JP2014016422A - Volume hologram transfer foil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a volume hologram transfer foil that suppresses foil rising and foil peeling between a substrate and a protective layer and having good foil cutting property.SOLUTION: The volume hologram transfer foil comprises a substrate, a protective layer containing a curable resin and an adhesive formed on the substrate, a volume hologram layer formed on the protective layer and having a volume hologram recorded therein, and a heat seal layer formed on the volume hologram layer. The content of the adhesive is controlled to such an amount that foil cutting property of the volume hologram can be retained.

Description

  The present invention relates to a volume hologram transfer foil that suppresses the occurrence of foil floating and foil peeling between a substrate and a protective layer and has good foil breakability.

At present, cards with holograms are widely used in plastic cards typified by credit cards and cash cards mainly from the viewpoint of preventing duplication and imparting design properties. Holograms are often used for security applications because they have the advantage of being difficult to duplicate in addition to their excellent three-dimensional expression and beauty.
The principle of the hologram is that the wavefront of the object light is recorded on the photosensitive material as interference fringes by making two light beams (object light and reference light) having the same wavelength interfere, and the same wavelength as the reference light at the time of interference fringe recording. When the light is applied, a diffraction phenomenon occurs due to the interference fringes, and the same wavefront as the original object light can be reproduced.

  Such holograms can be classified into several types according to the recording pattern of interference fringes, but typically can be classified into surface relief holograms and volume holograms. Here, the surface relief hologram is a hologram recorded by forming a fine uneven pattern on the surface of the hologram layer. On the other hand, a volume hologram is a hologram recorded by interference fringes generated by light interference being drawn three-dimensionally in the thickness direction as fringes having different refractive indexes. Volume holograms are those in which hologram images are recorded by the difference in refractive index of materials, and are therefore particularly difficult to replicate as compared to relief holograms. Therefore, the use as a means for preventing forgery of securities and cards is expected.

  Further, in the case of using a hologram as a design imparting or counterfeiting prevention means, various methods are known as a method for imparting a hologram to securities, cards, etc. depending on the object to which the hologram is imparted. As such a method, for example, a method of weaving a slit-shaped hologram or a method of embedding the hologram in a medium so that it can be visually recognized from the outside is known. Method is used. Among them, as a simpler method, a method of sticking a hologram layer at a predetermined position by transferring a hologram layer from a hologram transfer foil in which a hologram is formed on an arbitrary base material has been widely used.

  Here, a plurality of materials having different refractive indexes are generally used for the volume hologram, and usually a photopolymerizable material that can be polymerized by irradiating with specific light is used. For this reason, it is known that the hologram layer (volume hologram layer) in which the volume hologram is recorded tends to increase the mechanical strength. Moreover, the volume hologram has a property that a hologram image is recorded by three-dimensionally arranging the refractive index difference, so that the thickness of the layer on which the hologram is formed is thicker than that of the relief hologram. Tend to be. For this reason, it has been pointed out that the volume hologram layer has poor foil cutting properties and it is difficult to use a method of transferring a hologram layer using a volume hologram transfer foil.

  In addition, in view of the usefulness of providing designability and preventing forgery using holograms, further improvement in versatility is required. Along with this, the volume hologram transfer foil described above is formed in a long shape so that the volume hologram can be continuously applied to a predetermined position in the industrial production process, and the volume hologram is continuously transferred. A method has also been developed. However, it is necessary to partially transfer the volume hologram from the transfer foil, and higher foil cutting properties are required (see Patent Document 1).

  Further, in the manufacturing process of manufacturing the volume hologram transfer foil described above in a roll-to-roll manner, the process of recording and fixing the volume hologram on the hologram layer and curing the protective layer, for example, in the hologram layer In the bleaching step of destroying the pigment contained in the material and making it colorless and transparent, there is a problem that the foil floats or peels off between the protective layer and the substrate, and the interlayer adhesion cannot be maintained.

As a technique for improving interlayer adhesion, as disclosed in Patent Documents 2 to 4, a technique of providing an adhesive layer between layers where peeling easily occurs, a technique of adding an adhesive to the layer, and the like are used. However, while the interlayer adhesion between the protective layer and the base material is improved by the above method, there is a risk that the foil cutting property of the volume hologram transfer foil may be lowered.
Therefore, in the production process, a volume hologram transfer foil that does not cause foil floating or peeling off between the protective layer and the substrate and has good foil breakability is required.

JP 2004-345450 A JP-A-8-258216 JP 2010-173203 A JP 2000-304929 A

  The present invention has been made in view of the above circumstances, and provides a volume hologram transfer foil that suppresses the occurrence of foil floating and foil peeling between the base material and the protective layer and has good foil breakability. The main purpose is to do.

  In order to solve the above problems, the present invention provides a base material, a protective layer formed on the base material and containing a curable resin and an adhesive, and formed on the protective layer, and a volume hologram is recorded. A volume hologram transfer foil having a volume hologram layer and a heat seal layer formed on the volume hologram layer, wherein the pressure-sensitive adhesive content maintains the foil breakability of the volume hologram transfer foil Is provided in a volume hologram transfer foil characterized in that

  According to the present invention, by setting the content of the pressure-sensitive adhesive contained in the protective layer to a predetermined ratio, the volume hologram transfer foil of the present invention is maintained at the same time, and at the same time, the volume hologram transfer foil is rolled to roll. In the step of manufacturing in the above, it is possible to prevent the foil floating and foil peeling between the base material and the protective layer after the volume hologram layer and the protective layer are cured.

  In the said invention, it is preferable that content of the said adhesive is an quantity which makes the breaking elongation of the said protective layer in 23 degreeC in the range of 1.1%-2.1%. By adjusting the content of the pressure-sensitive adhesive in the protective layer so that the breaking elongation of the protective layer falls within the above range, the foil breakability of the volume hologram transfer foil of the present invention can be maintained, and This is because the occurrence of foil floating and foil peeling between the substrate and the protective layer can be suppressed.

  In the above invention, the curable resin is two types of ionizing radiation curable resins having different weight average molecular weights, and one of the two types of ionizing radiation curable resins has a weight average molecular weight of the other. It is preferable that it is 2 times or more. This is because by using two types of ionizing radiation curable resins having different weight average molecular weights, the breaking elongation of the protective layer can be made desired and flexibility can be imparted.

In the above invention, when the pressure-sensitive adhesive contained in the protective layer is an acrylic pressure-sensitive adhesive, and the two types of ionizing radiation curable resins are acrylic resins, the content of the pressure-sensitive adhesive is 2 It is preferable that it is less than 1 weight part with respect to 100 weight part of total content of a kind of ionizing radiation curable resin.
When the pressure-sensitive adhesive contained in the protective layer and the two types of ionizing radiation curable resins in the present invention are the above conditions, the protective layer is broken by setting the content of the pressure-sensitive adhesive contained in the protective layer to a predetermined ratio. The elongation can be within the above range. This is because it is possible to suppress the occurrence of foil floating and foil peeling between the base material and the protective layer without impairing the foil cutting property of the volume hologram transfer foil of the present invention.

  According to the present invention, in the volume hologram transfer foil, when the volume hologram transfer foil is produced in a roll-to-roll manner by containing a predetermined amount of the adhesive in the protective layer, It is possible to prevent the foil from being lifted or peeled off and to have a good foil cutting property when transferring using the volume hologram transfer foil.

It is a schematic sectional drawing which shows an example of the volume hologram transfer foil of this invention.

  Hereinafter, the volume hologram transfer foil of the present invention will be described.

A. Volume hologram transfer foil
The volume hologram transfer foil of the present invention includes a base material, a protective layer formed on the base material and containing a curable resin and an adhesive, and a volume hologram layer formed on the protective layer and having a volume hologram recorded thereon. And a heat-seal layer formed on the volume hologram layer, wherein the pressure-sensitive adhesive content can maintain the foil breakability of the volume hologram transfer foil. It is characterized by a quantity.

  Such a volume hologram transfer foil will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the volume hologram transfer foil of the present invention. As illustrated in FIG. 1, a volume hologram transfer foil 10 of the present invention is formed on a base material 1, a protective layer 2 formed on the base material 1, and the protective layer 2, and a volume hologram is recorded. The volume hologram layer 3 is formed, and the heat seal layer 4 is formed on the volume hologram layer 3.

