JP6432986B2 - Decorative products and laminates for thermal transfer - Google Patents

Description

  The present invention relates to a decorative product produced by a thermal transfer method and a laminate for thermal transfer used for producing the decorative product.

  As an exterior decorative product 98 such as a front grill of an automobile, there is one in which a decorative portion 94 including a metal layer is formed on the surface of a resin base 96 as shown in FIG. As a method for forming the decorative portion 94 on the surface of the substrate 96, for example, there is a thermal transfer method.

  In order to form the decorative portion 94 including the metal layer on the surface of the base material 96 by the thermal transfer method, a release layer (heat-resistant resin cured layer) is previously formed on the surface of the film (base film) 90 as shown in FIG. ) 91, a protective layer 92, a metal layer (metal vapor deposition layer) 93, and an adhesive layer 95 are laminated to form a thermal transfer laminate (hot stamping foil) 97. With the adhesive layer 95 facing the surface of the substrate 96, the thermal transfer laminate 97 is disposed on the surface of the substrate 96. The laminated body 97 for thermal transfer is heated while being pressed against the base material 96, and the decorative portion 94 composed of the metal layer 93 and the protective layer 92 is transferred to the surface of the base material 96 via the adhesive layer 95. The film 90 and the heat-resistant resin cured layer 91 are removed from the decorating unit 94. Thereby, the decoration product 98 formed by forming the decoration part 94 in the base-material 96 surface is obtained (refer patent document 1).

Japanese Patent Laid-Open No. 62-282969

  By the way, at the time of thermal transfer, the thermal transfer laminate 97 is heated while being pressed against the substrate 96. At this time, since the thermal transfer laminate 97 extends, a tensile stress is applied to the metal layer 93. When a metal having a high elastic modulus such as Cr is used as the metal layer 93, when a tensile stress is applied to the metal layer 93 as described above, the metal layer 93 itself or between the metal layer 93 and the protective layer 92 is used. There is a possibility that cracks are generated in the vicinity of the interface and the glitter feeling emitted from the metal layer 93 is lowered.

  The protective layer 92 accumulates internal stress generated by shrinkage during curing. The metal layer 93 having a weak cohesive force tends to cause cohesive failure due to the stress of the protective layer 92 contracting. Therefore, shear stress concentrates in the vicinity of the metal layer 93 itself or the interface between the metal layer 93 and the protective layer 92. When the decorative portion 94 to which such shear stress is applied is used in an environment with a temperature change or scratches are generated, the metal layer 93 causes cohesive failure, and the cracks in the decorative portion 94 and the metal layer 93 May cause delamination due to cohesive failure.

  When the elastic modulus of the metal layer 93 is high, cracks in the decorative portion 94 and cohesive failure of the metal layer 93 cause a part of the decorative portion 94 to peel off from the base material 96 after an adhesion test described later. When the elastic modulus of the protective layer 92 is high, the internal stress of the protective layer 92 is increased, and the metal layer 93 is likely to cohesively break in the same manner as described above. Cause peeling. Furthermore, when the elastic modulus of the protective layer 92 is low, peeling from the base material 96 due to cohesive failure of the metal layer 93 can be suppressed, but cracks occur in the metal layer 93 and the protective layer 92 during thermal transfer, There is a possibility of causing the appearance defect of the decorative product.

  This invention is made | formed in view of this situation, a metal layer does not raise | generate a cohesive failure, reduces the generation | occurrence | production of the crack of a decorating part, and a part of decorating part peeling from a base material after an adhesion test. It is an object of the present invention to provide a decorative product that can be used and a thermal transfer laminate used for producing the decorative product.

The decorative product of the present invention comprises a base material and a decorative part,
The decorative portion is formed by laminating an adhesive layer made of resin, a metal layer, and a protective layer made of resin in order from the surface side of the base material,
The metal layer is made of a metal having an elastic modulus of 10 GPa or more and 150 GPa or less,
The protective layer has an elastic modulus of 0.5 GPa or more and 2.0 GPa or less.

The laminated body for thermal transfer of the present invention is a laminated body for thermal transfer formed by laminating a protective layer made of a resin, a metal layer, and an adhesive layer made of a resin in order on a film,
The metal layer is made of a metal having an elastic modulus of 10 GPa or more and 150 GPa or less,
The protective layer has an elastic modulus of 0.5 GPa or more and 2.0 GPa or less.

  According to the present invention, since the above structure is provided, the metal layer does not cause cohesive failure, and it is possible to reduce the occurrence of cracks in the decorative portion and part of the decorative portion peeling from the substrate after the adhesion test. It is possible to provide a decorative product that can be made and a thermal transfer laminate used for producing the decorative product.

It is a section explanatory view of a decoration. It is sectional explanatory drawing of the laminated body for thermal transfer. The elastic modulus and cohesive energy of various metals are shown. It is explanatory drawing which shows an up-down type hot stamp construction method. It is explanatory drawing which shows a roll type hot stamp construction method. FIG. 4 is a cross-sectional explanatory view of a decorative article of Sample 2. 2 is an optical micrograph of a metal layer of Sample 1. FIG. 3 is a cross-sectional explanatory view of the vicinity of the metal layer before and after stretching of the laminate for thermal transfer of Sample 1. FIG. 9A is a cross-sectional explanatory diagram of the decorative product after thermal transfer of the sample 5, and FIG. 9B is a cross-sectional explanatory diagram of the decorative product showing a state in which stress is concentrated between the protective layer and the metal layer. FIG. 9C is an explanatory view showing a state in which the metal layer and the protective layer are peeled off from the base material by the adhesion test, and FIG. 9D is a diagram of the decorative product in which the metal layer is cohesively broken by the adhesion test. It is a photograph. 3 is a SEM photograph of a metal layer of Sample 5. It is explanatory drawing which shows the bridge | crosslinking density and elastic modulus of the decorative article of the samples 5-16. It is explanatory drawing which shows the compounding ratio and elastic modulus of the 2nd acrylic polymer of the decorative article of the sample 7 and the samples 10-16. It is sectional explanatory drawing of the decorative article of a prior art example. It is sectional explanatory drawing of the laminated body for thermal transfer of a prior art example.

  The decorative article of the embodiment of the present invention and the laminate for thermal transfer used for producing the same will be described in detail.

(Decoration)
The decorative product of the embodiment of the present invention includes a base material and a decorative portion. The decorative portion is formed by laminating an adhesive layer, a metal layer made of a metal having an elastic modulus of 10 GPa to 150 GPa, and a protective layer having an elastic modulus of 0.5 GPa to 2.0 GPa in order from the surface side of the substrate. Do it.

  In the decorative product of the present invention, by using a metal having a low elastic modulus for the metal layer and further using a protective layer having an elastic modulus matched to the metal of the metal layer, not only a planar shape but also a three-dimensional shape base material Even when the metal layer is stretched, cohesive failure of the metal layer is suppressed, and excellent glitter can be maintained.

  FIG. 3 shows the elastic modulus and cohesive energy of various metals. In this specification, the cohesive energy refers to the energy required to separate metal atoms in an aggregated state far infinitely, and is obtained by the first principle calculation method.

  The elastic modulus of the metal from 10 GPa to 150 GPa is low among the elastic moduli of various metals. For this reason, by using such a metal for the metal layer, the stretchability of the metal layer is improved, and the metal layer can be stretched together with the protective layer by the pressure during thermal transfer.

  When the base material is made of a material having a high thermal expansion coefficient such as a resin, the base material expands and contracts due to a change in environmental temperature. Since the metal of the metal layer of the decorating part has the above elastic modulus, the stretchability of the metal layer is high. For this reason, the metal layer can expand and contract as the base material expands and contracts. Therefore, even under an environment where the temperature changes, the metal layer does not cause cohesive failure, and it is possible to suppress a part of the decorating part from being peeled off from the base material after the cracking of the metal layer and the adhesion test. A high radiance feeling can be maintained by the metal layer of the decoration part, and the appearance of the decoration is good. In particular, when the decorative product is a vehicle exterior product, the temperature change of the outside air is large. Also in this case, it is possible to suppress the occurrence of cracks in the decorative portion and a part of the decorative portion after the adhesion test from being peeled off from the base material, and the excellent appearance of the decorative product can be maintained.

