阅读说明：本技术 装饰成型品、装饰成型品的制造方法、转印片和显示装置 (Decorative molded article, method for producing decorative molded article, transfer sheet, and display device ) 是由 波多野正弘 嶋田贵之 秋山健太郎 泷泽一树 于 2018-06-06 设计创作，主要内容包括：本发明提供一种凹凸面的亮度均匀并且抑制了白化的装饰成型品。一种装饰成型品,该装饰成型品在被附着体上包括具有凹凸表面的保护层,该装饰成型品满足下述条件1－1。＜条件1－1＞：制作在上述被附着体侧的面隔着透明粘合剂层贴合黑色板而成的样品A。使从上述样品A的法线方向倾斜10度的可见光线射入上述凹凸表面,以入射光的正反射方向作为基准角度,在以上述基准角度为中心的±5.0度的范围内,每隔0.2度测定视感反射率。在将相对于上述基准角度为－5.0度的视感反射率设为Y<Sub>－5.0</Sub>、将－4.8度的视感反射率设为Y<Sub>－4.8</Sub>时,将以[(Y<Sub>－4.8</Sub>－Y<Sub>－5.0</Sub>)/((Y<Sub>－4.8</Sub>+Y<Sub>－5.0</Sub>)/2)]×100表示的值作为－5.0度时的视感反射率的变化率。计算全部测定角度下的视感反射率的变化率,以测定角度为x轴、以变化率为y轴且利用最小二乘法制作近似直线时,该近似直线的斜率为－2.00以上－0.90以下。(The invention provides a decorative molded article having a uniform brightness of a concave-convex surface and suppressed whitening. A decorative molded article comprising a protective layer having an uneven surface on an adherend, the decorative molded article satisfying the following condition 1-1. < Condition 1-1 >: a surface formed on the side of the attached body with a transparent film therebetweenSample a, in which the clear adhesive layer was laminated to a black panel. Visible light beams inclined by 10 degrees from the normal direction of the sample a were incident on the uneven surface, and the perceived reflectance was measured at 0.2 degrees intervals within a range of ± 5.0 degrees around the reference angle with the normal reflection direction of the incident light as the reference angle. Y represents a reflectance of-5.0 degrees with respect to the reference angle －5.0 Y represents a visual reflectance of-4.8 degrees －4.8 Then, will be given with [ (Y) －4.8 －Y －5.0 )/((Y －4.8 +Y －5.0 )/2)]The value represented by X100 was defined as the rate of change of the perceived reflectance at-5.0 degrees. The change rate of the apparent reflectance at all measurement angles is calculated, and when an approximate line is created by the least square method with the measurement angle as the x-axis and the change rate as the y-axis, the slope of the approximate line is from-2.00 to 0.90.)

1. A decorative molded article characterized by:

the decorative molded article comprises a protective layer having a concave-convex surface on an adherend, and satisfies the following condition 1-1,

conditions 1 to 1:

preparing a sample A obtained by bonding a black plate to the surface on the adherend side through a transparent adhesive layer, allowing visible light inclined by 10 degrees from the normal direction of the sample A to enter the uneven surface, measuring the apparent reflectance at intervals of 0.2 degrees within a range of + -5.0 degrees with respect to a reference angle which is a regular reflection direction of incident light, and setting the apparent reflectance at-5.0 degrees with respect to the reference angle as Y_－5.0Y represents a visual reflectance of-4.8 degrees_－4.8Then, will be given with [ (Y)_－4.8－Y_－5.0)/((Y_－4.8+Y_－5.0)/2)]The change rate of the reflectance at each measurement angle of-5.0 degrees to +4.8 degrees is calculated from the expression, and when an approximate straight line is created by the least square method with the measurement angle being the x-axis and the change rate being the y-axis, the slope of the approximate straight line is from-2.00 to-0.90.

2. The decorative molding article according to claim 1, wherein:

the following conditions 1-2 are also satisfied,

conditions 1 to 2:

within a range of ± 5.0 degrees from the reference angle, an absolute value of a difference between a value of the apparent reflectance calculated from the approximate straight line and an actually measured value of the apparent reflectance at each measurement angle is calculated for each measurement angle, and a standard deviation of the absolute value of the difference calculated within the range of ± 5.0 degrees is 0.50 to 1.60%.