The volume hologram transfer foil of the present invention includes a curable resin and an adhesive in the protective layer. In addition, the content of the pressure-sensitive adhesive in the protective layer is an amount capable of maintaining the foil cutting property of the volume hologram transfer foil.
As a result, when the volume hologram transfer foil is manufactured by roll-to-toe, it is possible to prevent foil floating and foil peeling that occur between the base material and the protective layer after the volume hologram layer and protective layer curing step. In addition, when a volume hologram laminate is produced using the volume hologram transfer foil, the volume hologram laminate can be transferred to an adherend without impairing the foil cutting property.
That is, the volume hologram transfer foil of the present invention can improve both the physical properties of interlayer adhesion and foil breakability.

Such a volume hologram transfer foil of the present invention is usually used for producing a volume hologram laminate by transferring a volume hologram layer to an arbitrary adherend.
The volume hologram transfer foil of the present invention has at least a substrate, a protective layer, a volume hologram layer, and a heat seal layer, and may have any other configuration as necessary.
Hereafter, each structure used for the volume hologram layer of this invention is demonstrated in order.

1. Protective layer
The protective layer in the present invention contains a curable resin and an adhesive.
Further, the content of the pressure-sensitive adhesive is an amount capable of maintaining the foil cutting property of the volume hologram transfer foil.

Conventionally, since the volume hologram layer is a thick film, the foil cutting property is poor, and in the method of transferring the hologram layer using the volume hologram transfer foil, the foil cutting property of the volume hologram transfer foil has been a problem.
In addition, in order to make it possible to continuously apply a volume hologram to a predetermined position in an industrial production process, there is a method in which the volume hologram transfer foil described above is formed in a long shape and the volume hologram is continuously transferred. Although it has been developed, it is necessary to partially transfer the volume hologram from the volume hologram transfer foil, and higher foil cutting properties have been demanded.

Furthermore, when the volume hologram transfer foil is produced in a roll-to-roll shape in a long shape, usually, after the volume hologram layer and the protective layer are cured, for example, the color material contained in the volume hologram layer In the bleaching step of breaking and making it colorless and transparent, there is a problem that foil floating or foil peeling occurs between the protective layer and the substrate, and interlayer adhesion cannot be maintained.
For the reasons described above, the volume hologram transfer foil is required to have good physical properties in both the foil cutting property and the interlayer adhesion in the production process.

Therefore, in order to solve the above problems, in the present invention, the protective layer contains an adhesive, and the content of the adhesive is set to an amount that can maintain the foil breakability of the volume hologram transfer foil. With respect to both physical properties of adhesiveness and foil cutting property, it was possible to obtain a good volume hologram transfer foil.
That is, by adjusting the content of the pressure-sensitive adhesive to the above-mentioned amount, it is possible to maintain good foil breakability without impairing the breaking elongation of the protective layer in the present invention. Moreover, since a protective layer has surface tackiness by containing an adhesive, the adhesiveness between a base material and a protective layer can be improved, and generation | occurrence | production of foil floating and foil peeling can be suppressed.

Here, in the present invention, the content of the pressure-sensitive adhesive capable of “maintaining the foil cutting property of the volume hologram transfer foil” will be described.
Usually, when the pressure-sensitive adhesive is added to a layer such as a protective layer, since the pressure-sensitive adhesive has a low molecular weight, the elongation at break of the layer containing the pressure-sensitive adhesive is increased and the foil breakability is deteriorated.
On the other hand, in order to improve the interlayer adhesion between the base material and the protective layer, which is the problem described above, it is necessary to increase the content of the pressure-sensitive adhesive in the protective layer to improve the surface tackiness. However, since the breaking elongation of the protective layer increases as the content of the pressure-sensitive adhesive increases, the foil breakability of the protective layer is deteriorated.
For the above reasons, the amount of the pressure-sensitive adhesive added to the protective layer is required to be an amount that does not deteriorate the foil breakability of the protective layer.
Here, in the present invention, the content of the pressure-sensitive adhesive that “can maintain the foil cutting property of the volume hologram transfer foil” is specifically an amount such that the elongation at break of the protective layer is within the following range. Preferably there is.

That is, the range of elongation at break of the protective layer is preferably within a range of 1.1% to 2.1% at 23 ° C.
When the breaking elongation of the protective layer in the present invention is larger than the above range, the flexibility of the protective layer becomes excessively high, so that the foil breakability may be lowered. On the other hand, when it is smaller than the above range, there is a possibility of foil floating or peeling off between the base material and the protective layer after the volume hologram layer and the protective layer curing step when manufacturing with roll-to-toe Because.

In addition, the measuring method of breaking elongation is implemented according to JISK5600. For details, the measurement sample was allowed to stand for 24 hours or more in an atmosphere of 20 ° C. and 65% RH, and then pulled under the following conditions.
In addition, the measurement sample (test piece) is coated with a protective layer solution containing a protective layer material to be described later on the base material, cured by irradiating the entire surface with ultraviolet rays using a high-pressure mercury lamp, and then peeled off from the base material. A film-like test piece. In addition, if the base material surface is mold-released, peeling of a film-form test piece will be easy.

(Measurement of elongation at break)
・ Measuring equipment: Self-recording tester (INSTRON 5565 manufactured by INSTRON)
・ Distance between chucks: 25mm
・ RANGE: 1%
・ Measurement environment: 23 ° C., 50% RH atmosphere ・ Tensile speed: 10 mm / min
・ Sample piece: 15 mm width strip

The elongation at break in the present invention was defined as the elongation at break relative to the length of the elongation at break when a break or crack occurred during the pulling according to the measurement method and measurement conditions described above.
Note that the measurement of the elongation at break in the following description is also performed using the above method and conditions unless otherwise specified.

  The protective layer in the present invention contains a curable resin and an adhesive. Hereinafter, each structure of the protective layer in this invention is demonstrated.

(1) Adhesive The adhesive in the present invention will be described. The pressure-sensitive adhesive in the present invention is contained in the protective layer.
In the present invention, the pressure-sensitive adhesive is contained in the protective layer in a predetermined amount, so that the protective layer can be given surface tackiness, and the volume hologram transfer foil of the present invention can maintain the foil cutting property and the protection. Interlayer adhesion between the layer and the substrate can be improved.

Examples of the types of the pressure-sensitive adhesives include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, alpha-cyanoacrylate-based pressure-sensitive adhesives, maleimide-based pressure-sensitive adhesives, and styrene-based pressure-sensitive adhesives. Examples thereof include pressure-sensitive adhesives, polyolefin-based pressure-sensitive adhesives, resorcinol-based pressure-sensitive adhesives, and polyvinyl ether-based pressure-sensitive adhesives. Among them, it is preferable to use an acrylic pressure-sensitive adhesive that has excellent durability and adhesiveness and is low in cost.
Examples of the acrylic pressure-sensitive adhesive include an acrylic ester copolymer obtained by copolymerizing an acrylic ester and another monomer.
Examples of the acrylate ester include ethyl acrylate, acrylate-n-butyl, acrylate-2-ethylhexyl, isooctyl acrylate, isononyl acrylate, hydroxylethyl acrylate, propylene glycol acrylate, acrylamide, glycidyl acrylate, and the like. Is mentioned. These can be used alone or in combination of two or more.

  Other monomers include, for example, methyl acrylate, methyl methacrylate, styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, hydroxylethyl acrylate, hydroxylethyl methacrylate, propylene glycol acrylate, acrylamide Methacrylamide, glycidyl acrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, and n-ethylhexyl methacrylate. These can be used alone or in combination of two or more.

(2) Curable resin The said curable resin comprises a protective layer. Here, the curable resin in the present invention means a resin that has been cured by light or heat, that is, a cured curable resin.
As the kind of the curable resin, a thermosetting resin such as an ionizing ray curable resin or a two-component curable resin can be used, and an ionizing ray curable resin and a thermosetting resin can be used in combination. . In the present invention, among them, it is preferable to have an ionizing radiation curable resin, and it is particularly preferable to have two types of ionizing radiation curable resins having different weight average molecular weights.
By using two types of ionizing radiation curable resins having different weight average molecular weights as the protective layer, the elongation at break of the protective layer can be increased and flexibility can be imparted. This is because the volume hologram transfer foil of the present invention can have good foil cutting properties.
Hereinafter, the two types of ionizing radiation curable resins will be described separately for (a) a first ionizing radiation curable resin and (b) a second ionizing radiation curable resin.