  As shown in FIG. 3, for many metals having a low elastic modulus, the cohesive energy tends to be low, such as 350 kJ / mol or less. For this reason, about the metal layer which consists of a metal with a low elasticity modulus, it exists in the tendency for cohesion force to become small. Since the internal stress is accumulated in the protective layer due to shrinkage during curing, a metal layer with low cohesive force is less likely to follow the stress of the protective layer, and the metal layer itself or near the interface between the metal layer and the protective layer Shear stress is generated. In the decorative article having the decorative portion in such a state, the metal layer may cohesively break down due to factors such as temperature change and scratches, and the metal layer and the protective layer may peel from the base material.

  Therefore, in the decorative product of the present invention, the elastic modulus of the protective layer is as low as 0.5 GPa or more and 2.0 GPa or less. The protective layer having a low elastic modulus is relatively soft. For this reason, the internal stress accumulated by shrinkage at the time of hardening of a protective layer can also be made small, and the shear stress generated near the interface of metal layer itself or a metal layer and a protective layer can be reduced. Even if the produced decorative article is subjected to a stimulus such as a temperature change or a scratch, the metal layer is prevented from cohesive failure. Peeling of the metal layer and the protective layer from the substrate can also be suppressed.

  In addition, when the decorative part is produced by the thermal transfer method, the protective layer has the elastic modulus described above, and therefore the part adhered to the surface of the base material in the decorative part is on the surface of the base material in the decorative part. Foil cutting property is good when it is cut off from the unbonded part.

  Moreover, the decorative article of the present invention has a relatively small elastic modulus of the metal of the metal layer and the protective layer. For this reason, the stress which arises in a metal layer and a protective layer at the time of thermal transfer can be made small. Due to factors such as temperature changes and scratches, it is possible to suppress a part of the decorative portion after the cohesive failure of the metal layer and the adhesion test from peeling off from the substrate. Therefore, according to the decorative product of the present invention, a high glitter feeling of the metal layer can be maintained.

  The decorative article of the present invention has a base material and a decorative part formed on the surface of the base material by a thermal transfer method. In order to form a decoration part by a thermal transfer method, it is good to heat, pressing the below-mentioned laminated body for thermal transfer mentioned later which laminated | stacked the protective layer, the metal layer, and the contact bonding layer on the base material in order with respect to the film. A decoration part has said adhesive layer, a metal layer, and a protective layer. On the surface of the base material, an adhesive layer, a metal layer, and a protective layer are laminated in this order.

  In the decorative article of the present invention, the metal layer has an elastic modulus of 10 GPa to 150 GPa. When the elastic modulus of the metal of the metal layer is 10 GPa or more and 150 GPa or less, the metal layer can be highly stretched, and the metal layer does not cause cohesive failure at the time of expansion / contraction of the base material of the decorative product, and the decorative portion cracks It can suppress that a part of decorating part peels from a base material after generation | occurrence | production and an adhesion test. When the metal elastic modulus of the metal layer is less than 10 GPa, it is difficult to follow the stress of the protective layer, and shear stress is generated near the metal layer itself or the interface between the metal layer and the protective layer, causing the metal layer to cohesive failure There is a risk. When the metal elastic modulus of the metal layer exceeds 150 GPa, the stretchability of the metal layer is reduced, and the metal layer causes cohesive failure during pressurization during thermal transfer and during expansion and contraction of the base material of the decorative product. There is a possibility that a part of the decorating part may be peeled off from the base material after the occurrence of cracks in the decorating part or after the adhesion test.

The metal elastic modulus of the metal layer is preferably 10 GPa or more and 100 GPa or less, and preferably 10 GPa or more and 60 GPa or less. In the case of 10 GPa or more and 100 GPa or less, the high stretchability of the metal layer is further improved.
The metal elastic modulus of the metal layer is measured according to JIS Z 2280.

  The metal cohesive energy of the metal layer may be, for example, 350 kJ / mol or less, and more preferably 300 kJ / mol or less, 250 kJ / mol or less.

  The metal having an elastic modulus of 10 GPa or more and 150 GPa or less is preferably composed of one or more selected from the group consisting of indium, tin, silver, aluminum, and copper. Among these, indium and tin are preferable because of their low elastic modulus. The metal may be a single metal or an alloy as long as it has the above elastic modulus.

  It is preferable that the metal layer has a sea-island structure in which metals are scattered in an island shape. In this case, when the metal layer is stretched, the stress is divided by the metal scattered in the island shape, and the occurrence of cracks in the metal layer is suppressed. Therefore, the glitter feeling of the metal layer can be maintained. Further, the entire metal layer can be uniformly stretched during thermal transfer. For this reason, the reflectance of the light incident on the metal layer can be maintained constant, and the same appearance and color as before stretching can be maintained after stretching.

  The metal layer can be formed by, for example, wet plating or dry plating. In order to form the metal layer having the above-described sea-island structure, dry plating is preferable. Specific examples of the dry plating include vapor deposition such as vacuum vapor deposition, electron beam vapor deposition, and chemical vapor deposition, and sputtering. Examples of the wet plating include chemical plating and electroplating.

  The thickness of the metal layer is preferably 10 nm or more and 150 nm or less, and more preferably 20 nm or more and 60 nm or less. When the thickness of the metal layer is 10 nm or more and 150 nm or less, the metal layer easily forms a sea-island structure, and even when the metal has a sea-island structure, the metal is uniform and uniform when the decorative product is visually observed. It can be seen that it is formed, and the glitter can be maintained.

  In the decorative product of the present invention, the protective layer is made of a resin. The protective layer has an elastic modulus of 0.5 GPa or more and 2.0 GPa or less. When producing a decorative product, shear stress is applied to the vicinity of the interface between the protective layer and the metal layer or to the metal layer itself due to internal stress accumulated in the protective layer. However, in the manufactured decorative article, the protective layer having the relatively low elastic modulus adheres to the metal layer having a small cohesive force and extends to weaken the shear stress. Therefore, it can suppress that a part of decorating part peels from a base material after the cohesive failure and adhesion test of a metal layer. If the elastic modulus of the protective layer is less than 0.5 GPa, the protective layer may crack. When the elastic modulus of the protective layer exceeds 2.0 GPa, the shear stress acting between the protective layer and the metal layer is not weakened by the internal stress accumulated in the protective layer. There is a risk of peeling.

Furthermore, in the decorative article of the present invention, the elastic modulus of the protective layer is preferably 0.5 GPa or more and 1.8 GPa or less, and more preferably 1.0 GPa or more and 1.6 GPa or less. When the elastic modulus of the protective layer is 0.5 GPa or more and 1.8 GPa or less, it is effective for the cohesive failure of the metal layer and the peeling of the metal layer and the protective layer from the base material while maintaining the foil breakability of the protective layer. Can be suppressed.
The elastic modulus of the protective layer is measured according to JIS K 7161 by forming a sheet from the resin constituting the protective layer.

  In the decorative article of the present invention, the protective layer is preferably transparent to such an extent that the metal layer can be visually recognized. The protective layer is a layer formed by crosslinking a polymer with a curing agent, and preferably has a urethane resin. The urethane resin is preferably formed by crosslinking the first acrylic polymer with a curing agent having an isocyanate group. In this case, the protective layer can have flexibility while maintaining a certain degree of rigidity.

  Moreover, in the decorative article of the present invention, the urethane resin of the protective layer may be formed by crosslinking the first acrylic polymer and the second acrylic polymer with a curing agent having an isocyanate group. The OH group of the acrylic polymer is a bonding point of the curing agent and is a portion that becomes a crosslinking point. The hydroxyl value of the second acrylic polymer is smaller than that of the first acrylic polymer. For this reason, the crosslinking point of the second acrylic polymer by the curing agent is less than that of the first acrylic polymer. The urethane resin formed by crosslinking the first acrylic polymer and the second acrylic polymer has a crosslinking point in the protective layer relative to the urethane resin formed by crosslinking only the first acrylic polymer. It becomes soft because it decreases. Therefore, when a shear stress is generated between the metal layer and the protective layer due to the internal stress accumulated in the protective layer, the protective layer can adhere to the metal layer and extend. Therefore, the metal layer can be prevented from cohesive failure due to temperature change, scratching, and the like, and peeling of the metal layer and the protective layer from the substrate is also suppressed.

  In the decorative article of the present invention, the protective layer is preferably formed by crosslinking a polymer with a curing agent. In this case, the crosslinking density of the protective layer and the type of curing agent affect the elastic modulus of the protective layer. The crosslinking density refers to the molar amount of crosslinking points by the curing agent in the protective layer per volume of the protective layer. Examples of the curing agent include a chain aliphatic compound, an aromatic compound, and an alicyclic compound. The preferable range of the crosslinking density of the protective layer differs depending on which compound the curing agent is made of.

