described above, or Those having a cationically polymerizable unsaturated group such as an epoxy group introduced (bonded in the molecule) are used. For example, those represented by the following structural formulas (Formula 1 and 2) are preferably used. .

[0030]

Embedded image

[0031]

Embedded image

By adding the above-mentioned reactive ultraviolet absorber to the hard coating layer 3 and reacting with the ultraviolet absorber and the crosslinkable resin forming the hard coating layer 3 and binding, the ultraviolet absorber is added. It is possible to prevent a decrease in the crosslink density of the crosslinkable resin, and it is possible to more effectively prevent the bleeding or outflow of the ultraviolet absorber, and the deterioration of the weather resistance due to it, and to further improve wear resistance and scratch resistance. It is possible to achieve both surface properties such as properties and weather resistance.

On the other hand, the ultraviolet absorber added to the adhesive layer 4 is a non-reactive ultraviolet absorber having no functional group chemically bonded to the resin forming the adhesive layer 4, that is, a conventionally known one as described above. It is preferable to use the organic UV absorber as it is. By making the UV absorber added to the adhesive layer 4 non-reactive, the resin forming the adhesive layer 4 reacts with the UV absorber. It is possible to prevent the adhesive force of the adhesive layer 4 from being lowered due to the storage.

In the present invention, the physical properties of the hard coating layer 3,
In particular, in order to further improve abrasion resistance, it is preferable to disperse spherical particles 7 having a hardness higher than that of the crosslinkable resin forming the hard coating layer 3 in the hard coating layer 3.

The spherical particles 7 may have a surface surrounded by a smooth curved surface, such as a true sphere, an elliptic sphere having a flat sphere, a shape close to the true sphere or an ellipsoid.
The spherical particles 7 are preferably spherical particles having no protrusions or corners on the particle surface, that is, a so-called cutting edge.

The spherical particles 7 greatly improve the abrasion resistance of the surface resin layer itself as compared with the irregular particles of the same material, do not abrade the coating apparatus, and even after curing the coating film, It is characterized in that it does not abrade other objects that come into contact with it, and the transparency of the coating film is also high, and its effect is particularly great when there is no cutting edge.

Here, the action of dispersing such spherical particles 7 in the hard coating film will be described. Incidentally, FIG. 2 is an explanatory diagram for explaining the action of dispersing the spherical particles 7 in the hard coating film, and FIG.
Shows a state in which the vicinity of the surface is enlarged when stress is applied to the surface of the hard coating layer 3 (the surface that appears when it is transferred to a transfer target) in which the irregular shape is It shows a state in which the vicinity of the surface is enlarged when stress is applied to the surface of the hard coating film layer 3 using the polygonal particles 9.

When stress is applied to the surface of the hard coating layer 3 by another contact material 8 as shown in FIG. 3 (a), since the spherical particles 7 have a smooth surface, the surface of the particle is contacted with the contact material. Not only 8 becomes slippery, but also stress is difficult to be transmitted to the particles, and the transmitted stress is dispersed. Therefore, there is no fear that the spherical particles 7 will fall off from the crosslinkable resin.
On the other hand, when the irregular-shaped particles 9 are used as shown in FIG. 3B, the contact object 8 is apt to be caught by the contact object 8 at the protrusion-shaped portion of the surface of the particle, which causes the The fixed particles 9 easily fall off from the crosslinkable resin. Therefore, the surface of the hard coating layer 3 is slippery and wear resistance is significantly improved. Further, the spherical particles 7 on the surface are less likely to be caught in the case of scooping or the like as compared with the irregular-shaped particles 9, and the surface of the other contact object 8 is not damaged or worn.

Further, as shown in FIG. 3B, when the irregular particles 9 are used, the voids 10 and the like tend to exist between the crosslinkable resin and the irregular particles, but the spherical particles 7 When using, such voids are unlikely to occur. Therefore, an air layer is not easily formed in the abrasion resistant resin layer, and the surface is not whitened, so that the designability is not deteriorated. Further, the absence of the gap also enhances the bonding strength with the crosslinkable resin, which also contributes to the improvement of the wear resistance. Further, when the hard coating layer 3 is formed by coating, there is no possibility that the spherical particles 7 contained in the coating composition will abrade a roll of a coating device, a doctor knife or the like.