(A) 1st ionizing-ray curable resin The 1st ionizing-ray curable resin contained in the protective layer in this invention is demonstrated. The first ionizing radiation curable resin used in the present invention imparts a hardness that allows the protective layer to maintain its shape as a layer and desired foil breakability.

  The first ionizing ray curable resin used in the present invention is not particularly limited as long as it is made of a raw material composition that can be cured by irradiation with ionizing rays, but generally, as a film forming component. The polymer is polymerized mainly with a monomer, oligomer, or polymer having a radically polymerizable active group in the structure. Among these, those polymerized mainly with monomers or oligomers are preferred. When the raw material composition of the first ionizing radiation curable resin is used as a coating liquid, the monomer or oligomer has an advantage that it has a relatively low viscosity and can be easily used as compared with the case of using a polymer. It is. In the present invention, an oligomer is particularly preferable.

The ionizing rays may be classified according to the quantum energy of the electromagnetic waves. In the present invention, all ultraviolet rays (UV-A, UV-B, UV-C), visible rays, gamma rays, X-rays are used. , Defined to include electron beams and the like.
Accordingly, ultraviolet rays (UV), visible rays, gamma rays, X-rays or electron beams can be applied as the ionizing rays for curing the raw material composition of the first ionizing ray curable resin before curing. Is preferred. This is because the versatility is high. That is, as the first ionizing radiation curable resin in the present invention, an ultraviolet curable resin is preferable.

  The ultraviolet curable resin is not particularly limited, but an acrylic resin is preferably used. Specific examples include acrylic and methacrylic resins such as polymethyl acrylate and polymethyl methacrylate, epoxy-modified acrylate resins, urethane-modified acrylate resins, and acrylic-modified polyesters. Among them, polymerized by using a derivative of (meth) acrylic acid ester as a monomer, and urethane acrylate (SP value: 9.05), polyester acrylate (SP value: 9-14) or the like as an oligomer. Any polymerized ultraviolet curable resin may be used.

Moreover, in this invention, it is preferable that the weight average molecular weights of the oligomer which is a raw material composition of said 1st ionizing-beam curable resin are 10000 or less, and it is more preferable to exist in the range of 1000-5000 especially.
If the weight average molecular weight of the oligomer that is the raw material composition of the first ionizing ray curable resin is too large, the degree of freedom of the molecular chain of the oligomer is likely to be excessive, and it is difficult to have an appropriate hardness. There is a possibility that it will not be possible to show a good foil cutting property.
On the other hand, if the weight average molecular weight of the oligomer is too small, the degree of freedom of the molecular chain of the oligomer tends to be too small and the hardness tends to be excessively increased, so that cracking or the like may occur during or after the volume hologram layer transfer. It is possible.

(B) Second ionizing ray curable resin Next, the second ionizing ray curable resin contained in the protective layer in the present invention will be described. The second ionizing radiation curable resin used in the present invention increases the elongation at break of the protective layer and imparts surface tackiness.

  The second ionizing radiation curable resin in the present invention is mixed with the hard first ionizing radiation curable resin and contained in the protective layer, so that the elongation at break of the protective layer is increased and appropriate flexibility is obtained. Can be given. Therefore, the foil breakability of the protective layer can be improved. Further, by including the second ionizing radiation curable resin, it is possible to impart surface tackiness to the protective layer, and it is possible to maintain adhesiveness with the base material to be laminated.

The second ionizing radiation curable resin preferably has a breaking elongation in the range of 50% to 1000%, and more preferably in the range of 100% to 500%.
When the elongation at break is larger than the above range, the flexibility tends to be excessively increased when the protective layer is formed by mixing with the above-mentioned first ionizing radiation curable resin, and the protective layer has a good foil. There is a possibility that the cutting property cannot be maintained.
On the other hand, when the elongation at break is smaller than the above range, when the protective layer is formed by mixing with the first ionizing radiation curable resin, it becomes impossible to give an appropriate flexibility to the protective layer, The hardness of the protective layer tends to be excessively high. As a result, surface tackiness cannot be imparted to the protective layer, and adhesion with the base material may not be maintained, and defects such as cracks may occur during transfer or after transfer.
In addition, the value of the breaking elongation is measured in the same manner as the measuring method and measuring conditions of the breaking elongation described above.
In addition, the measurement sample (test piece) was coated with a coating liquid containing the above-mentioned second ionizing ray curable resin raw material composition on a substrate, and was cured by irradiating the entire surface with ultraviolet rays. The film-like test piece is peeled off from the material.

The second ionizing radiation curable resin in the present invention is not particularly limited as long as it is cured by irradiation with ionizing radiation. For example, an ultraviolet curable resin, an electron beam curable resin, and a visible light curable resin are used. Resin, near infrared curable resin, and the like.
Especially, it is preferable that it is an ionizing ray curable resin which has a softness | flexibility and can provide surface tackiness.

The second ionizing ray curable resin is more flexible than the first ionizing ray curable resin, and therefore the second ionizing ray curable resin is mixed with the first ionizing ray curable resin to form the protective layer in the present invention. When formed, flexibility can be imparted to the protective layer. Therefore, it is possible to prevent the protective layer from becoming excessively hard, and to prevent defects such as cracks during or after the transfer, while maintaining good foil breakability and surface tackiness.
Here, the flexibility is not particularly limited as long as cracking or the like can be prevented when the protective layer is formed. However, the flexibility in the present invention is the range described above. It may have a breaking elongation within.

The raw material composition of the second ionizing radiation curable resin in the present invention is not particularly limited as long as it has flexibility and can impart surface tackiness. Those having a main component of a monomer, oligomer or polymer having the active group are preferred. Among these, monomers or oligomers are preferable, and those obtained by polymerizing oligomers as main components are particularly preferable.
The reason why the ionizing curable resin that polymerizes the above-mentioned oligomer as a main component is preferable is the same as the reason described in the above-mentioned “(a) first ionizing radiation curable resin”. Omitted.

  Moreover, as an ionizing ray used for this invention, what was described in the above-mentioned "(a) 1st ionizing ray curable resin" can be used, However, Among these, an ultraviolet-ray is preferable. This is because the versatility is high. Accordingly, the second ionizing radiation curable resin used in the present invention is preferably an ultraviolet curable resin among the ionizing radiation curable resins described above.

  Specific examples of the ultraviolet curable resin include epoxy-modified acrylate resin, urethane-modified acrylate resin, acrylic-modified polyester, and the like. Among them, (meth) acrylic acid ester derivatives are used as the main monomer. Examples of the polymerized polymer include ultraviolet curable resins radically polymerized using urethane acrylate or polyester acrylate as the main oligomer.

  In the present invention, the weight average molecular weight of the oligomer that is the raw material composition of the second ionizing radiation curable resin is preferably in the range of 3000 to 20000, and more preferably in the range of 8000 to 15000. preferable.

Moreover, it is preferable that the weight average molecular weight of the second ionizing radiation curable resin is larger than the weight average molecular weight of the first ionizing radiation curable resin.
That is, the weight average molecular weight of the oligomer that is the raw material composition of the second ionizing radiation curable resin is larger than the weight average molecular weight of the oligomer that is the raw material composition of the first ionizing radiation curable resin. Preferably, the weight average molecular weight is preferably 2 times or more, and more preferably in the range of 2.5 to 10 times.
When the difference in weight average molecular weight is larger than the above range, the hardness of the second ionizing ray curable resin tends to be too low. Therefore, the protection is performed by mixing with the first ionizing ray curable resin described above. When forming the layer, the hardness of the protective layer may be too low, and it may not be possible to obtain good foil breakability.
On the other hand, when it is smaller than the above range, the second ionizing radiation curable resin tends to be unable to obtain sufficient flexibility and may not be able to impart flexibility to the protective layer. The hardness of the layer becomes high, and there is a possibility that problems such as cracking occur at the time of or after the volume hologram layer transfer. Moreover, when the hardness of the said protective layer becomes high, the said protective layer does not have surface tackiness, and there exists a possibility that adhesiveness with the base material to laminate | stack cannot be hold | maintained.