When the curing agent is composed of a chain aliphatic compound, the crosslink density of the protective layer is preferably 9.0 × 10 ⁻¹² mol / cm ³ or more and 2.0 × 10 ⁻¹⁰ mol / cm ³ or less. 9.0 × 10 ⁻¹² mol / cm ³ or more and 1.8 × 10 ⁻¹⁰ mol / cm ³ or less is preferable. When the curing agent is made of an aromatic compound, the crosslink density of the protective layer is preferably 2.0 × 10 ⁻¹¹ mol / cm ³ or more and 4.0 × 10 ⁻¹⁰ mol / cm ³ or less. When the curing agent is made of an alicyclic compound, the crosslink density of the protective layer is preferably 1.0 × 10 ⁻¹² mol / cm ³ or more and 2.5 × 10 ⁻¹⁰ mol / cm ³ or less. When the crosslink density of the protective layer is less than the above range, the protective layer may be too soft and easily damaged. When the crosslinking density of the protective layer is excessively higher than the above range, the rigidity of the protective layer is too high, and a cohesive failure occurs in the metal layer due to the shear stress between the protective layer and the metal layer generated at the time of curing shrinkage. There is a possibility that a part of the decorative portion may be peeled off from the substrate after the adhesion test.

The crosslinking density (n) of the protective layer is calculated by the following formula (A).
n = E '/ 3RT ... Formula (A)
(E ': storage modulus, R: gas constant, T: absolute temperature)
The storage elastic modulus of the protective layer can be measured with a dynamic viscoelasticity measuring device (device manufacturer: Rheology, device name: FT Rheospectra, model: DVE-V4).

  The urethane resin of the protective layer may have a group having light stability and / or a group having ultraviolet absorption performance. Further, the urethane resin of the protective layer preferably has a group having water resistance. These groups are preferably contained in the first acrylic polymer and / or the second acrylic polymer before thermosetting. Examples of the group having photostability include a group having a hindered amine skeleton. Examples of the group having ultraviolet absorption performance include a group having a benzotriazole skeleton and a group having a triazine skeleton. Examples of the group having water resistance include a saturated aliphatic ring. When the urethane resin has a group having such functionality, the protective layer can have light stability, ultraviolet absorption, and water resistance. By including the urethane resin having these groups in the protective layer, the decorative article can exhibit sufficient weather resistance and durability without covering the protective layer with the overcoat coating film.

  In the decorative article of the present invention, the protective layer may have a first acrylic polymer and a curing agent having an isocyanate group. Furthermore, the protective layer is preferably formed by crosslinking the first acrylic polymer with a curing agent having an isocyanate group. The protective layer preferably has a urethane resin formed by crosslinking the first acrylic polymer with a curing agent having an isocyanate group. The urethane resin formed by crosslinking the first acrylic polymer with a curing agent having an isocyanate group is also referred to as an acrylic urethane resin. The acrylic urethane resin has a first acrylic polymer block.

  Examples of the monomer of the first acrylic polymer include acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester. Among these, the acrylic ester or methacrylic ester preferably has a functional group ester-bonded to acrylic acid or methacrylic acid. Examples of the functional group include a group having light stability performance, a group having ultraviolet absorption performance, and a group having water resistance performance. Examples of the group having photostability include a group having a hindered amine skeleton. Examples of the group having ultraviolet absorption performance include a group having a benzotriazole skeleton and a group having a triazine skeleton. Examples of the group having water resistance include a saturated aliphatic ring. By polymerizing an acrylic ester or a methacrylic ester having such a functional group, the protective layer can have various functions.

  The various monomers of the first acrylic polymer may be bonded in any arrangement in the first acrylic polymer.

  The first acrylic polymer can be synthesized, for example, by causing an acrylic reaction by performing a known method such as heat or addition of a polymerization initiator to the monomer of the acrylic polymer.

  The first acrylic polymer preferably has a structural unit in which a group having a hindered amine skeleton is ester-bonded. In this case, light stability is imparted to the first acrylic polymer.

  The first acrylic polymer preferably has a structural unit in which a group having a benzotriazole skeleton or a triazine skeleton is ester-bonded. In this case, ultraviolet absorption performance is imparted to the first acrylic polymer.

  The first acrylic polymer includes acrylic acid or methacrylic acid, an acrylic ester or methacrylic ester having a group having a hindered amine skeleton, and an acrylic ester or methacrylic ester having a benzotriazole skeleton or a group having a triazine skeleton. It is preferable to polymerize. The decorative portion formed from the first acrylic polymer and the curing agent can also exhibit light stability and ultraviolet absorption performance.

  The first acrylic polymer is preferably represented by the following formula (1).

(In Formula (1), A is a group having a benzotriazole skeleton or a triazine skeleton, B is a group having a hindered amine skeleton, and R ₁ is a carbon-containing group. N1, n2, and n3 are integers of 0 or more. (However, n1 = n2 = n3 = 0 is excluded.)

  The hydroxyl value of the first acrylic polymer is preferably 20 mgKOH / g or more and 200 mgKOH / g or less, more preferably 20 to 100 mgKOH / g. A hydroxyl value means the mg number of KOH required in order to acetylate the OH group contained in 1g of samples. The hydroxyl value of the first acrylic polymer is measured according to JIS K 0070.

  The hydroxyl group of the first acrylic polymer can be a crosslinking point that crosslinks with the isocyanate group of the curing agent by a urethane bond. When the hydroxyl value of the acrylic polymer is too small, the reactivity between the acrylic polymer and the isocyanate group of the curing agent is low, the elastic modulus of the protective layer is too low, and cracks occur in the metal layer and protective layer during thermal transfer There is a risk. On the other hand, when the hydroxyl value of the acrylic polymer is excessive, the elastic modulus of the protective layer is too high, and the curing shrinkage force of the protective layer during curing shrinkage is large, and there is a shear stress between the protective layer and the metal layer. There is a risk that the metal layer may be cracked or peeled off due to a change in temperature or scratches.

  Since the resin of the protective layer further has a second acrylic polymer having a hydroxyl value lower than that of the first acrylic polymer, it is easy to adjust the elastic modulus of the protective layer to a desired elastic modulus. ,preferable.

  The protective layer preferably has a second acrylic polymer having a hydroxyl value smaller than the hydroxyl value of the first acrylic polymer in addition to the first acrylic polymer and the curing agent. Furthermore, the protective layer is preferably formed by crosslinking the first acrylic polymer and the second acrylic polymer with a curing agent having an isocyanate group. The protective layer preferably has a urethane resin formed by crosslinking the first acrylic polymer and the second acrylic polymer with a curing agent having an isocyanate group. The urethane resin formed by crosslinking the first acrylic polymer and the second acrylic polymer with a curing agent having an isocyanate group is also referred to as an acrylic urethane resin. The acrylic urethane resin has a first acrylic polymer block and a second acrylic polymer block.

  The hydroxyl group of the second acrylic polymer can be a crosslinking point that reacts with the isocyanate group of the curing agent. The protective layer has a first acrylic polymer having a crosslinking point and a second acrylic polymer having a crosslinking point less than the crosslinking point of the first acrylic polymer, so that the elastic modulus of the protective layer is increased. Furthermore, it can be lowered appropriately. For this reason, accumulation of internal stress due to hardening shrinkage of the protective layer is reduced, and the shear stress between the protective layer and the metal layer can be suppressed low, and the occurrence of cracks in the metal layer and the peeling of the protective layer can be further suppressed.

The hydroxyl value of the second acrylic polymer is preferably more than 0 and 30 mg KOH / g or less, more preferably more than 0 and 15 mg KOH / g or less.
The method for measuring the hydroxyl value of the second acrylic polymer is the same as the hydroxyl value of the first acrylic polymer.

  The various skeletons of the second acrylic polymer are preferably the same as those of the first acrylic polymer. The first acrylic polymer and / or the second acrylic polymer preferably has at least one selected from the group consisting of a group having a hindered amine skeleton, a group having a benzotriazole skeleton, and a group having a triazine skeleton. . Moreover, as a monomer of a 2nd acrylic polymer, the thing similar to the monomer of a 1st acrylic polymer can be used, for example.