A coating composition for forming the hard coating layer 3 such that the amount of the spherical particles 7 dispersed in the hard coating layer 3 is 1 to 20 parts by weight based on 100 parts by weight of the crosslinkable resin after curing. Is preferably adjusted. The particle size of the spherical particles 7 is usually 0.1 to 0.1 when the hard coating layer 3 has a thickness of 3 μm.
Those having a particle size of 3 μm (average particle diameter) can be used and are appropriately selected according to the thickness of the hard coating layer 3. If the particle size of the spherical particles 7 is small, the wear resistance is low, while if the particle size is large, the wear resistance is improved, but if the particle size is too large with respect to the thickness of the hard coating layer 3, it becomes hard. Uniform coating when forming the coating layer 3 by coating becomes difficult. For example, when forming the hard coating layer 3 to have a thickness of 10 to 30 μm, the particle diameter of the spherical particles 7 is preferably in the range of 5 to 30 μm.

The spherical particles 7 may be made of any material as long as they have a hardness higher than that of the crosslinkable resin forming the hard coating layer 3, and both inorganic particles and organic resin particles can be used. The difference in hardness between the spherical particles 7 and the crosslinkable resin is measured by a method such as Mohs hardness or Vickers hardness. For example, when expressed in Mohs hardness, it is preferably 1 or more.

Specific examples of the material of the spherical particles 7 include α-alumina, silica, chromium oxide, iron oxide, diamond,
Examples thereof include inorganic particles such as graphite, and organic resin particles such as synthetic resin beads such as crosslinked acryl. A particularly preferable spherical particle 7 is spherical α-alumina because it has a very high hardness and a large effect on wear resistance and a spherical particle can be obtained relatively easily.

Spherical α-alumina is alumina hydrate,
Mineralizers or crystallization agents such as halogen compounds and boron compounds are added in small amounts to crushed products of fused alumina or sintered alumina, and heat-treated at a temperature of 1400 ° C or higher for 2 hours or more, the cutting edge in alumina is The number is reduced and at the same time the shape is spherical. Such spherical alumina is available from Showa Denko KK as “spherical alumina (S
physical Alumina) AS-10, AS
-20, AS-30, AS-40, AS-50 "having various average particle sizes are commercially available.

The spherical particles 7 can be treated on the surface thereof. For example, dispersibility is improved by treating with a fatty acid such as stearic acid. Further, by treating the surface with a silane coupling agent, the adhesion with the crosslinkable resin and the dispersibility of particles in the coating composition are improved. As the silane coupling agent, an alkoxysilane having a radical polymerizable unsaturated bond such as vinyl or methacryl in the molecule,
Examples thereof include alkoxysilanes having a functional group such as epoxy, amino and mercapto in the molecule.

The silane coupling agent may be, for example, (meth), depending on the type of crosslinkable resin forming the hard coating layer 3.
In the case of an electron beam curable resin such as acrylate, an alkoxysilane having a radical polymerizable unsaturated bond is used, and in the case of a two-component curable urethane resin, an alkoxysilane having an epoxy group or an amino group is used. It is preferable to select the type of radically polymerizable unsaturated bond or functional group.

Specific examples of the alkoxysilane having a radical-polymerizable unsaturated bond include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane and γ-methacryloxy. Propyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane , Γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, and other alkoxysilanes having a radical-polymerizable unsaturated bond in the molecule, and epoxies, aminos, and mercuras in the molecule. There are alkoxysilanes having a functional group bets like.

The method of treating the surface of the spherical particles 7 with the silane coupling agent is not particularly limited, and a known method can be used. For example, a dry method is a method of spraying a predetermined amount of a silane coupling agent while vigorously stirring the spherical particles 7, and a wet method is a method in which the spherical particles 7 are immersed in a solvent such as toluene.
After dispersing, a predetermined amount of silane coupling agent is added and reacted. As the treatment amount (required amount) of the silane coupling agent with respect to the spherical particles 7, a treatment amount with which the minimum coverage area of the silane coupling agent is 10 or more relative to 100 of the specific surface area of the spherical particles 7 is preferable. The minimum coverage area of the spherical particles 7 is 100 of the specific surface area of the spherical particles 7.
On the other hand, if it is less than 10, it is not so effective.

In forming the hard coating layer 3, the coating composition containing a crosslinkable resin as a binder includes a coloring agent such as a dye or pigment in addition to the ultraviolet absorber and the spherical particles 7.
Other fillers such as CaCO ₃ , BaSO ₄ , nylon resin beads, and other known matting modifiers and extenders, and other additives may be added as necessary.