The content of the second ionizing radiation curable resin in the present invention is not particularly limited as long as it can impart flexibility and surface tackiness to the protective layer, but the first ionizing radiation curing is not limited. The weight ratio with the conductive resin is preferably in the range of the first ionizing radiation curable resin: the second ionizing radiation curable resin = 3 to 9: 7-1, and among them, the first ionizing radiation curing is particularly preferable. Resin: second ionizing ray curable resin = preferably in the range of 5-8: 5-2.
If the content of the second ionizing ray curable resin is too low, sufficient protection may not be imparted to the protective layer in the present invention, and the hardness of the protective layer is excessively increased, resulting in a volume hologram layer. Cracks may occur during or after transfer. In addition, if the content of the second ionizing ray curable resin is too low, the protective layer does not have surface tackiness and may not be able to maintain adhesiveness with the substrate to be laminated.
On the other hand, if the content of the second ionizing ray curable resin is too high, the flexibility of the protective layer may become excessively high, and the foil breakability may be reduced.

(3) Other materials The protective layer in the present invention includes at least the curable resin and the pressure-sensitive adhesive described above, but may include any material other than these materials as necessary.
The arbitrary material used in the present invention is not particularly limited as long as a desired function can be imparted to the protective layer in the present invention and the volume hologram transfer foil in the present invention.
Examples of the optional material used for the protective layer include a foil breakage control component, an ultraviolet absorber, and a photopolymerization initiator. Hereinafter, among the above materials, the foil breakability control component will be described.

(A) Foil breakability control component When the protective layer in this invention contains a foil breakability control component, the brittleness of the whole protective layer can be improved, and it is set as the protective layer which has more favorable foil breakability. be able to.

  The foil breakability control component in the present invention is preferably incompatible with the above-mentioned pressure-sensitive adhesive and two types of ionizing radiation curable resins. This is because the foil breakability control component can be dispersed in the protective layer in the form of fine particles.

In the present invention, the determination of whether or not incompatibility can be made using an index indicating general compatibility. For example, it is preferable to use a solubility index (SP value).
The SP value is used as an index indicating compatibility and incompatibility in a mixed system composed of at least two components, and is calculated, for example, from a SMALL calculation method. It is known that the smaller the SP value difference, the higher the compatibility, and the larger the SP value, the higher the incompatibility. In the present invention, the foil breakability control component is not particularly limited as long as it is incompatible to the extent that it is dispersed in the protective layer.
In the present invention, the foil breakage control component is not particularly limited as long as it is incompatible to the extent that it is dispersed in the protective layer, but the difference in SP value is 1 or more. preferable.
When the difference in SP value is small, the foil breakage control component tends to have good compatibility with other components, and therefore may not be dispersed in the form of fine particles in the protective layer. It may be difficult to generate strain or microcracks that increase the brittleness of the protective layer, and the foil breakability of the protective layer may be reduced.

  Moreover, it is preferable that the foil breakability control component in this invention has a thermal expansion coefficient different from said 2 types of ionizing-ray curable resin. By having a thermal expansion coefficient different from that of the above two types of ionizing ray curable resins, by mixing with a protective layer containing the above two types of ionizing ray curable resins crosslinked by ionizing ray irradiation, This is because, in the protective layer, the two types of ionizing radiation curable resins cross-linked existing around the foil breakability control component can be distorted and microcracked to increase the brittleness of the protective layer. .

  The thermal expansion coefficient of the foil breakability control component in the present invention is different from the above two types of ionizing radiation curable resins, and the thermal expansion of the foil breakability control component and the above two types of ionizing radiation curable resins. There is no particular limitation as long as the stress is generated due to the difference in the coefficient and causes strain and microcracks. In addition, as a thermal expansion coefficient in this invention, the value measured using the thermodynamic analyzer (TMA) can be used.

  Moreover, it is preferable that the foil breakability control component in this invention has melting | fusing point below the heating temperature at the time of cutting | disconnection of transfer foil. This is because the foil breakage control component is dissolved at the time of thermal transfer, so that the space where the foil breakability control component was present becomes a state similar to a hole, and the brittleness of the protective layer is further increased. Therefore, the foil breakability of the protective layer can be improved.

The melting point of the foil breakability control component is not particularly limited as long as it is equal to or lower than the heating temperature at the time of cutting the transfer foil, but generally, the temperature applied to the transfer foil at the time of cutting the transfer foil is 60 ° C. to 200 ° C. Since it is in the range of ° C., the melting point of the above-mentioned foil breakability control component is preferably in the range of 40 ° C. to 200 ° C., particularly preferably in the range of 60 ° C. to 120 ° C.
If the melting point of the foil breakability control component is higher than within the above temperature range, the foil breakage control component does not dissolve when the transfer foil is cut, and a volume change occurs, but it does not become the same state as the hole. This is because the foil breakability cannot be improved.
On the other hand, if the melting point of the foil breakability control component is lower than within the above temperature range,
This is because it may be difficult to produce a transfer foil.

  Specific examples of the foil breakability control component include polyethylene resin particles and beads. More specific examples include polyethylene wax (SP value: 8.0), fatty acids and the like. Among these, polyethylene wax is more preferable. This is because by dissolving during heating, a large volume change is likely to occur, and the foil breakability of the protective layer can be further improved.

  As the content of the foil breakability control component, the weight ratio of the foil breakability control component when the total content of the two types of ionizing radiation curable resins contained in the protective layer is 100 parts by weight is as follows. It is preferably in the range of 1 to 10 parts by weight, and more preferably in the range of 2 to 5 parts by weight.

(4) Protective layer The protective layer in this invention contains the adhesive mentioned above and two types of ionizing radiation curable resins, uses an acrylic adhesive as said adhesive, and uses acrylic as said two types of ionizing radiation curable resin. When the weight average molecular weight of one of the acrylic resins is more than twice the weight average molecular weight of the other, the pressure sensitive adhesive content is the total content of the two types of ionizing radiation curable resins. The amount is preferably less than 1 part by weight with respect to 100 parts by weight, and more preferably within the range of 0.3 part by weight to 0.8 part by weight.
In the protective layer made of the above-mentioned material, the content of the pressure-sensitive adhesive is 0 part by weight, that is, when the pressure-sensitive adhesive is not contained in the protective layer at all, the surface tackiness of the protective layer is small, and the protective layer and the base material The adhesion between the two cannot be strengthened. Therefore, there is a possibility that foil floating or foil peeling is likely to occur between the protective layer and the substrate during the manufacturing process.
On the other hand, when the content of the pressure-sensitive adhesive is 1 part by weight or more, the tensile strength and elongation of the protective layer are increased, so that the foil cutability of the obtained volume hologram transfer foil may be deteriorated.
Therefore, in the volume hologram transfer foil having the protective layer made of the above-mentioned material, in order to improve both the interlaminar adhesion and the foil breakability, the content of the adhesive contained in the protective layer is It is preferable to be within the above-mentioned range.

The protective layer in the present invention preferably has a desired tensile strength. Specifically, at 23 ° C., the tensile strength of the protective layer is preferably in the range of 5 MPa to 30 MPa, and more preferably in the range of 10 MPa to 20 MPa.
If the tensile strength of the protective layer is larger than the above range, the protective layer becomes a strong protective layer, so that the foil breakability may be deteriorated. On the other hand, if the thickness is smaller than the above range, the protective layer is too weak in film strength, so that the protective layer may be easily peeled off from the substrate or the volume hologram layer when bent or rolled.
The tensile strength can be measured by the same method as the measuring method of elongation at break. Therefore, the value of the tensile strength is a value measured using the same measurement method and measurement conditions as the above-described breaking elongation of the protective layer.

In addition, the thickness of the protective layer in the present invention is preferably in the range of 0.5 μm to 10 μm, and more preferably in the range of 2.0 μm to 5.0 μm.
When the thickness of the protective layer in the present invention is larger than the above range, a foil breakage defect is likely to occur or a significant unevenness may occur at the time of partial transfer, whereas, when the thickness is smaller than the above range This is because the volume hologram may not be protected.