  In the protective layer of the decorative article of the present invention, when the total mass of the first acrylic polymer and the second acrylic polymer is 100% by mass, the content of the second acrylic polymer exceeds 0 and is 85% by mass. % Or less, and more preferably 5% by mass or more and 75% by mass or less. If it exceeds 0 and is less than or equal to 85% by mass, internal stress due to shrinkage during curing of the protective layer can be reduced, and the protective layer can be reliably adhered to a metal layer having a weak cohesive force. When the content of the second acrylic polymer is 0, a large amount of internal stress is accumulated due to curing shrinkage of the protective layer, and the metal layer is caused by shear stress generated between the protective layer and the metal layer having a weak cohesive force. May cause cohesive failure, or the metal layer and the protective layer may peel off from the substrate. When the content of the second acrylic polymer exceeds 85% by mass, the cohesive force of the protective layer is weak, and cracks may occur during thermal transfer.

  In the decorative article of the present invention, the protective layer has a curing agent having an isocyanate group. Examples of the curing agent having an isocyanate group include a chain aliphatic compound, an aromatic compound, and an alicyclic compound. Among these, a chain aliphatic compound is preferable. Examples of the chain aliphatic compound include HDI (hexadiisocyanate). Examples of the alicyclic compound include IPDI (isophorone diisocyanate). Examples of the aromatic compound include TDI (tolylene diisocyanate) and XDI (xylene diisocyanate). The HDI system is particularly preferred. Urethane resins crosslinked with an HDI curing agent tend to have a low elastic modulus. The protective layer having an HDI-based curing agent is difficult to peel from the metal layer after thermal transfer. Here, HDI type, IPDI type, TDI type, and XDI type mean various isocyanates and their modified forms. Examples of modified forms include adducts, isocyanurates, burettes and allophanates of various isocyanates.

  In the decorative product of the present invention, when the total mass of the first acrylic polymer and the second acrylic polymer contained in the protective layer is 100 parts by mass, the mass of the curing agent contained in the protective layer is 5 masses. The amount is preferably not less than 80 parts by mass and more preferably not less than 15 parts by mass and not more than 50 parts by mass. In the case of 5 parts by mass or more and 80 parts by mass or less, the first acrylic polymer and the second acrylic polymer can be appropriately crosslinked with a curing agent. If the curing agent is less than 5 parts by mass, the foil breakability of the protective layer may be reduced. When the amount of the curing agent is more than 80 parts by mass, the protective layer is in an unreacted state with an excess of the curing agent more than the OH group that is a crosslinking point of the first acrylic polymer and the second acrylic polymer. And is not efficient.

  Moreover, when the protective layer is 100% by mass, the total mass of the first acrylic polymer, the second acrylic polymer and the curing agent is preferably 60% by mass or more and 100% by mass or less, and further 80 to 100%. It is preferable that it is mass%, and it is desirable that it is 90 mass% or more and 100 mass% or less.

  In the decorative article of the present invention, the protective layer includes the first acrylic polymer, the curing agent, and, if necessary, the second acrylic polymer. In addition to these, the protective layer may contain an additive. Examples of additives that can be included in the protective layer include well-known additives such as yellowing inhibitors. Moreover, when the protective layer is 100% by mass, the additive is preferably more than 0 and less than 40% by mass, and more preferably more than 0 and less than 20% by mass.

  In addition, the decorative product of the present invention includes a structure having various functions as a bonding group, which is included in the urethane resin, unlike the case where the urethane resin is mixed as an additive. For this reason, various functions can be exhibited for a long time.

  The thickness of the protective layer is preferably 1 μm or more and 10 μm or less, and more preferably 1 μm or more and 7 μm or less. On the surface of the protective layer (the outermost surface of the decorative product), an overcoat coating film may be further formed, or an overcoat coating film may not be formed. In the case where the protective layer is composed of a polymer having a group having light stability performance or a group having ultraviolet absorption performance, excellent weather resistance of the decorative portion can be exhibited without an overcoat coating film.

  In the decorative product of the present invention, a top layer is preferably interposed between the adhesive layer and the metal layer. In this case, the adhesive melted and softened at the time of thermal transfer and the metal layer with a small amount of deformation do not need to be in direct contact, and cracking of the metal layer can be suppressed. The top layer is made of a resin. The top layer is preferably made of the same resin as that of the protective layer. Furthermore, it is preferable that the resin component ratio of the protective layer (the ratio of the first acrylic polymer, the second acrylic polymer, and the curing agent) and the resin component ratio of the top layer are the same. When the metal layer has a sea-island structure, it is preferable that the resin of the top layer and the resin of the protective layer enter the metal layer and become sea components of the metal layer. By making the resin of the top layer and the resin of the protective layer the same, the compatibility of both is improved, and a strong anchor effect can be exerted on the metal layer. The thickness of the top layer is preferably 0.01 μm or more and 2 μm or less, and more preferably 0.01 μm or more and 1 μm or less.

  In the decorative article of the present invention, an adhesive layer is formed between the metal layer and the substrate, or when the top layer is formed, between the top layer and the substrate. The adhesive layer has a function of bonding the base material and the decorative portion. Examples of the resin contained in the adhesive layer include acrylic resins, chlorinated polypropylene resins, vinyl chloroacetate resins, and polyester resins. The thickness of the adhesive layer is preferably 0.5 μm or more and 5 μm or less.

  Examples of the substrate include resin, metal, and wood. Of these, the substrate is preferably a resin.

  The decorative article of the present invention can be used, for example, for exterior parts and interior parts for vehicles such as a front grille, a back panel, and ornaments.

  The decorative article of the present invention may be produced by a thermal transfer method using the following thermal transfer laminate, but is not limited thereto.

(Laminate for thermal transfer)
The laminate for thermal transfer according to the embodiment of the present invention is a transfer foil having a film and a decorative portion formed on the film. Examples of the material used for the film include polyesters such as polyethylene terephthalate (PET), polypropylene, polycarbonate, vinyl chloride, and polystyrene. The thickness of the film is preferably 16 μm or more and 50 μm or less.

  A decorative portion is formed on the film. A release layer may be interposed between the film and the decorative portion in order to improve the release property of the decorative portion. The release layer is a layer made of a resin, and the resin used for the release layer is not particularly limited as long as it can achieve the above-mentioned purpose, and a polyethylene resin, a polypropylene resin, a polystyrene resin, Various known resins such as vinyl chloride resin, polyester resin, acrylic resin, urethane resin, melamine resin, epoxy resin, fluorine resin, or wax can be used, any one of these, or Two or more kinds of mixed resins may be used, and may be appropriately selected according to the purpose. The thickness of the release layer is preferably 0.1 μm or more and 2 μm or less.

  In the laminate for thermal transfer of the present invention, the decorative portion is formed by laminating a protective layer, a metal layer, and an adhesive layer in order from the film side.

  The protective layer in the laminate for thermal transfer of the present invention can be the same as the protective layer of the decorative product of the present invention.

  In the thermal transfer laminate of the present invention, a top layer may be laminated between the metal layer and the adhesive layer. The top layer is made of a resin. The top layer preferably has the same resin as that of the protective layer. For example, when the protective layer has a first acrylic polymer and a curing agent, it is preferable that the top layer also has the first acrylic polymer and a curing agent.

  Furthermore, it is preferable that the resin component ratio of the protective layer (the ratio of the first acrylic polymer, the second acrylic polymer, and the curing agent) and the resin component ratio of the top layer are the same. When the metal layer has a sea-island structure, the resin of the top layer and the resin of the protective layer enter the metal layer as sea components of the metal layer. By making the resin of the top layer and the resin of the protective layer the same, the compatibility of both is improved, and a strong anchor effect can be exerted on the metal layer. The thickness of the top layer is preferably 0.01 μm or more and 2 μm or less, and more preferably 0.01 μm or more and 1 μm or less.

  In the laminated body for thermal transfer of the present invention, the adhesive layer has a function of adhering the decorative portion to the counterpart substrate for thermal transfer. Examples of the resin contained in the adhesive layer include acrylic resins, chlorinated polypropylene resins, vinyl chloroacetate resins, and polyester resins. The thickness of the adhesive layer is preferably 0.5 to 5 μm.

  The release layer, the protective layer, the top layer, and the adhesive layer can each be formed by a conventionally known coating method such as a gravure coating method, a reverse coating method, or a die coating method.

  The decorative portion of the laminate for thermal transfer of the present invention is thermally transferred onto the substrate. In thermal transfer, a thermal transfer laminate is disposed on a substrate, and the thermal transfer laminate is pressed against the surface of the substrate by applying pressure while heating. When the decorative portion is cooled, the bonded portion that is bonded to the surface of the base material in the decorative portion is bonded to the base material. Thereafter, when the film is removed from the surface of the base material, the non-adhesive portion that is not adhered to the surface of the base material in the decoration portion is separated from the adhesion portion of the decoration portion and removed from the base material surface together with the film. Thereby, the part which is in contact with the base material surface of the decorating part is transferred to the base material surface.