The crosslinkable resin used for forming the hard coating layer 3 has a higher wear resistance as the crosslink density increases.
Although scratch resistance and the like are improved, flexibility and flexibility are reduced, and therefore the crosslink density of the crosslinkable resin depends on the surface physical properties of the hard coating layer 3 required by the application of the transfer sheet 1 and the like. It is preferable to select it appropriately according to the type of the base material. The crosslink density can be represented by, for example, the average molecular weight between crosslinks shown in the following Expression 2.

[0050]

## EQU00002 ## Average molecular weight between crosslinks = total molecular weight / number of crosslinking points [2] However, the overall molecular weight is Σ (moles of each component blended × molecular weight of each component) ), And the number of crosslinking points is Σ [{(number of functional groups of each component-1) x 2} x number of moles of each component].

Table 1 below shows an experimental example showing the relationship between abrasion resistance and flexibility when the average molecular weight between crosslinks of the crosslinkable resin was changed.

Table 1 shows that a urethane acrylate oligomer and two kinds of acrylate monomers are used as the crosslinkable resin, and the average molecular weight between crosslinks is adjusted by changing the mixing ratio of the components, and spherical particles 7 having a spherical shape with an average particle size of 30 μm are used. Α
-Alumina was added to a support sheet at a coating amount of 25 g / m ² with a composition obtained by adding 11 parts by weight to 100 parts by weight of a crosslinkable resin to cure the composition, which was then cured with a heat-sensitive adhesive on a synthetic resin plate. It is a comparison of abrasion resistance and flexibility when used for transfer.

The abrasion resistance test was conducted according to JIS K6902, and the number of times until the thickness of the resin layer was reduced to half was shown.
As for the flexibility, as shown in FIG. 3, the state of the transfer sheet after being bent by 180 ° with a radius of curvature r1 mm was observed, and no trace was left as ◎, and a trace was left. ○, those with slight cracks partially found, △,
The mark "X" indicates that the transfer layer was peeled off due to large cracks. In addition, the experiment No. 6 is a conventional α- which has an irregular shape with an average particle diameter of 30 μm without using the spherical particles 7.
Alumina was used as an experiment No. The same amount as 1 to 5 was added. In the above resin system, the average molecular weight between crosslinks is 100 to 1.
Although it can be used in the range of 000, it is more preferably 200 to 700. Further, when a flexible base material is used, it is more preferable to use one having an average molecular weight between crosslinks of 300 to 700. Within the above range, a cosmetic material having good flexibility and abrasion resistance can be obtained. . If the average molecular weight between crosslinks is less than 200, the flexibility is insufficient, and the transfer layer is unfavorably cracked when transferred to the transfer target having an uneven shape. Further, if the average molecular weight between crosslinks exceeds 700, the difference in abrasion resistance from the case of using amorphous particles is eliminated, which is not preferable.

[0054]

[Table 1]

The experimental results in Table 1 above show that, when the type of crosslinkable resin is the same, the smaller the average molecular weight between crosslinks (that is, the higher the crosslink density), the more the crosslinkable resin firmly holds the spherical particles 7 and It shows that the wear property is further improved. Therefore, the abrasion resistance can be further improved by adjusting the average molecular weight between crosslinks of the crosslinkable resin to be small within the range of not impairing the flexibility.

The electron beam curable resin preferably used as the crosslinkable resin in the present invention is a radical polymerizable unsaturated group such as a (meth) acryloyl group or a (meth) acryloyloxy group, or a cation such as an epoxy group in the molecule. The main component is a monomer, prepolymer, or polymer having two or more polymerizable functional groups or thiol groups. These monomers, prepolymers, or polymers alone,
Alternatively, a plurality of them may be mixed and used. In addition, in the present specification, for example, the term “(meth) acroyl group” means an acryloyl group or a methacryloyl group.

Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate and epoxy (meth).
Acrylate, melamine (meth) acrylate, triazine (meth) acrylate and the like can be mentioned, and the molecular weight is usually 100 to 10,000, more preferably 10
The thing of 0-5000 is used. In the present invention, either an acrylate or a methacrylate can be used, but the crosslinking curing rate by electron beam is high, high speed,
Acrylate is more advantageous in that it can be cured efficiently in a short time. As the polymer having a radically polymerizable unsaturated group, a polymer having a degree of polymerization of the above prepolymer of about 10,000 or more is used.