  As a function of the protective layer in the present invention, when the volume hologram layer is transferred to the adherend using the volume hologram transfer foil of the present invention, the surface of the volume hologram laminate can be covered with the protective layer. The transferred volume hologram layer can be protected.

2. Base material The base material in this invention is demonstrated. As a base material in this invention, each structure of the volume hologram transfer foil of this invention is supported.

The substrate in the present invention preferably has a low glass transition temperature (Tg).
For example, polyethylene terephthalate film, polyethylene film, polypropylene film, polyvinyl fluoride film, polyvinylidene fluoride film, polyvinyl chloride film, polyvinylidene chloride film, ethylene-vinyl alcohol copolymer film, polyvinyl alcohol film, polymethyl methacrylate film And polyester films such as polyethersulfone film, polyetheretherketone film, polyamide film, tetrafluoroethylene-perfluoroalkylvinylether copolymer film, and resin films such as polyimide film. Among these, in the present invention, it is preferable to use a polyethylene terephthalate film. This is because it is inexpensive, versatile, and has excellent dimensional stability.

  The thickness of the substrate in the present invention is appropriately selected according to the use or type of the volume hologram transfer foil, but is usually in the range of 2 μm to 200 μm, preferably in the range of 10 μm to 50 μm. It is said.

Moreover, the base material in the present invention may be one in which a release treatment is performed on the surface in contact with the protective layer. This is because peeling between the substrate and the protective layer is facilitated during transfer.
Specific examples of such a release treatment include dipping application, spray application, roll coat application method and the like of a fluorine type release agent, a stearate type release agent, a wax type release agent and the like.

  The substrate in the present invention may be formed in a long shape, or may be other than the one formed in a long shape. “Long” means the ratio of the distance in the longitudinal direction to the distance in the direction perpendicular to the longitudinal direction (width direction) (distance in the longitudinal direction / distance in the direction perpendicular to the longitudinal direction (width direction)). It means 5 or more.

3. Volume hologram layer Next, the volume hologram layer in the present invention will be described. The volume hologram layer in the present invention has a volume hologram recorded thereon, and is transferred to an adherend using the volume hologram transfer foil of the present invention.
Hereinafter, such a volume hologram layer will be described in detail.

(1) Constituent material The material constituting the volume hologram layer in the present invention is not particularly limited as long as it can record a volume hologram, and any material generally used for a volume hologram can be arbitrarily selected. Can be used. Examples of such materials include known volume hologram recording materials such as silver salt materials, dichromated gelatin emulsions, photopolymerizable resins, and photocrosslinkable resins. a) a first photosensitive material containing a binder resin, a photopolymerizable compound, a photopolymerization initiator and a sensitizing dye, or (b) a cationic polymerizable compound, a radical polymerizable compound, a photo radical polymerization initiator and light A second photosensitive material containing a cationic polymerization initiator system can be suitably used.
Hereinafter, the first photosensitive material and the second photosensitive material will be described in order.

(A) First photosensitive material The first photosensitive material will be described. As described above, the first photosensitive material contains a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a sensitizing dye.

(Binder resin)
As the binder resin, for example, at least one of a copolymerizable monomer group such as poly (meth) acrylic acid ester or a partially hydrolyzed product thereof, polyvinyl acetate or a hydrolyzed product thereof, acrylic acid or an acrylic acid ester is used. Copolymer as a polymerization component, or a mixture thereof, polyisopropylene, polybutadiene, polychloropyrene, polyvinyl acetal which is a partial acetalization product of polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, etc. Or a mixture thereof.
Here, when the volume hologram layer is formed, a step of moving the monomer by heating may be performed in order to stabilize the recorded volume hologram. For this reason, it is preferable that the binder resin used in the present invention has a relatively low glass transition temperature and can easily move the monomer.

(Photopolymerizable compound)
As the photopolymerizable compound, there can be used a photopolymerizable and photocrosslinkable monomer, oligomer, prepolymer and mixture thereof having at least one ethylenically unsaturated bond in one molecule as described later. . Specific examples include esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amide compounds of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and the like.

  Here, specific examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like. Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetra Examples include methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, and the like.

  Examples of the methacrylic acid ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolethane trimethacrylate. Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, and 1,3-butanediol diitaconate. Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Furthermore, examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Furthermore, examples of the maleic ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Examples of the halogenated unsaturated carboxylic acid include 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and the like. Can be mentioned.
Specific examples of the amide monomer of the unsaturated carboxylic acid and the aliphatic polyvalent amine compound include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bis. And methacrylamide.

(Photopolymerization initiator)
Examples of the photopolymerization initiator used in the present invention include 1,3-di (t-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone, Examples thereof include N-phenylglycine, 2,4,6-tris (trichloromethyl) -s-triazine, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, and imidazole dimers. Among them, the photopolymerization initiator used in the present invention is preferably one that is decomposed after hologram recording from the viewpoint of stabilizing the recorded volume hologram. From such a viewpoint, it is preferable to use an organic peroxide photopolymerization initiator in that it is easily decomposed by irradiation with ultraviolet rays.

(Sensitizing dye)
Sensitizing dyes used in the present invention include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamines And dyes, thiopyrylium salt dyes, pyrylium ion dyes, diphenyliodonium ion dyes, and the like.

(B) Second photosensitive material Next, the second photosensitive material used in the present invention will be described. As described above, the second photosensitive material contains a cationic polymerizable compound, a radical polymerizable compound, a photo radical polymerization initiator system, and a cationic polymerization initiator system.

  Here, when such a second photosensitive material is used, a method for recording a volume hologram on the volume hologram layer is to irradiate light such as laser light that is photosensitized by a photo radical polymerization initiator system, and then to photo cation. A method of irradiating light having a wavelength different from that of the laser light that the polymerization initiator system is sensitive to will be used.

(Cationically polymerizable compound)
As the cationic polymerizable compound, a liquid compound at room temperature is preferably used because it is preferable that the polymerization of the radical polymerizable compound is performed in a composition having a relatively low viscosity. Examples of such cationically polymerizable compounds include diglycerol diether, pentaerythritol polydiglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, 1,6- Examples thereof include hexanediol glycidyl ether, polyethylene glycol diglycidyl ether, and phenyl glycidyl ether.

(Radically polymerizable compound)
As the radical polymerizable compound, those having at least one ethylenically unsaturated double bond in the molecule are preferable. The average refractive index of the radical polymerizable compound used in the present invention is preferably larger than the average refractive index of the cationic polymerizable compound, and more preferably 0.02 or more. This is because a volume hologram is formed by the difference in refractive index between the radical polymerizable compound and the cationic polymerizable compound. Therefore, when the average refractive index difference is not more than the above value, the refractive index modulation becomes insufficient.
Examples of the radical polymerizable compound used in the present invention include acrylamide, methacrylamide, styrene, 2-bromostyrene, phenyl acrylate, 2-phenoxyethyl acrylate, 2,3-naphthalenedicarboxylic acid (acryloxyethyl) monoester, Examples thereof include methylphenoxyethyl acrylate, nonylphenoxyethyl acrylate, and β-acryloxyethyl hydrogen phthalate.

(Photo radical polymerization initiator system)
As the radical photopolymerization initiator system used in the present invention, any active radical can be generated by the first exposure when the volume hologram is recorded, and the active radical can polymerize the radical polymerizable compound. It is not particularly limited. Moreover, you may use combining the sensitizer which is a component which generally absorbs light, an active radical generating compound, and an acid generating compound.
A sensitizer in such a radical photopolymerization initiator system often uses a colored compound such as a dye to absorb visible laser light, but in the case of a colorless transparent hologram, a cyanine dye is used. Is preferred. Since cyanine dyes are generally easily decomposed by light, the dyes in the hologram are decomposed and absorbed in the visible range by being left exposed for several hours to several days under post-exposure or indoor light or sunlight in the present invention. This is because a colorless and transparent volume hologram can be obtained.