  The film is removed from the substrate surface after the protective layer, the top layer, and the adhesive layer are cooled and solidified. The foil cutting property is improved, and the film is removed after the decorative portion is securely bonded to the base material, so that the decorative portion is reliably transferred to the base material.

  Examples of the thermal transfer include a hot stamp method and an in-mold (simultaneous molding transfer method) method. Examples of the hot stamping method include a method using an up-down hot stamping device 8 shown in FIG. 4 and a roll hot stamping device 8 shown in FIG. The up-down type hot stamp apparatus 8 includes a pressurizer 84 having a hot plate 81 and a rubber plate 82, and a table 83. The rubber plate 82 heated by the hot plate 81 moves up and down so that the thermal transfer laminate 1 is movable. The thermal transfer laminate 1 is arranged on the base material 3 on the table 83 and the thermal transfer laminate 1 is pressed against the base material 3 by the rubber plate 82 to decorate the thermal transfer laminate 1 on the base material 3. The part 4 is thermally transferred.

  The roll-type hot stamp apparatus 8 includes a movable table 87 and a pressurizer 84 having a rotating rubber roller 85 and a heat source 86 disposed around the rotary rubber roller 85. In this method, the rotating rubber roller 85 heated by the heat source 86 is lowered and the movable table 87 is moved while pressurizing the heat transfer laminate 1 to thermally transfer the decorative portion 4 of the heat transfer laminate 1 to the substrate 3. is there.

  In both the up-down type and the roll type, the thermal transfer laminate is preferably heated to a temperature of 100 to 150 ° C.

  About the various decoration goods of the samples 1-16, it manufactured with the thermal transfer method using the laminated body for thermal transfer, and used for evaluation. Samples 7 to 15 are products of the present invention, and samples 1 to 6 and sample 16 are reference products.

(Sample 1)
As shown in FIG. 1, the decorative product 2 of the sample 1 includes a base material 3 and a decorative portion 4 formed on the surface of the base material 3. The decorative portion 4 is formed by laminating an adhesive layer 15, a top layer 14, a metal layer 13, and a protective layer 12 in order from the surface side of the substrate 3. The base material 3 consists of polypropylene resin. The adhesive layer 15 is made of a chlorinated polypropylene resin. The top layer 14 and the protective layer 12 are made of an acrylic urethane resin formed by crosslinking a first acrylic polymer and a second acrylic polymer described later with a curing agent. The metal layer 13 is made of chromium. Hereinafter, the manufacturing method of the decorative article 2 will be described.

  First, the thermal transfer laminate 1 is prepared. As shown in FIG. 2, the thermal transfer laminate 1 is formed by sequentially laminating a release layer 11, a protective layer 12, a metal layer 13, a top layer 14, and an adhesive layer 15 on a film 10.

  In order to produce a laminate for thermal transfer, first, a film 10 made of polyethylene terephthalate and having a thickness of 25 μm was prepared. A thermoplastic resin made of melamine resin was applied on the film 10 by a gravure coating method to form a release layer 11 having a thickness of 0.5 μm.

  The 1st acrylic polymer, the 2nd acrylic polymer, and the hardening | curing agent were mixed, and the mixed resin A was obtained. The first acrylic polymer and the second acrylic polymer are each a methacrylic acid ester having a hydroxyl group (HMA), a methacrylic acid ester having a hindered amine skeleton (HAMA), or a methacrylic acid ester having a benzotriazole skeleton (BTMA). And a methacrylic acid ester (CHMA) having a cyclohexane ring is polymerized. These blending molar ratios are HMA: HAMA: BTMA: CHMA = 12: 2: 5: 81 in the first acrylic polymer, and MA: HAMA: BTMA: CHMA = 3 in the second acrylic polymer. : 2: 5: 90. The hydroxyl value of the first acrylic polymer was 39 mgKOH / g, and the hydroxyl value of the second acrylic polymer was 8 mgKOH / g. The hydroxyl value was measured according to JIS K 0070. The weight average molecular weight of the first acrylic polymer was 30000, and the weight average molecular weight of the second acrylic polymer was 80000.

  The first acrylic polymer and the second acrylic polymer have a structure represented by the formula (2). In the first acrylic polymer and the second acrylic polymer, the benzotriazole skeleton and acrylic acid are chemically bonded, and the hindered amine skeleton and acrylic acid are chemically bonded.

(In the formula, A represents a group having a benzotriazole skeleton, B represents a group having a hindered amine skeleton, C represents a cyclohexyl group, and R ₁ represents a carbon-containing group. N1, n2, n3, and n4 are integers of 1 or more. )

  A hardening | curing agent is a TDI nurate type trimer which has a structure shown to Formula (3).

  When the total mass of the first acrylic polymer and the second acrylic polymer in the mixed resin is 100% by mass, the mass ratio of the first acrylic polymer is 50% by mass. The mass ratio was 50% by mass. When the total mass of the first acrylic polymer and the second acrylic polymer was 100 parts by mass, the mass of the curing agent was 25 parts by mass. The mixed resin A was applied to the surface of the release layer 11 by a gravure coating method to form a protective layer 12 having a thickness of 4 μm. In the formed protective layer 12, the crosslinking reaction proceeds with heat during drying of the gravure coat printing, and a part of both the first acrylic polymer and the second acrylic polymer is crosslinked with a curing agent, and the acrylic urethane A resin is formed.

  Chromium was deposited on the surface of the protective layer 12 by physical vapor deposition (PVD) to form a metal layer 13 made of chromium with a thickness of 30 nm. In the laminate for thermal transfer, the metal layer 13 made of chromium had a flat structure without a sea-island structure. It was 279 GPa when the elasticity modulus of the chromium of the metal layer 13 was measured according to JISZ2280. The cohesive energy of chromium was 389 kJ / mol.

  The above mixed resin A was applied to the surface of the metal layer 13 by a gravure coating method to form a top layer 14 having a thickness of 0.1 μm. In the formed top layer 14, the crosslinking reaction proceeds due to the heat during drying of the gravure coat printing, and both of the first acrylic polymer and the second acrylic polymer are crosslinked with a curing agent, and the acrylic urethane A resin is formed.

  An adhesive layer made of chlorinated polypropylene was applied to the surface of the top layer 14 by a gravure coating method to form an adhesive layer 15 having a thickness of 1.5 μm. Thus, a thermal transfer laminate 1 was obtained.

  The decorative portion 4 was formed on the substrate 3 using the thermal transfer laminate 1 and the hot stamp device 8. The material of the base material 3 was a polypropylene resin. As the hot stamping apparatus, an up-down type shown in FIG. 4 was used. The up-down type hot stamp apparatus 8 includes a pressurizer 84 having a hot plate 81 and a rubber plate 82, and a table 83. The rubber plate 82 heated to 180 ° C. by the hot plate 81 moves up and down, so that the thermal transfer laminate 1 is movable. The thermal transfer laminate 1 is placed on the substrate 3 on the table 83, and the thermal transfer laminate 1 is pressed against the substrate 3 by the rubber plate 82. The decorative portion 4 of the thermal transfer laminate 1 is fixed to the surface of the substrate 3 by softening or melting the adhesive layer 15. In the protective layer 12 and the top layer 14 of the decorative portion 4, the first acrylic polymer and the second acrylic polymer are further subjected to a crosslinking reaction by the curing agent, and an acrylic urethane resin is further formed.

  After the transfer, the pressurizer 84 is raised. Then, the decoration part 4 is cooled and the film 10 is lifted. The adhesion part 4a adhered to the surface of the base material 3 of the decoration part 4 is separated from the non-adhesion part 4b not adhered to the surface of the base material 3 of the decoration part 4 and remains on the surface of the base material 3. The non-adhesive portion 4 b of the decorative portion 4 is removed from the base material 3 together with the film 10. Thereby, the adhesion part 4a of the decorating part 4 is transcribe | transferred to the base-material 3 surface, and the decorating goods 2 are obtained.

It was 1.60 GPa when the elasticity modulus of the protective layer 12 of the decorative article 2 was measured according to JIS K 7161. The crosslink density of the protective layer 12 was 9.75E-11 mol / cm ³ . This crosslink density is a value calculated by measuring the storage elastic modulus of the protective layer 12 using a dynamic viscoelasticity measuring apparatus and using the above formula (A).