Among the monomers having a radical-polymerizable unsaturated group, the monofunctional monomer of the (meth) acrylate compound is, for example, methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth) acrylate. ,
Methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N,
N-dimethylaminoethyl (meth) acrylate, N,
N-diethylaminoethyl (meth) acrylate, N,
N-diethylaminopropyl (meth) acrylate,
N, N-dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate,
Tetilahydroxyfurfuryl (meth) acrylate, methoxytripropylene glycol (meth) acrylate,
Examples include 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate and 2- (meth) acryloyloxypropyl hydrogen phthalate.

As the polyfunctional monomer having a radical polymerizable unsaturated group, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexyldiol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenol A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Over DOO, glycerin polyethylene oxide tri (meth) acrylate, tris (meth)
Acryloyloxyethyl phosphate etc. can be illustrated.

Examples of the prepolymer having a cationically polymerizable functional group include epoxy resins such as bisphenol type epoxy resin, novolac type epoxy resin, alicyclic type epoxy resin and aliphatic type epoxy resin, aliphatic type vinyl ether and aromatic type resin. Examples thereof include vinyl ether resins such as vinyl ether, urethane vinyl ether and ester vinyl ether, and prepolymers such as cyclic ether compounds and spiro compounds. Further, as an example of the monomer having a cationically polymerizable functional group, the above-mentioned prepolymer monomer can be used.

Examples of the monomer having a thiol group include:
Examples thereof include trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate.

Among these compounds, the radical polymerization type urethane (meth) acrylate is preferable from the viewpoints of surface physical properties after transfer, elongation and flexibility. Further, a cationic polymerization type epoxy is preferable from the viewpoint that curing inhibition by oxygen in air is unlikely to occur.

Usually, one of the above compounds is used,
Alternatively, two or more kinds of them are mixed and used, but in order to impart ordinary coating suitability to the electron beam curable resin, the weight ratio of the prepolymer or polymer to the monomer is the prepolymer or polymer. / It is preferable that the above-mentioned monomer = 5/95 to 95/5.

In selecting the monomer, when flexibility of the cured product is required, the amount of the monomer may be decreased or monofunctional or bifunctional in a range that does not hinder coating suitability. An acrylate monomer is used, and the structure has a relatively low crosslinking density. In addition, when abrasion resistance, heat resistance, solvent resistance, etc. of the cured product are required, increase the amount of the monomer within a range that does not hinder the coating suitability, or use a monofunctional tri- or higher functional acrylate alone. A structure having a high cross-linking density can be obtained by using the body. still,
The suitability for coating and the physical properties of the cured product can be adjusted by mixing a mono- or di-functional monomer and a tri- or higher functional monomer.

The monofunctional acrylate monomer is 2
-Hydroxy acrylate, 2-hexyl acrylate, phenoxyethyl acrylate and the like can be mentioned. Further, as the bifunctional acrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate and the like, and as the trifunctional or higher functional acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol. Hexaacrylate etc. are mentioned.

Further, an electron beam non-curable resin may be added to the electron beam curable resin for adjusting the physical properties such as flexibility and surface hardness of the cured product (hard coating layer 3). As the electron beam non-curable resin, a thermoplastic resin such as acrylic resin, urethane resin, fibrin resin, polyester resin, butyral resin, polyvinyl chloride, or polyvinyl acetate is used.
In particular, when the cured coating film has flexibility (deformation during transfer sheet 1 production or transfer, prevention of cracks due to bending) and scratch resistance and abrasion resistance, and when the coating film is solvent dried, It is preferable to use the non-crosslinking type thermoplastic acrylic resin as the electron beam non-curing resin because it can be dried by touch even in the uncured state and the decorative layer 5 and the adhesive layer 4 can be formed thereon.

As the non-crosslinking type thermoplastic acrylic resin,
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) Isobutyl acrylate,
(Meth) acrylic acid-n-amyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-octyl,
(Meth) acrylic acid alkyl ester such as lauryl (meth) acrylate, 2-chloroethyl (meth) acrylate, alkyl (meth) acrylate halide such as (meth) acrylic acid-2-chloropropyl, (meth) 2-Hydroxyethyl acrylate, -2- (meth) acrylic acid
(Meth) acrylic acid ester having an OH group such as hydroxypropyl, methyl α-chloro (meth) acrylate,
Halogenated (meth) acrylic acid ester such as α-chloro (meth) acrylic acid ethyl ester, (meth) acrylic acid-1
Α having an OH group such as chloro-2-hydroxyethyl
-Alkyl (meth) acrylic acid ester, or (meth)
1 of (meth) acrylic monomers such as glycyl acrylate
Or a homopolymer consisting of two or more kinds, or a copolymer, and having an average molecular weight of 50,000 to 600,000 and a glass transition temperature of 50 to 130 ° C, preferably 80 to 110.
What is ° C can be used.