  Specific examples of the cyanine dye include anhydro-3,3′-dicarboxymethyl-9-ethyl-2,2′thiacarbocyanine betaine, anhydro-3-carboxymethyl-3 ′, 9′-diethyl-2. , 2 'thiacarbocyanine betaine, 3,3', 9-triethyl-2,2'-thiacarbocyanine iodine salt, 3,9-diethyl-3'-carboxymethyl-2,2'-thiacarbocyanine Iodine salt, 3,3 ′, 9-triethyl-2,2 ′-(4,5,4 ′, 5′-dibenzo) thiacarbocyanine iodine salt, 2- [3- (3-ethyl-2-benzo Thiazolidene) -1-propenyl] -6- [2- (3-ethyl-2-benzothiazolidene) ethylideneimino] -3-ethyl-1,3,5-thiadiazolium iodine salt, 2- [[3-Allyl-4 Oxo-5- (3-n-propyl-5,6-dimethyl-2-benzothiazolidene) -ethylidene-2-thiazolinylidene] methyl] 3-ethyl-4,5-diphenylthiazolinium-iodine salt, 1 , 1 ', 3,3,3', 3'-hexamethyl-2,2'-indotricarbocyanine / iodine salt, 3,3'-diethyl-2,2'-thiatricarbocyanine / perchlorate Anhydro-1-ethyl-4-methoxy-3'-carboxymethyl-5'-chloro-2,2'-quinothiocyanine betaine, anhydro-5,5'-diphenyl-9-ethyl-3,3'- Examples thereof include disulfopropyloxacarbocyanine hydroxide and triethylamine salts, and one or more of these can be used in combination.

  Examples of the active radical generating compound include diaryliodonium salts and 2,4,6-substituted-1,3,5-triazines. The use of diaryliodonium salts is particularly preferred when high photosensitivity is required. Specific examples of the diaryl iodonium salts include diphenyl iodonium, 4,4′-dichlorodiphenyl iodonium, 4,4′-dimethoxydiphenyl iodonium, 4,4′-ditertiary butyl diphenyl iodonium, 3,3′-dinitrodiphenyl iodonium. Such as chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate, 9,10-dimethoxyanthracene-2-sulfonate, and the like. Specific examples of 2,4,6-substituted-1,3,5-triazines include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,4 6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 (P-methoxyphenylvinyl) -1,3,5-triazine, 2- (4′-methoxy-1′-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like. It is done.

(Photocationic polymerization initiator system)
The cationic photopolymerization initiator system used in the present invention has low photosensitivity for the first exposure when a volume hologram is recorded, and is sensitive to post-exposure by irradiating light having a wavelength different from that of the first exposure. The initiator system is not particularly limited as long as it generates a Bronsted acid or a Lewis acid and polymerizes a cationically polymerizable compound. In particular, in the present invention, it is particularly preferable to use a compound that does not polymerize the cationic polymerizable compound during the first exposure. Examples of such a cationic photopolymerization initiator system include diaryliodonium salts, triarylsulfonium salts, iron allene complexes, and the like. Preferable diaryliodonium salts include iodonium tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and the like shown in the radical photopolymerization initiator system described above. Preferable triarylsulfonium salts include triphenylsulfonium, 4-tertiarybutyltriphenylsulfonium, and the like.

(Other)
In the second photosensitive material, a binder resin, a thermal polymerization inhibitor, a silane coupling agent, a plasticizer, a colorant, and the like may be used in combination as necessary. Binder resin is stable for improving the film formability and thickness uniformity of the composition before recording the hologram layer, and for preventing interference fringes formed by polymerization by irradiation with light such as laser light until post-exposure. Used to be present. The binder resin only needs to be compatible with the cationic polymerizable compound or the radical polymerizable compound. For example, a copolymer of chlorinated polyethylene, polymethyl methacrylate, methyl methacrylate and other alkyl (meth) acrylates. And a copolymer of vinyl chloride and acrylonitrile, polyvinyl acetate, and the like. The binder resin may have reactivity such as a cation polymerizable group in its side chain or main chain.

(2) Volume hologram layer As the volume hologram layer in the present invention, fine particles may be added as required in addition to the photosensitive material described above. When such fine particles are contained in the volume hologram layer, defects can be intentionally formed, and brittleness can be imparted to the volume hologram layer, so that it is possible to have good foil breakability. .

Here, the fine particles are not particularly limited as long as they have a predetermined particle size. For example, as the resin skeleton, low density polyethylene, high density polyethylene, polypropylene, (meth) acryl, polyvinyl chloride, Polyamide, polyimide, polycarbonate, epoxy or urethane, organic fine particles containing these copolymers, silica, mica, talc, clay, graphite, calcium carbonate, alumina, aluminum hydroxide, ferrite, china clay, kaolin, titanium dioxide, glass Inorganic fine particles such as flakes, asbestos, wax stone powder, silica stone powder, barium sulfate, Shelben, chamotte, and titania can be used. These fine particles may be used alone or in combination of two or more.
Among them, the present invention is a fluorine-based fine particle or a titania fine particle which is a fine particle of a fluorine-containing resin in which a part or all of hydrogen in the skeleton or side chain in the resin of the organic fine particle is substituted with a fluorine atom. Is preferred. This is because the foil breakage can be made better.

  In addition, the fluorine-based fine particles, which are the fine particles of the fluorine-containing resin, have a small friction coefficient, and thus have little interaction with other components contained in the volume hologram layer, and impart a brittleness to the volume hologram layer in a small amount. It becomes possible to do. As the fluorine-based fine particles, those obtained by partially or fully fluorinating the organic fine particles exemplified above, or those obtained by treating the surface of the fine particles with a fluorine-containing compound can be used. In particular, it is preferable to use fluorine-based fine particles utilizing a (meth) acrylic acid ester compound. Specific examples of such fine particles include a fluorine-containing acrylic ester described in JP-A-5-194322, a fluorine-containing (meth) acrylic compound described in JP-A-9-104655, and JP-A-2001-72646. A monomer polymer using at least one fluorine monomer represented by the fluorine-containing polyfunctional (meth) acrylic acid ester compound described above, or having at least one ethylenically unsaturated bond in one molecule not containing other fluorine Monomer copolymer copolymerized with compound, fluorine-containing resin composite fine particles disclosed in JP-A-6-73137, fluorine-containing (meth) acrylic acid ester copolymer disclosed in JP-A-5-194668, etc. Is mentioned. These fluorine-based fine particles can be used alone or in combination.

The thickness of the volume hologram layer in the present invention is not particularly limited as long as it is within a range in which a predetermined volume hologram image can be recorded, and can be appropriately adjusted according to the type of the constituent material described above. Especially, it is preferable that the thickness of the volume hologram layer in this invention exists in the range of 50 micrometers or less, and it is especially preferable that it exists in the range of 1 micrometer-25 micrometers.
In addition, when the thickness of the volume hologram layer is increased, when the volume hologram transfer foil of the present invention is used, defective foil breakage of the volume hologram layer is likely to occur.

Further, specifically, the breaking elongation of the volume hologram layer in the present invention is preferably such that the breaking elongation at 23 ° C. is in the range of 0.5% to 15%, and in particular, 1.0% to 10%. It is preferable to be within the range.
When the breaking elongation of the volume hologram layer in the present invention is larger than the above range, the flexibility of the volume hologram layer becomes excessively high, so that the foil breakability may be lowered, whereas it is smaller than the above range. In this case, it is because cracks are likely to occur in the laminated structure.
The value of the elongation at break is a value measured by the measurement method and measurement conditions described in the above-mentioned section “A. Volume hologram transfer foil 1. Protective layer”. In addition, the measurement sample (test piece) is a film-like test piece that is applied to the volume hologram recording material described above on a base material, hardens the volume hologram layer by irradiation with ionizing rays, and then peeled off from the base material. .

In addition, the tensile strength of the volume hologram layer in the present invention is preferably within a range of 20 MPa to 40 MPa at 23 ° C., and more preferably within a range of 25 MPa to 35 MPa.
When the tensile strength of the volume hologram layer in the present invention is larger than the above range, the volume hologram layer becomes strong, so that the foil breakage is deteriorated and it may be difficult to transfer to the adherend during transfer. On the other hand, when it is smaller than the above range, there is a possibility that the volume hologram transfer foil of the present invention cannot be stably passed through the duplication process.
The method for measuring the tensile strength of the volume hologram layer can be the same as the method for measuring the breaking elongation of the volume hologram layer. Therefore, the value of the tensile strength of the volume hologram layer is a value measured by the measurement method and measurement conditions of the elongation at break described in the above-mentioned section “A. Volume hologram transfer foil 1. Protective layer” and the same measurement method. It is.