(Sample 2)
In the decorative product 2 of the sample 2, the protective layer 12 includes a lower layer 121 and an upper layer 122 as shown in FIG. The lower layer 121 is made of an acrylic urethane resin formed by crosslinking an acrylic polymer with a curing agent. The upper layer 122 is made of an acrylic polymer. The acrylic polymer of the upper layer 122 is not crosslinked. The acrylic polymer monomers of the lower layer 121 and the upper layer 122 do not contain any of a methacrylic acid ester having a hindered amine skeleton and a methacrylic acid ester having a benzotriazole skeleton. The thickness of the lower layer 121 was 3 μm, and the thickness of the upper layer 122 was 1.5 μm.

  The decorative product 2 of the sample 2 is formed by the thermal transfer method using the thermal transfer laminate as in the case of the sample 1. In the thermal transfer laminate, the lower layer 121 is made of a mixed resin composed of an acrylic polymer and a curing agent, and the upper layer 122 is made of an acrylic polymer. When a decorative product was formed by the thermal transfer method using the laminate for thermal transfer, the lower layer 121 was formed with an acrylic urethane resin, and the upper layer 122 was still an acrylic polymer.

The elastic modulus of the lower layer 121 of the protective layer 12 of the decorative article 2 of Sample 2 was 2.50 GPa, and the crosslinking density was 7.50E-10 mol / cm ³ . The elastic modulus of the upper layer 122 of the protective layer 12 of the decorative article 2 of Sample 2 was 0.35 GPa.

  Other points of the decorative article 2 of the sample 2 are the same as those of the sample 1.

(Sample 3)
The upper layer 122 of the protective layer 12 of the decorative article 2 of the sample 3 is composed of 88% by mass of an acrylic polymer, 4% by mass of a hindered amine compound (trade name: TINUVIN123, manufactured by BASF), and a triazine type when the upper layer 122 is 100% by mass. And 8% by mass of a compound (trade name: TINUVIN 384-2, manufactured by BASF). The elastic modulus of the upper layer 122 of the protective layer 12 of the decorative article 2 of the sample 3 was 0.34 GPa.
In the decorative article 2 of the sample 3, the configuration other than the upper layer 122 of the protective layer 12 was the same as that of the sample 2.

(Sample 4)
The thickness of the upper layer 122 of the protective layer 12 of the decorative article 2 of the sample 4 is the same as that of the sample 3 except that the thickness is 3 μm. The elastic modulus and crosslinking density of the upper and lower layers of the protective layer of the decorative article of Sample 4 are the same as those of Sample 3.

<Experiment 1>
The decorative articles of Samples 1 to 4 were evaluated for adhesion, foil breakability, ultraviolet absorption, and appearance.

-Adhesion was evaluated by conducting a tape adhesion test according to JIS 5401. The test conditions were a cut interval of 2 mm and a 100 (10 × 10) mass. The case where there was no peeling in the decorative part by the tape adhesion test was evaluated as “◯”, and the case where there was peeling was evaluated as “X”.
-Foil cutting property evaluated the ease of separation when the part which is in contact with the base material of the decorative part of the laminate for thermal transfer is separated from the part which is not in contact with the base material during thermal transfer. When the burr | flash generate | occur | produced in the decorating part transcribe | transferred to the base-material surface at the time of cut | disconnecting, or the case where a chip | tip generate | occur | produces at the time of transcription | transfer, it was set as x, and the case where a burr | flash or a chip | tip has not generate | occur | produced was set as (circle).
-The ultraviolet absorptivity formed the thin film which consists only of the same decorating part as the decorating part for every sample on PET film. About each thin film, the light transmittance when the light of a wavelength 300-360 nm ultraviolet region was irradiated was measured. The case where the light transmittance was 10% or less was evaluated as ◯, the case where it exceeded 10% and 80% or less was Δ, and the case where it exceeded 80% was evaluated as x.
-Appearance is x when there is no glitter due to the occurrence of cracks in the decorative part due to the occurrence of cracks, the metal layer is visible but the luminance (gross) is JIS 5600-4-7 (1999), the measurement angle is 60 The case where the brightness (gross) at a degree is less than 400 GU and the glitter feeling is low is Δ, and the case where the metal layer is visible and the brightness of the metal layer is 400 GU or more is high.

  Table 1 shows various evaluation results.

  About the decorative article of the sample 1, foil cutting property was favorable. However, the appearance of the decorative article of Sample 1 was low in glitter. When the metal layer of Sample 1 was observed with an optical microscope, microcracks having a size of about 2 to 10 μm were generated as shown in FIG. From this, as shown in FIG. 8, tensile stress is applied to the metal layer 13 by pressurization to the thermal transfer laminate during thermal transfer, but since the Cr constituting the metal layer 13 has a high elastic modulus, it is stretched. Is insufficient, and cracks are generated non-uniformly. For this reason, it is considered that the incident light is irregularly reflected on the surface of the metal layer 13 and the brightness is lowered.

  For the decorative product of Sample 3, the ultraviolet absorption performance was Δ.

  About the decorative article of the sample 4, foil cutting property was not good. In the decorative article of Sample 4, the elastic modulus of the upper layer 122 of the protective layer 12 is too low, and the thickness of the upper layer 122 is large. Therefore, when the film is removed after transfer, it is fixed to the substrate surface of the decorative portion 4. The part was not quickly separated from the part that is not fixed to the substrate surface, and burrs were generated at the periphery of the decorative part 4.

  For sample 2, the acrylic urethane resin constituting the protective layer did not contain a portion having a triazine skeleton or a benzotriazole skeleton having an ultraviolet absorption performance, and therefore the ultraviolet absorption performance was poor.

<Experiment 2>
About the decoration of the sample 1, the sample 2, and the sample 3, the sustainability of the ultraviolet absorption function was evaluated. In this experiment 2, a transparent thin film having a thickness of 4 μm consisting only of the same protective layer as that of the decorative product of each sample 1, 2, 3 was formed on the PET film. Each thin film was subjected to a water resistance test for 240 hours under conditions of immersion in warm water at 40 ° C. The light transmittance when each thin film was irradiated with light having a wavelength of 300 to 450 nm was measured before and after the test.

  In the thin film of Sample 1, the light transmittance in the ultraviolet region having a wavelength of 300 to 360 nm was almost zero before and after the water resistance test, and the light transmittance did not change. On the other hand, the thin film of Sample 2 did not contain a portion having a triazine skeleton or a benzotriazole skeleton having an ultraviolet absorption performance, and thus the ultraviolet absorption performance was poor. In the thin film of Sample 3, the light transmittance in the ultraviolet region before the water resistance test was good, but the light transmittance in the ultraviolet region after the water resistance test was lowered. This is because, in sample 3, the triazine compound having ultraviolet absorbing performance was exposed to the surface of the thin film during the water resistance test and pulverized (bleeded out). On the other hand, in the sample 1, the benzotriazole skeleton having an ultraviolet absorbing ability is chemically bonded to acrylic acid, and therefore, the bleed-out did not occur as in the thin film of the sample 3.

  From the above, it can be seen that when the protective layer is made of an acrylic urethane resin obtained by cross-linking an acrylic polymer having a group having a triazine skeleton or a group having a benzotriazole skeleton with a curing agent, the ultraviolet absorption performance is sustained. It was.

(Sample 5)
The decorative article of Sample 5 is the same as Sample 1 except that the metal layer is made of indium and the mixed resin constituting the protective layer does not contain the second acrylic polymer.

  The laminated body for thermal transfer used for producing the decorative article of Sample 5 is that a metal layer made of indium is formed, and that the mixed resin constituting the protective layer does not contain the second acrylic polymer. Is the same as the laminated body for thermal transfer of Sample 1. The metal layer 13 of the thermal transfer laminate of Sample 5 was made of indium having a thickness of 50 nm and formed by physical vapor deposition (PVD). In FIG. 10, the SEM photograph of the metal layer of a decorative article is shown. The metal layer 13 had a sea-island structure in which indium was scattered in an island shape having a size of 0.2 μm or more and 0.4 μm or less. The elastic modulus of indium used for the metal layer 13 was 11 GPa, and the cohesive energy of indium was 230 kJ / mol. A protective layer consists of mixed resin which consists of a 1st acrylic polymer and a hardening | curing agent. In the mixed resin, the content of the curing agent is 49 parts by mass with respect to 100 parts by mass of the first acrylic polymer.