When the average molecular weight is less than 50,000, the scratch resistance of the hard coating layer 3 after curing is extremely reduced. When the average molecular weight exceeds 600,000, the elongation of the hard coating film layer 3 at the time of transfer is reduced, so that the hard coating film layer 3 is cracked due to the deformation at the time of transfer. When the glass transition temperature is less than 50 ° C., the scratch resistance of the hard coating layer 3 after curing is extremely lowered, and after the solvent is dried, the non-adhesiveness (dryness to the touch) in an uncured state is obtained. ) Becomes insufficient. When the glass transition temperature exceeds 130 ° C., the elongation of the hard coating layer 3 during transfer is reduced.

The above-mentioned acrylic resin added to the electron beam curable resin as the electron beam non-curable resin contains 30 to 90 parts of the electron beam curable resin composed of the above-mentioned prepolymer per 100 parts by weight of the acrylic resin. It is added so that it may be part by weight. When the amount of the electron beam curable resin is 30 parts by weight or less, the crosslink density of the hard coating film layer 3 by electron beams becomes extremely rough, the strength of the hard coating film layer 3 itself is insufficient, and the scratch resistance is lowered. To do. When the amount of the electron beam curable resin is 90 parts by weight or more, the non-adhesiveness of the coating film in the uncured state becomes insufficient after solvent drying, and the hard coating layer 3 has a high electron beam crosslinking density. Therefore, the elongation of the protective layer itself decreases, and deformation, damage, cracks, etc. occur during transfer.

The average molecular weight is 50,000 to 600,000,
A hard coating layer made of a non-crosslinked thermoplastic acrylic resin having a glass transition temperature of 50 to 130 ° C. and an electron beam curable resin in which a prepolymer having two or more (meth) acryloyl groups in one molecule is compatible with each other. 3 is formed, when the acrylic resin is applied onto the base sheet 2 and the diluting solvent is dried and volatilized, the acrylic resin is compatible with the prepolymer to form the uncured hard coating layer 3. In the melted state, the part where the acrylic resin molecule simple substance is entangled with the prepolymer molecule simple substance, the part where the acrylic resin molecule group is entangled with the prepolymer molecule group, and the part where the prepolymer molecule simple substance enters the acrylic resin molecule group , And is presumed to be formed by being mixed with a portion where the acrylic resin molecule simple substance enters the prepolymer molecule population.

Therefore, since the acrylic resin molecule or the molecule group and the prepolymer molecule are in close proximity to each other and are entwined and fixed by the intermolecular force, fluidity is suppressed,
Since they are non-adhesive solids, but do not have chemical bonds with each other, the uncured hard coating layer 3 at this stage has a moderate elastic limit and sufficient plastic deformability (that is, flexibility) at room temperature, It behaves as a flexible solid film.

When a stress is applied to the uncured hard coating layer 3, the hard coating layer 3 is elastically deformed as long as a force within a range not exceeding the intermolecular force is applied between each molecule.
Easily bends and deforms, and when the stress disappears, it returns to its original shape. Moreover, when a force exceeding the intermolecular force is applied between the molecules, it is considered that slippage occurs between the molecules or the group of molecules and plastic deformation occurs. Therefore, the hard coating layer 3 has sufficient flexibility in the uncured state due to external stress.

Furthermore, when the hard coating layer 3 is heated to a high temperature, the thermal kinetic energy of the molecules gradually releases each molecule from the constraint of the potential energy of the intermolecular force, and the elastic restoring force between the molecules decreases. Therefore, the plastic deformation becomes stronger, the temperature becomes higher, and when the thermal kinetic energy of the molecule completely overcomes the potential energy of the intermolecular force, fluidity occurs, and the hard coating layer 3 becomes thermoplastic. Have. Due to this flexibility, plastic deformability, and thermoplasticity, the hard coating layer 3 in an uncured state has sufficient moldability, and such an electron beam curable resin is in an uncured state after coating. However, if the solvent is volatilized and dried, it becomes a non-adhesive solid.