4). Next, the heat seal layer in the present invention will be described. The heat seal layer in the present invention contains a thermoplastic resin, and has a function of adhering the volume hologram layer and the adherend when producing the volume hologram laminate using the volume hologram transfer foil of the present invention. I have it. The heat seal layer in the present invention is formed on the volume hologram layer described above.
Hereinafter, the heat seal layer in the present invention will be described in detail.

As the thermoplastic resin used for the heat seal layer in the present invention, the volume hologram layer and the adherend can be bonded according to the kind of the adherend to which the volume hologram layer is transferred from the volume hologram transfer foil of the present invention. If it is a thing, it will not specifically limit.
Examples of such thermoplastic resins include ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, polyamide resin, polyester resin, polyethylene resin, ethylene-isobutyl acrylate copolymer resin, butyral resin, polyacetic acid. Vinyl and its copolymer resins, ionomer resins, acid-modified polyolefin resins, acrylic / methacrylic (meth) acrylic resins, acrylic ester resins, ethylene / (meth) acrylic acid copolymers, ethylene / (Meth) acrylic acid ester copolymer, polymethyl methacrylate resin, cellulose resin, polyvinyl ether resin, polyurethane resin, polycarbonate resin, polypropylene resin, epoxy resin, phenol resin, vinyl resin, maleic acid resin, Al Resin, polyethylene oxide resin, urea resin, melamine resin, melamine alkyd resin, silicone resin, rubber resin, styrene butadiene styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS), styrene ethylene Examples include butylene styrene block copolymer (SEBS) and styrene ethylene propylene styrene block copolymer (SEPS). In the present invention, any of these thermoplastic resins can be suitably used.

  In addition, the thermoplastic resin used for this invention may be only 1 type, or 2 or more types may be sufficient as it.

  The heat seal layer in the present invention may contain other additives in addition to the thermoplastic resin. Examples of the additive used in the present invention include a dispersant, a filler, a plasticizer, and an antistatic agent.

The thickness of the heat seal layer in the present invention is not particularly limited. The constituent material of the volume hologram layer described above, the type of adherend to which the volume hologram layer is transferred using the volume hologram transfer foil of the present invention, and the like. Is appropriately selected. Among them, the thickness of the heat seal layer in the present invention is preferably in the range of 1 μm to 50 μm, and more preferably in the range of 1 μm to 25 μm.
This is because if the thickness of the heat seal layer is thinner than the above range, the adhesion with the adherend may be insufficient. On the other hand, if it is thicker than the above range, when transferring the volume hologram layer from the volume hologram transfer foil of the present invention, the temperature for heating the heat seal layer becomes too high, and the adherend or the like may be damaged. Because there is sex.

5. Other Configurations The volume hologram transfer foil of the present invention has at least a base material, a protective layer, a volume hologram layer, and a heat seal layer, but has an optional configuration other than these as necessary. Also good. The arbitrary configuration used in the present invention is not particularly limited as long as a desired function can be imparted to the volume hologram transfer foil of the present invention.
Examples of such an arbitrary configuration include a primer layer, a barrier layer, and an ultraviolet prevention layer.

6). Production Method of Volume Hologram Transfer Foil The volume hologram transfer foil of the present invention can use a known method described below as a method for producing a volume hologram transfer foil.
First, a protective layer-forming coating solution is applied to a base material to form a protective layer, and a volume hologram recording material is applied to another base material, and a volume hologram is photographed using laser light. A recorded volume hologram layer is formed. Next, after heating the volume hologram layer and irradiating the entire surface with ultraviolet rays to fix the volume hologram layer, both the substrates are stacked so that the volume hologram layer is in contact with the protective layer, and the substrate / volume hologram is obtained. A layer / protective layer / substrate laminate is obtained. Thereafter, the substrate on the volume hologram layer side of the laminate is peeled off and then irradiated with ultraviolet rays to cure the protective layer, and a primer layer and a heat seal layer are formed on the side of the volume hologram layer that does not have the protective layer. By doing so, the volume hologram layer of the present invention can be formed. This series of manufacturing steps is performed by roll-to-roll.

7). Application The volume hologram transfer foil of the present invention is used for producing a volume hologram laminate having a configuration in which a volume hologram layer is bonded to an adherend by transferring the volume hologram layer onto the adherend.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the embodiment of this invention is not limited to a following example.

[Example 1]
(First laminate)
A PET film (Lumirror T60 (thickness 50 μm) manufactured by Toray Industries, Inc.) is prepared as a first film, and a volume hologram recording material having the following composition is applied with a gravure coat so as to have a dry thickness of 6 μm, A surface release treatment PET film (SP-PET (thickness 50 μm) manufactured by Tosero Co., Ltd.) was laminated on the coated surface to prepare a first laminate.

Binder resin {polymethyl methacrylate resin (weight average molecular weight; 200,000)} 50 parts by weight 3,9-diethyl-3′-carboxylmethyl-2,2′-thiacarbocyanine iodine salt 0.5 Part by weight-Diphenyliodonium hexafluoroantimonate ... 6 parts by weight-2,2-bis [4- (acryloxydiethoxy) phenyl] propane ... 80 parts by weight-1,6-hexanediol diglycidyl ether ... 80 parts by weight Fluorine-based fine particles: 8 parts by weight ・ Solvent (Methyl isobutyl ketone / n-butanol = 1/1 (weight ratio))
... 200 parts by weight

(Substrate / protective layer second laminate)
A PET film (SG-1 (thickness 38 μm) manufactured by Panac Co., Ltd.) is prepared as a second film (base material), and a protective layer solution having the following composition is used as a protective layer so that the dry thickness is 3 μm. It was coated with a gravure coat.

・ Urethane acrylate resin (purple UV-7620EA, manufactured by Nippon Synthetic Chemical Co., Ltd., weight average molecular weight; 4100, 9 functional groups, pencil hardness: 3H) 60 parts by weight ・ Urethane acrylate resin (purple UV-3500BA, manufactured by Nippon Synthetic Chemical Co., Ltd .; weight average molecular weight; 13000, functional Radix 2 Glass transition temperature 1 ° C. Pencil hardness 6B>Young's modulus 4 N / mm ² Breaking strength 5 N / mm ² Breaking elongation 140%) 40 parts by weight Acetophenone photopolymerization initiator (Irgacure 184 Ciba Specialty Chemicals Co., Ltd.) Made by company: 4 parts by weight ・ Polyethylene wax (weight average molecular weight; 10000 average particle size; 5 μm)
... 1 part by weight-Acrylic adhesive (SK Dyne 2094, manufactured by Soken Chemical Co., Ltd.) ... 0.5 part by weight-Solvent (methyl ethyl ketone) ... 400 parts by weight

(Volume hologram recording)
First film / layer of volume hologram recording material / surface release treatment A first laminate of PET film was photographed and recorded using a laser beam having a wavelength of 532 nm. Thereafter, the laminate was heated in an atmosphere of 100 ° C. for 10 minutes, and the entire surface was irradiated with ultraviolet rays having an irradiation dose of 1000 mJ / cm ² using a high-pressure mercury lamp.
Next, an 80 ° C. heated roller that is overlapped and nipped with the volume hologram layer exposed by peeling the surface release-treated PET film so that the protective layer side of the second laminate of the second film / protective layer is in contact After passing between the pair to obtain a laminate of the first film / volume hologram layer / protective layer / second film, the whole surface was irradiated with ultraviolet rays of 2500 mJ / cm ² using a high-pressure mercury lamp. Irradiation was performed to fix the volume hologram layer.

(Coating of heat seal layer)
The first film is peeled from the first film / volume hologram layer / protective layer / second film obtained above, and a material having the following composition is gravured on the volume hologram layer so as to have a dry thickness of 4 μm. Coated with a coat.