In the decorative article of Sample 5, the protective layer is made of an acrylic urethane resin obtained by crosslinking the first acrylic polymer with a curing agent made of a TDI nurate trimer. The first acrylic polymer used in Sample 5 is the same as the first acrylic polymer used in Sample 1. The crosslinking density of the protective layer of the decorative article of Sample 5 was 7.50E-10 (7.50 × 10 ⁻¹⁰ ) mol / cm ³ , and the elastic modulus of the protective layer was 2.50 GPa.

  The various characteristics of the decorative product of Sample 5 were evaluated in the same manner as in <Experiment 1>. As a result, the decorative product of Sample 5 had a high glitter feeling expressed from the metal layer and a good appearance. As shown in FIG. 10, since the indium of the metal layer has a sea-island structure, the sea-island structure is uniformly stretched in the plane direction even after being stretched by thermal transfer or the like. This is probably because the same light reflectance as before stretching was maintained.

Moreover, about the adhesiveness of the decorative article of the sample 5, the protective layer peeled from the base material by the adhesion test, and was x. FIG.9 (d) shows the photograph of the decoration product after an adhesion test. After the adhesion test, as shown in FIG. 9 (d), the metal layer was agglomerated and broken, and the metal layer 13 and the protective layer 12 were peeled off from the substrate 3. As shown in FIG. 9A, internal stress due to curing shrinkage is accumulated in the protective layer 12. The metal layer 13 in contact with the protective layer 12 is made of indium. Indium has a low elastic modulus, a low cohesive energy, and a low cohesive force (FIG. 3). For this reason, the metal layer 13 can follow the aggregation of the protective layer 12. On the other hand, as shown in FIG. 9B, the elastic modulus of the protective layer 12 is as high as 2.50 GPa, and shear stress is accumulated between the protective layer 12 and the metal layer 13. As shown in FIG. 9 (c), when the tape adhesion test was performed on the decorative product in which shear stress was accumulated, the metal layer 13 was agglomerated and the metal layer 13 and the protective layer 12 were separated from the surface of the base material 3. It is considered a thing.
The decorative article of Sample 5 had good foil breakability and ultraviolet absorption.

(Sample 6)
The decorative product of Sample 6 was manufactured in the same manner as Sample 5 except that an HDI adduct was used as a curing agent. The protective layer is made of an acrylic urethane resin obtained by crosslinking the first acrylic polymer with an HDI adduct. The crosslinking density of the protective layer of the decorative article of Sample 6 was 1.50E-10 (1.50 × 10 ⁻¹⁰ ) mol / cm ³ , and the elastic modulus of the protective layer was 2.10 GPa.

  The various properties of the decorative product of Sample 6 were evaluated in the same manner as in <Experiment 1>, and the foil cutting property and the UV absorption property were ◯. However, with regard to adhesion, the protective layer was peeled off from the substrate by the adhesion test. X. The decorative product had a high radiance and the appearance was good.

(Sample 7)
The decorative product of Sample 7 was manufactured in the same manner as Sample 5 except that an HDI nurate trimer was used as a curing agent. The protective layer is made of an acrylic urethane resin obtained by crosslinking the first acrylic polymer with an HDI nurate trimer. The crosslinking density of the protective layer of the decorative article of Sample 7 was 1.90E-10 (1.90 × 10 ⁻¹⁰ ) mol / cm ³ , and the elastic modulus of the protective layer was 1.90 GPa.

  Various characteristics of the decorative article of Sample 7 were evaluated in the same manner as in <Experiment 1>. About the decorative article of the sample 7, foil cutting | disconnection property, ultraviolet-ray absorptivity, and external appearance were (circle), peeling did not arise also at the time of an adhesion test, and adhesiveness was (circle).

(Sample 8)
The decorative product of Sample 8 was produced in the same manner as Sample 5, except that HDI nurate 5,7-mer was used as the curing agent. The protective layer is made of an acrylic urethane resin obtained by crosslinking the first acrylic polymer with HDI nurate 5,7-mer. The crosslinking density of the protective layer of the decorative article of Sample 8 was 1.80E-10 (1.80 × 10 ⁻¹⁰ ) mol / cm ³ , and the elastic modulus of the protective layer was 2.00 GPa.

  When the various characteristics of the decorative article of Sample 8 were evaluated in the same manner as in <Experiment 1>, all of adhesion, foil breakage, ultraviolet absorptivity, and appearance were evaluated as ◯.

(Sample 9)
The decorative product of Sample 9 was manufactured in the same manner as Sample 5 except that an IPDI adduct was used as the curing agent. The protective layer is made of an acrylic urethane resin obtained by crosslinking the first acrylic polymer with an IPDI adduct. The crosslinking density of the protective layer of the decorative article of Sample 9 was 2.30E-10 (2.30 × 10 ⁻¹⁰ ) mol / cm ³ , and the elastic modulus of the protective layer was 2.00 GPa.

  When the various characteristics of the decorative article of Sample 9 were evaluated in the same manner as in <Experiment 1>, all of adhesion, foil breakage, ultraviolet absorption, and appearance were evaluated as ◯.

(Sample 10)
The decorative article of Sample 10 is Sample 5 except that a laminate for thermal transfer having a protective layer comprising a first acrylic polymer, a second acrylic polymer, and an HDI nurate trimer as a curing agent is used. Manufactured in the same manner. The first acrylic polymer and the second acrylic polymer used in Sample 10 are the same as the first acrylic polymer and the second acrylic polymer used in Sample 1. When the total mass of the first acrylic polymer and the second acrylic polymer contained in the protective layer of the thermal transfer laminate is 100% by mass, the mass ratio of the first acrylic polymer and the second acrylic polymer Of the first acrylic polymer: second acrylic polymer = 95% by mass: 5% by mass.

The protective layer of the decorative article of Sample 10 is made of an acrylic urethane resin obtained by crosslinking the first acrylic polymer and the second acrylic polymer with an HDI nurate trimer. The crosslinking density of the protective layer of the decorative article of Sample 10 was 1.77E-10 (1.77 × 10 ⁻¹⁰ ) mol / cm ³ . The elastic modulus of the protective layer of the decorative article of Sample 10 was 1.62 GPa.

  When the various characteristics of the decorative article of Sample 10 were evaluated in the same manner as in <Experiment 1>, all of adhesion, foil breakage, ultraviolet absorption, and appearance were evaluated as ◯.

(Sample 11)
When the total mass of the first acrylic polymer and the second acrylic polymer contained in the protective layer of the thermal transfer laminate is 100% by mass, the decorative article of Sample 11 is the first acrylic polymer and the second acrylic polymer. The acrylic polymer was produced in the same manner as Sample 10, except that the mass ratio of the acrylic polymer was set to 1st acrylic polymer: 2nd acrylic polymer = 85 mass%: 15 mass%.

The crosslinking density of the protective layer of the decorative article of Sample 11 was 1.55E-10 (1.55 × 10 ⁻¹⁰ ) mol / cm ³ . The elastic modulus of the protective layer of the decorative article of Sample 11 was 1.48 GPa.

  The various properties of the decorative article of Sample 11 were evaluated in the same manner as in <Experiment 1>. As a result, the foil breakability, ultraviolet absorption, and appearance were good, and the adhesion of the protective layer was strong against the substrate. It was adhering to ◎.

(Sample 12)
When the total mass of the first acrylic polymer and the second acrylic polymer contained in the protective layer of the laminate for thermal transfer is 100% by mass, the decorative product of Sample 12 is the first acrylic polymer and the second acrylic polymer. The acrylic polymer was manufactured in the same manner as Sample 10, except that the mass ratio of the acrylic polymer was set to 1st acrylic polymer: 2nd acrylic polymer = 70 mass%: 30 mass%.

The crosslinking density of the protective layer of the decorative article of Sample 12 was 9.30E-11 (9.30 × 10 ⁻¹¹ ) mol / cm ³ . The elastic modulus of the protective layer of the decorative article of Sample 12 was 1.52 GPa.

  The various properties of the decorative article of Sample 12 were evaluated in the same manner as in <Experiment 1>. The tearability, ultraviolet absorption, and appearance were good, and the protective layer was strong against the substrate with respect to adhesion. It was adhering to ◎.

(Sample 13)
When the total mass of the first acrylic polymer and the second acrylic polymer contained in the protective layer of the laminate for thermal transfer is 100% by mass, the decorative product of Sample 13 is the first acrylic polymer and the second acrylic polymer. The acrylic polymer was produced in the same manner as Sample 10, except that the mass ratio of the acrylic polymer was set to 1st acrylic polymer: 2nd acrylic polymer = 50 mass%: 50 mass%.