The hardening timing of the hard coating layer 3 is as follows: before the transfer, when the hard coating layer 3 is in the uncured state, but is dry to the touch (non-adhesive, non-fluid) after solvent drying. Simultaneously with or after transfer, the electron beam curable resin added with the non-crosslinking type thermoplastic acrylic resin is more excellent than the case where the acrylic resin is not added even after being cured with an electron beam. It has great flexibility, elasticity, and plasticity. In addition, it has the same level of abrasion resistance, scratch resistance, chemical resistance, heat resistance, etc. as compared with the case where the acrylic resin is not added.

This is because the hard coating layer after cross-linking and curing has 3 parts of non-cross-linking type thermoplastic acrylic resin molecules and pre-polymer molecules.
A dimensional cross-linking structure intermingles with each other and is entwined with each other (so-called interpolymer network), a part consisting only of the three-dimensional cross-linking structure of the prepolymer molecule, and a part consisting only of the non-cross-linking type thermoplastic acrylic resin molecule population. Comprised of a hybrid polymer of 3D, the mechanical strength of the three-dimensional crosslinked structure of prepolymer molecules and the deformability, slipperiness, and shock absorption of the acrylic resin molecule group work together to counteract external stress during wear. In addition, it is considered that sufficient abrasion resistance is produced by absorbing and relaxing a part thereof.
With respect to external stress at the time of molding, the acrylic resin molecule group, the three-dimensional cross-linking structure of the acrylic resin molecules and the prepolymer molecules enter each other, and the entangled structural parts follow the deformation, thereby providing a greater moldability. Is considered to be capable of expressing.

Therefore, the hard coating layer 3 formed of the electron beam curable resin to which the non-crosslinking type thermoplastic acrylic resin is added
The hard coating layer 3 is harder than the case where only the liquid monomer and the prepolymer are electron beam cured even when the coating composition is cured on the base sheet 2 and then transferred. Has high flexibility (although the thermoplasticity is lost), and when transferred to a transfer target having an uneven shape,
The cracks and damages are less likely to occur, the conformability to the uneven shape is good, and the scratch resistance, heat resistance, and chemical resistance of the hard coating layer 3 are better, so that there is an inherent contradiction. The heat resistance, chemical resistance, and wear resistance of the hard coating layer 3
It is possible to achieve both the concavo-convex shape moldability.

As the electron beam for curing the electron beam curable resin, Cockloft-Walton type, Van de Graaff type, resonance transformer type, insulating core transformer type, or straight type,
Electrons having energy of 100 to 1000 keV that are irradiated by using various electron beam accelerators such as dynamitron type and high frequency type are used. The electron beam irradiation dose is 0.5
-30 Mrad is preferable.

The transfer sheet 1 of the present invention is suitable for various uses, and is useful as a decorative material for buildings, vehicles, ships, furniture, musical instruments, cabinets, etc., and a decorative material for packaging materials, etc. It is suitable for outdoor use.

Examples of the transfer method using the transfer sheet 1 of the present invention include the following various transfer methods. (A) Japanese Patent Publication No. 2-4080, Japanese Patent Publication No. 4-199
Injection molding simultaneous transfer method as disclosed in Japanese Patent No. 24. (B) JP-A-4-288214 and JP-A-5-57
Vacuum forming simultaneous transfer method as disclosed in Japanese Patent No. 786. (C) Japanese Patent Publication No. 59-51900, Japanese Patent Publication No. 61-5
Lapping simultaneous transfer method as disclosed in Japanese Patent Publication No. 895, Japanese Patent Publication No. 3-2666, etc. (D) A V-cut processing simultaneous transfer method disclosed in Japanese Patent Publication No. 56-7866. (E) A so-called hot stamping method in which the transfer layer 6 side of the transfer sheet 1 is superposed on the surface of the transfer target and is pressed by a heating roller to bond the transfer layer 6 to the transfer target.

Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.

Example 1 An acrylic-melamine resin of 0.6 g / m ^{2 was} coated on a biaxially stretched polyethylene terephthalate sheet having a thickness of 38 μm and then heated at 140 ° C. for 20 seconds to form a release layer. The base sheet 2 was formed.
The following coating composition was applied onto the base sheet 2 by roll coating at 20 g / m ² and cured by electron beam irradiation to give a film thickness of 5
A hard coating layer 3 having a thickness of μm was formed by coating.