Polyester resin (Byron 550, manufactured by TOYOBO, Tg; -15 ° C, weight average molecular weight 28000) ... 20 parts by weight Solvent (methyl ethyl ketone / toluene = 1/1 (mass ratio)) ... 80 parts by weight

[Example 2]
A protective layer solution was prepared in the same manner as in Example 1 except that the composition of the protective layer solution was changed as follows.
・ Urethane acrylate resin (purple UV-7620EA, manufactured by Nippon Synthetic Chemical Co., Ltd., weight average molecular weight; 4100, 9 functional groups, pencil hardness: 3H) 60 parts by weight ・ Urethane acrylate resin (purple UV-3500BA, manufactured by Nippon Synthetic Chemical Co., Ltd .; weight average molecular weight; 13000, functional Radix 2 Glass transition temperature 1 ° C. Pencil hardness 6B>Young's modulus 4 N / mm ² Break strength 5 N / mm ² Break elongation 140%) 40 parts by weight UV-absorbing monomer {2-hydroxy-4- (2-acryloyloxy) ) Ethoxybenzophenone} 1 part by weight Acetophenone photopolymerization initiator (Irgacure 184 Ciba Specialty Chemicals) 2 parts by weight Phosphorus photopolymerization initiator {2,4,6-trimethylbenzoyldiphenyl Phosphine oxide (Lucirin TPO BASF) } ... 2 parts by weight acrylic adhesive (manufactured by SK Dyne 2094 manufactured by Soken Chemical & Engineering Co., Ltd.) ... 0.5 parts by weight Solvent (methyl ethyl ketone) ... 400 parts by weight

[Example 3]
A protective layer solution was prepared in the same manner as in Example 1 except that the composition of the protective layer solution was changed as follows.
・ Urethane acrylate resin (purple UV-7620EA, manufactured by Nippon Synthetic Chemical Co., Ltd., weight average molecular weight; 4100, 9 functional groups, pencil hardness: 3H) 60 parts by weight ・ Urethane acrylate resin (purple UV-3500BA, manufactured by Nippon Synthetic Chemical Co., Ltd .; weight average molecular weight; 13000, functional Radix 2 Glass transition temperature 1 ° C. Pencil hardness 6B>Young's modulus 4 N / mm ² Break strength 5 N / mm ² Break elongation 140%) 40 parts by weight UV-absorbing monomer {2-hydroxy-4- (2-acryloyloxy) ) Ethoxybenzophenone} 1 part by weight Acetophenone photopolymerization initiator (Irgacure 184 Ciba Specialty Chemicals) 2 parts by weight Phosphorus photopolymerization initiator {2,4,6-trimethylbenzoyldiphenyl Phosphine oxide (Lucirin TPO BASF) } ... 2 parts by weight of polyethylene wax (weight average molecular weight; 10000, average particle size; 5 [mu] m)
... 1 part by weight-Acrylic adhesive (SK Dyne 2094, manufactured by Soken Chemical Co., Ltd.) ... 0.5 part by weight-Solvent (methyl ethyl ketone) ... 400 parts by weight

[Comparative Example 1]
A volume hologram transfer foil was produced in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive was removed from the protective layer solution of Example 1.

[Comparative Example 2]
A volume hologram transfer foil was produced in the same manner as in Example 2 except that the acrylic adhesive was removed from the protective layer solution of Example 2.

[Comparative Example 3]
A volume hologram transfer foil was produced in the same manner as in Example 3 except that the acrylic pressure-sensitive adhesive was removed from the protective layer solution of Example 3.

[Comparative Example 4]
In the production of the second laminate, a volume hologram transfer foil was produced in the same manner as in Example 3 except that the acrylic pressure-sensitive adhesive was changed to the following.
-Acrylic adhesive (SK Dyne 2094, manufactured by Soken Chemical Co., Ltd.) ... 1.0 part by weight

[Comparative Example 5]
In the production of the second laminate, a volume hologram transfer foil was produced in the same manner as in Example 3 except that the acrylic pressure-sensitive adhesive was changed to the following.
・ Acrylic adhesive (SK Dyne 2094, manufactured by Soken Chemical Co., Ltd.) ... 1.5 parts by weight

[Break elongation measurement]
The breaking elongation was measured for the protective layers of Examples 1 to 3 and the protective layers of Comparative Examples 1 to 5. In addition, the measurement method of the said breaking elongation used the following measuring apparatus and measurement conditions according to JIS-K-5600. The results are shown in Table 1.
As shown in Table 1, the breaking elongation of the protective layers of Examples 1 to 3 is in the range of 1.1% to 2.1%, and the breaking elongation of the protective layers of Comparative Examples 1 to 3 is 1. The elongation at break of the protective layers of Comparative Examples 4 to 5 was over 2.1%.

(Measurement of elongation at break)
・ Measuring equipment: Self-recording tester (INSTRON 5565 manufactured by INSTRON)
・ Distance between chucks: 25mm
・ RANGE: 1%
・ Measurement environment: 23 ° C., 50% RH atmosphere ・ Tensile speed: 10 mm / min
・ Sample piece: 15 mm width strip

  In addition, about the volume hologram layer formed from the volume hologram recording material used in Examples 1-3 and Comparative Examples 1-5, when breaking elongation was measured according to the above-mentioned measuring method, the breaking elongation in 23 degreeC was 1 -10%.

[Tensile strength measurement]
About the protective layer of Examples 1-3 and the protective layer of Comparative Examples 1-5, the tensile strength was measured according to the measuring method of the breaking elongation mentioned above. Table 1 shows the results of the above measurement performed a plurality of times.

  In addition, about the tensile strength of the volume hologram layer of Examples 1-3 and Comparative Examples 1-5, when measured according to the measuring method similar to the tensile strength of the above-mentioned protective layer, the tensile strength in 23 degreeC was 25-35 MPa.

[Process suitability evaluation]
In the manufacturing process of the transfer foils of Examples 1 to 3 and the manufacturing process of the transfer foils of Comparative Examples 1 to 5, the occurrence of foil floating or peeling of the foil occurs between the second film (base material) and the protective layer. Visual confirmation was made whether there was any. The results are shown in Table 1. In Table 1, “No” indicates that there is no occurrence of foil floating or peeling off, and “X” indicates that occurrence of foil floating or peeling is confirmed.
In the manufacturing processes of the transfer foils of Examples 1 to 3 and Comparative Examples 4 to 5, it was possible to proceed with the manufacturing processes without causing foil floating and foil peeling. On the other hand, in the manufacturing process of the transfer foils of Comparative Examples 1 to 3, it was confirmed that foil floating or foil peeling occurred.

[Transfer evaluation]
The transfer foils of Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated for transfer at a transfer temperature of 150 ° C. and a transfer speed of 1 m / min using a commercially available thermal laminator for paper transfer. The results are shown in Table 1. In Table 1, when the transfer foil was well cut at the time of transfer and transferred without any trouble such as breakage, ○, when the transfer foil did not break at the time of transfer and when trouble such as breakage occurred To do.
In the transfer foils of Examples 1 to 3 and the transfer foils of Comparative Examples 1 to 3, transfer was possible from the transfer start portion to the transfer end portion. On the other hand, in the transfer foils of Comparative Examples 4 to 5, the transfer foil did not break at the transfer start portion, and the paper was broken and wound on the transfer foil side.

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Protective layer 3 ... Volume hologram layer 4 ... Heat seal layer 10 ... Volume hologram transfer foil

Claims (4)

A substrate;
A protective layer formed on the substrate and containing a curable resin and an adhesive;
A volume hologram layer formed on the protective layer and having a volume hologram recorded thereon;
A volume hologram transfer foil having a heat seal layer formed on the volume hologram layer,
The volume hologram transfer foil, wherein the content of the pressure-sensitive adhesive is an amount capable of maintaining the foil cutting property of the volume hologram transfer foil.   2. The volume hologram transfer according to claim 1, wherein the content of the pressure-sensitive adhesive is such that the breaking elongation of the protective layer at 23 ° C. falls within a range of 1.1% to 2.1%. Foil. The curable resin is two types of ionizing radiation curable resins having different weight average molecular weights,
3. The volume hologram transfer foil according to claim 1, wherein the weight average molecular weight of one of the two types of ionizing radiation curable resins is twice or more of the other weight average molecular weight. 4.   When the pressure-sensitive adhesive contained in the protective layer is an acrylic pressure-sensitive adhesive and the two types of ionizing radiation curable resins are acrylic resins, the content of the pressure-sensitive adhesive is the two types of ionizing radiation curing. The volume hologram transfer foil according to claim 3, wherein the content is less than 1 part by weight with respect to 100 parts by weight of the total content of the conductive resin.

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