The crosslinking density of the protective layer of the decorative article of Sample 13 was 5.02E-11 (5.02 × 10 ⁻¹¹ ) mol / cm ³ . The elastic modulus of the protective layer of the decorative article of Sample 13 was 1.38 GPa.

  The various characteristics of the decorative article of Sample 13 were evaluated in the same manner as in <Experiment 1>. As a result, the foil breakability, ultraviolet absorption, and appearance were good, and the adhesion of the protective layer was strong against the substrate. It was adhering to ◎.

(Sample 14)
When the total mass of the first acrylic polymer and the second acrylic polymer contained in the protective layer of the thermal transfer laminate is 100% by mass, the decorative product of Sample 14 is the first acrylic polymer and the second acrylic polymer. The acrylic polymer was produced in the same manner as Sample 10, except that the mass ratio of the acrylic polymer was set to 1st acrylic polymer: 2nd acrylic polymer = 40 mass%: 60 mass%.

The crosslinking density of the protective layer of the decorative article of Sample 14 was 2.69E-11 (2.69 × 10 ⁻¹¹ ) mol / cm ³ . The elastic modulus of the protective layer of the decorative article of Sample 14 was 1.08 GPa.

  Various characteristics of the decorative article of Sample 14 were evaluated in the same manner as in <Experiment 1>. The decorativeness of sample 14 had a foil breakability, ultraviolet absorptivity, and appearance. For the decorative product of Sample 14, the protective layer adhered firmly to the substrate even after the adhesion test, and the adhesion was ◎.

(Sample 15)
When the total mass of the first acrylic polymer and the second acrylic polymer contained in the protective layer of the laminate for thermal transfer is 100% by mass, the decorative product of Sample 15 is the first acrylic polymer and the second acrylic polymer. The acrylic polymer was manufactured in the same manner as Sample 10, except that the mass ratio of the acrylic polymer was set to 1st acrylic polymer: 2nd acrylic polymer = 30 mass%: 70 mass%.

The crosslinking density of the protective layer of the decorative article of Sample 15 was 1.35E-11 (1.35 × 10 ⁻¹¹ ) mol / cm ³ . The elastic modulus of the protective layer of the decorative article of Sample 15 was 0.92 GPa.

  Various characteristics of the decorative article of Sample 15 were evaluated in the same manner as in <Experiment 1>. The adhering property, the foil cutting property, the ultraviolet ray absorbing property and the appearance of the decorative product of Sample 15 were good.

(Sample 16)
When the total mass of the first acrylic polymer and the second acrylic polymer contained in the protective layer of the thermal transfer laminate is 100% by mass, the decorative product of Sample 16 is the first acrylic polymer and the second acrylic polymer. The acrylic polymer was manufactured in the same manner as Sample 10, except that the mass ratio of the acrylic polymer was set to 1st acrylic polymer: 2nd acrylic polymer = 15 mass%: 85 mass%.

The crosslinking density of the protective layer of the decorative article of Sample 16 was 8.74E-12 (8.74 × 10 ⁻¹² ) mol / cm ³ . The elastic modulus of the protective layer of the decorative article of Sample 16 was 0.47 GPa.

  Various characteristics of the decorative product of Sample 16 were evaluated in the same manner as in <Experiment 1>. The adhering property, foil cutting property, and ultraviolet absorption property of the decorative product of Sample 16 were good.

  Table 2 summarizes the blending ratio of the acrylic polymer of the protective layer of the laminate for thermal transfer of Samples 5 to 16 and the type of curing agent, the crosslinking density and elastic modulus of the protective layer of the decorative product, and the appearance of the decorative product. It was. Moreover, it showed in FIG. 11 about the crosslinking density and elastic modulus of the protective layer of the decorative article of Samples 5 to 16. FIG. 12 shows the relationship between the blending ratio of the second acrylic polymer in the protective layer of the decorative article of Samples 7 and 10 to 16 and the elastic modulus of the protective layer of the decorative article. In FIG. 12, when the adhesion of the decorative part of the decorative product is good and the appearance is good, ○, when the adhesion of the decorative part is good but the appearance is not good, Δ, when the adhesion of the decorative part is not good Was displayed as x.

  As shown in FIG. 11 and Table 2, it was found that the relationship between the elastic modulus and the crosslinking density was greatly different depending on the type of the curing agent. It has been found that when the curing agent is the same as that of the HDI nurate trimer, the elastic modulus of the protective layer of the decorative article decreases when the mass ratio of the second acrylic polymer is increased.

  As shown in FIG. 12, when the blending ratio of the second acrylic polymer in the protective layer was 5 to 85% by mass, the adhesion and appearance of the decorative part of the decorative product were good.

  Samples 5 to 16 were evaluated for the durability of the ultraviolet absorption function in the same manner as in <Experiment 2>. As a result, the light transmittance in the ultraviolet region with a wavelength of 300 to 360 nm was almost zero before and after the water resistance test for the thin films of Sample 5 to Sample 16, and the light transmittance did not change. It was. In Samples 5 to 16, as in Sample 1, the benzotriazole skeleton having ultraviolet absorbing ability was chemically bonded to acrylic acid, and thus it was found that the ultraviolet absorbing ability was sustained.

1: Laminated body for thermal transfer, 10: film, 11: release layer, 12: protective layer, 13: metal layer, 14: top layer, 15: adhesive layer, 2: decorative product, 3: base material, 4: added Decoration part, 8: Hot stamping device.

Claims (14)

A base material and a decoration part are provided,
The decorative portion is formed by laminating an adhesive layer made of resin, a metal layer, and a protective layer made of resin in order from the surface side of the base material,
The metal layer is made of a metal having an elastic modulus of 10 GPa or more and 150 GPa or less,
The protective layer, Chi also 2.0GPa modulus below than 0.5 GPa,
The protective layer includes a first acrylic polymer, a curing agent having an isocyanate group, and a second acrylic polymer having a hydroxyl value smaller than the hydroxyl value of the first acrylic polymer. Characteristic decoration. The decorative product according to claim 1 , wherein the hydroxyl value of the first acrylic polymer is 20 mgKOH / g or more and 200 mgKOH / g or less. The decorative product according to claim 1 or 2 , wherein the hydroxyl value of the second acrylic polymer is more than 0 and not more than 30 mgKOH / g. The first acrylic polymer and / or the second acrylic polymer has at least one selected from the group consisting of a group having a hindered amine skeleton, a group having a benzotriazole skeleton, and a group having a triazine skeleton. Item 5. The decorative product according to any one of Items 1 to 3 . The said decoration part is a decoration article in any one of Claims 1-4 which has interposed the top layer which has the same resin as the said protective layer between the said contact bonding layer and the said metal layer. The said metal of the said metal layer consists of 1 or more types chosen from the group which consists of indium, tin, silver, aluminum, and copper, The decorating article in any one of Claims 1-5 . The said metal layer is the decorating article in any one of Claims 1-6 which has the sea island structure in which the said metal is scattered in island shape. On the film, in order, a laminate for thermal transfer formed by laminating a protective layer made of resin, a metal layer, and an adhesive layer made of resin,
The metal layer is made of a metal having an elastic modulus of 10 GPa or more and 150 GPa or less,
The protective layer, Chi also 2.0GPa modulus below than 0.5 GPa,
The protective layer includes a first acrylic polymer, a curing agent having an isocyanate group, and a second acrylic polymer having a hydroxyl value smaller than the hydroxyl value of the first acrylic polymer. A laminate for thermal transfer. The laminate for thermal transfer according to claim 8 , wherein the first acrylic polymer has a hydroxyl value of 20 mgKOH / g or more and 200 mgKOH / g or less. The thermal transfer laminate according to claim 8 or 9 , wherein the second acrylic polymer has a hydroxyl value of more than 0 and not more than 30 mgKOH / g. The first acrylic polymer and / or the second acrylic polymer has at least one selected from the group consisting of a group having a hindered amine skeleton, a group having a benzotriazole skeleton, and a group having a triazine skeleton. Item 11. The thermal transfer laminate according to any one of Items 8 to 10 . The laminate for thermal transfer according to any one of claims 8 to 11 , wherein a top layer having the same resin as that of the protective layer is interposed between the adhesive layer and the metal layer. The thermal transfer laminate according to any one of claims 8 to 12 , wherein the metal of the metal layer is one or more selected from the group consisting of indium, tin, silver, aluminum, and copper. The laminate for thermal transfer according to any one of claims 8 to 13 , wherein the metal layer has a sea-island structure in which the metal is scattered in an island shape.