[Coating composition] 25 parts by weight of dipentaerythritol hexaacrylate 50 parts by weight of polymethylmethacrylate 25 parts by weight of silica powder 3 parts by weight of polyethylene wax 5 parts by weight of benzotriazole ultraviolet absorber (Ciba)・ Geigy: Tinuvin 900) ・ Hindered amine radical scavenger 2 parts by weight (Sankyo Kasei: Sanol LS292) ・ Benzophenone heat stabilizer 1 part by weight (Ciba / Geigy: Irganox 1010) ・ Methyl ethyl ketone / toluene 300 parts by weight

Then, a wood grain pattern was gravure printed on the hard coating film with a gravure ink using an acrylic resin as a binder, and further overlaid thereon to 300 parts by weight of an acrylic resin adhesive (solid content 30% by weight). On the other hand, 5 g by weight of benzotriazole (manufactured by Ciba-Geigy: Tinuvin 900) was added to the roll coating at 3 g / m ² to give a film thickness of 1
A transfer sheet 1 was obtained by forming an adhesive layer 4 having a thickness of μm.

[Example 2] A hard coating layer 3 was formed by coating using the following coating composition, and was added to 300 parts by weight of an acrylic resin adhesive (solid content 30% by weight).
(2-Hydroxy-3,3-di (l, l-dimethylbenzyl) phenyl) -2 benzotriazole (non-reactive ultraviolet absorber) 10 parts by weight was added except that the adhesive layer 4 was formed. A transfer sheet 1 was obtained in the same manner as in Example 1.

[Coating composition] -Dipentaerythritol hexaacrylate 25 parts by weight-Polymethylmethacrylate 50 parts by weight-Silica powder 25 parts by weight-Polyethylene wax 3 parts by weight-2,2,6,6-tetramethyl- 4-piperidyl methacrylate (reactive UV absorber) 10 parts by weight-benzophenone-based heat stabilizer 1 part by weight (Ciba-Geigy: Irganox 1010) -methyl ethyl ketone / toluene 300 parts by weight

Example 3 A transfer sheet 1 was obtained in the same manner as in Example 1 except that 5 parts by weight of spherical α-alumina having an average particle size of 0.6 μm was added to the coating composition of Example 1. .

Comparative Example 1 Acrylic resin-based release ink (manufactured by Showa Ink: Haku 46-, manufactured by Showa Ink Co., Ltd.) was prepared by adding 10 parts by weight of benzotriazole (manufactured by Ciba Geigy: Tinuvin 900) on the same base sheet 2 as in Example 1. 7), the hard coating layer 3 is formed by coating, and the adhesive layer 4 is further formed on the hard coating layer 3 by an acrylic resin adhesive (solid content 30% by weight) without addition of an ultraviolet absorber, and then transferred. Sheet 1 was obtained.

Comparative Example 2 A coating having the same composition as the coating composition of Example 1 except that benzotriazole (manufactured by Ciba Geigy: Tinuvin 900) was not added on the same base sheet 2 as in Example 1. A hard coating layer 3 is formed by coating with the composition, and further overlaid thereon, benzotriazole (manufactured by Ciba / Geigy: Tinuvin 900) is added to 300 parts by weight of an acrylic resin adhesive (solid content 30% by weight). ) 10 parts by weight was added by roll coating at 3 g / m ² to form an adhesive layer 4 having a film thickness of 4 μm to obtain a transfer sheet 1.

Comparative Example 3 On the same base sheet 2 as in Example 1, the following coating composition was roll-coated at 5 g / m.
² coating, cured by ultraviolet irradiation to form a hard coating layer 3 with a film thickness of 5 μm, and further overlaid on it by an acrylic resin adhesive (solid content 30% by weight) to which no ultraviolet absorber is added A transfer sheet 1 was obtained by applying and forming the adhesive layer 4.

[Coating composition] Dipentaerythritol hexaacrylate 25 parts by weight Polymethylmethacrylate 50 parts by weight Silica powder 25 parts by weight Polyethylene wax 3 parts by weight Photoreaction initiator (benzophenone-based) 3 parts by weight Part-Benzophenone-based heat stabilizer 1 part by weight (Ciba-Geigy: Irganox 1010) -Methyl ethyl ketone / toluene 300 parts by weight

Using the transfer sheets 1 obtained in Examples 1 to 3 and Comparative Examples 1 to 3, simultaneous injection molding transfer using a polycarbonate resin (Made by Mitsubishi Kasei: Novalex) was performed.
A molded product having a size of 3 × 13 cm and a thickness of 2 mm was prepared, and then the base sheet 2 was peeled off to obtain a test body. The following tests 1 to 5 were tried on the obtained test body, and the results are shown in Table 2. A molded product obtained by simply injection-molding a polycarbonate resin without transfer was set as Comparative Example 4, and the results of using this as a test body are also shown in Table 2.

[Test 1] The molded product was subjected to ultraviolet irradiation tester (Iwasaki Electric: Eye Super UV SUV-F11) 3
After irradiation with 00 MJ / m ² , color difference measurement (ΔE ^* ab) was performed with a color difference measuring instrument (Murakami Color Co., Ltd.) to evaluate weather resistance (weather resistance test). However, ΔE ^* ab is by CIE1976_nenkiteino L ^* a ^* b ^* color system.

[Test 2] The whitening of the surface due to the bleeding of the ultraviolet absorbent was observed after the end of the weather resistance test.

[Test 3] JIS K5400 6.14
Was used to measure the pencil hardness.

[Test 4] The surface of the molded product was lightly pressed with a gauze soaked with methyl ethyl ketone and reciprocated 20 times, and then the surface was observed (solvent resistance test).

[Test 5] The surface of the molded product was pressed with a load of 500 g and reciprocated 10 times with steel wool, and then the surface was observed (scratch resistance test).

Tests 3 to 5 were carried out on those before the weather resistance test.

[0098]

[Table 2] * ₁ : Decorative layer 5 disappeared * ₂ : Transfer layer 6 cracked and exfoliated

[0099]

As described above, in the transfer sheet of the present invention, the ultraviolet absorber is added only to the hard coating layer by adding the ultraviolet absorber to both the hard coating layer and the adhesive layer. Abrasion resistance of the hard coating layer by suppressing a decrease in the crosslinking density of the crosslinkable resin forming the hard coating layer in comparison with the case,
While maintaining surface properties such as scratch resistance, water resistance, chemical resistance, high heat resistance, and acid resistance, the hard coating layer transferred to the transfer target as the transfer layer and the adhesive layer are exposed to sunlight (ultraviolet rays). Even when exposed to, it is possible to obtain excellent weather resistance without causing inconveniences such as discoloration, cracking and deterioration of these layers. In addition, the hard coating layer having a three-dimensional crosslinked structure cured with a sufficient crosslink density can suppress the bleeding of the ultraviolet absorber to the surface as much as possible.

Further, a reactive ultraviolet absorber is added to the hard coating layer, and the ultraviolet absorber and the crosslinkable resin forming the hard coating layer are reacted and bonded to each other, whereby the crosslinkable resin by addition of the ultraviolet absorber is added. It is possible to prevent a decrease in the cross-linking density of the UV absorbent, and it is possible to more effectively prevent the bleeding or outflow of the ultraviolet absorbent, and the deterioration of the weather resistance due to the UV absorbent, and further improve the wear resistance, the scratch resistance, etc. It becomes possible to have both surface physical properties and weather resistance, and by using a non-reactive ultraviolet absorber as an ultraviolet absorber added to the adhesive layer,
It is possible to prevent a decrease in the adhesive force of the adhesive layer due to the reaction between the resin forming the adhesive layer and the ultraviolet absorber.

Further, by dispersing spherical particles having a hardness higher than that of the crosslinkable resin forming the hard coating layer in the hard coating layer, the physical properties of the hard coating layer, particularly abrasion resistance, are further improved. You can look down.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of a transfer sheet of the present invention.

FIG. 2 is an explanatory diagram for explaining the action of dispersing spherical particles in a hard coating film.

FIG. 3 is an explanatory view illustrating a test performed for evaluation of flexibility in an experimental example showing a relationship between abrasion resistance and flexibility when the average molecular weight between crosslinks of a crosslinkable resin is changed. It is a figure.

[Explanation of symbols]

 1 Transfer Sheet 2 Base Sheet 3 Hard Coating Layer 4 Adhesive Layer 7 Spherical Particles

Claims (3)

[Claims] 1. A transfer sheet in which at least a hard coating layer and an adhesive layer are sequentially laminated on a base sheet having releasability, wherein the hard coating layer is formed by a crosslinkable resin and is hard. A transfer sheet comprising an ultraviolet absorber added to both the coating layer and the adhesive layer. 2. A reactive ultraviolet absorber having a functional group in the molecule that chemically bonds to the resin forming the hard coating layer is used as the ultraviolet absorber added to the hard coating layer and is added to the adhesive layer. The transfer sheet according to claim 1, wherein a non-reactive ultraviolet absorber having no functional group chemically bonded to the resin forming the adhesive layer is used as the ultraviolet absorber. 3. The transfer sheet according to claim 1, wherein spherical particles having a hardness higher than that of the resin forming the hard coating layer are dispersed in the hard coating layer.