3. A decorative molding article according to claim 1 or 2, characterized in that:

the following conditions 1 to 3 are also satisfied,

conditions 1 to 3:

when the angle of the 1/2 apparent reflectance indicating the apparent reflectance at the reference angle is α, the average of the absolute values of α is 2.5 to 5.0 degrees.

4. A decorative molding according to any one of claims 1 to 3, wherein:

the following conditions 1 to 4 are also satisfied,

conditions 1 to 4: a perceived reflectance Y at the reference angle₀Is 2.0% or less.

5. A decorative molding according to any one of claims 1 to 4, wherein:

the protective layer includes a region P having the uneven surface and a region Q adjacent to the region P, the region P and the region Q satisfying the following conditions 1 to 5,

conditions 1 to 5:

the method comprises the steps of allowing visible light rays inclined by 10 degrees from the normal direction of the sample A to enter the surface of the region P and the region Q of the sample A, measuring the apparent reflectance at intervals of 0.2 degrees within a range of + -5.0 degrees around the reference angle with the regular reflection direction of the incident light as the reference angle, and setting the apparent reflectance at the reference angle of the region P as Y_0PAnd Y represents the apparent reflectance at the reference angle of the region Q_0QWhen, Y_0Q－Y_0PIs more than 1.5 percent.

6. A transfer sheet characterized by:

the transfer sheet having a protective layer on a release sheet, at least a part of a surface of the release sheet on a side contacting the protective layer having a concave-convex surface, the transfer sheet satisfying the following condition 2-1,

condition 2-1:

bonding the transfer sheet to a black plate via a transparent adhesive layer on the surface of the transfer sheet on the side of the protective layer, and then peeling off the release sheet to produce a sample B having the black plate, the transparent adhesive layer, and a protective layer having a surface shape complementary to the surface shape of the transfer sheet in this order, allowing visible light inclined by 10 degrees from the normal direction of the sample B to enter the uneven surface of the protective layer, measuring the apparent reflectance at intervals of 0.2 degrees within a range of + -5.0 degrees with the reference angle as the center thereof with the normal reflectance direction of the incident light as the reference angle, and setting the apparent reflectance Y at-5.0 degrees with respect to the reference angle as the apparent reflectance Y_－5.0Y represents a visual reflectance of-4.8 degrees_－4.8Then, will be given with [ (Y)_－4.8－Y_－5.0)/((Y_－4.8+Y_－5.0)/2)]The change rate of the reflectance at each measurement angle of-5.0 degrees to +4.8 degrees is calculated from the above formula, and when an approximate straight line is created by the least square method with the measurement angle being the x-axis and the change rate being the y-axis, the slope of the approximate straight line is from-2.00 to-0.90.

7. A method for manufacturing a decorative molded article, characterized in that:

the following steps (1) and (2) are sequentially carried out,

(1) a step of obtaining a laminate by bringing an adherend into close contact with the surface of the transfer sheet according to claim 6 on the side of the protective layer with respect to the release sheet;

(2) and a step of separating the release sheet of the transfer sheet from the laminate.

8. A display device, characterized in that:

a decorative molding according to any one of claims 1 to 5 provided on the front surface of a display element.

Technical Field

The invention relates to a decorative molded article, a method for manufacturing the decorative molded article, a transfer sheet, and a display device.

Background

Conventionally, in the fields of household electrical appliances, automobile interior parts, miscellaneous goods, and the like, high functionality and design are exhibited by decorating the surface of an adherend with characters, patterns, and the like.

As a method for decorating the surface of the adherend, there is a transfer method. The transfer method is a method in which: the decoration is performed by forming a transfer sheet having a transfer layer including a release layer, a pattern layer, an adhesive layer, and the like on a base material, heating and pressurizing the transfer sheet to adhere the transfer layer to an adherend, and then releasing the base material to transfer only the transfer layer to the adherend surface.

Depending on the application, the surface of the adherend may be required to have excellent design properties in which different textures such as a glossy feel and a matte (mat) feel are mixed.

For example, patent document 1 discloses a partially matte transfer sheet in which a release layer containing a matting agent (matting agent) over the entire surface, a mask layer partially containing an active energy ray-curable resin, and a release layer and a pattern layer as transfer layers are formed on a base sheet. Further, patent document 1 discloses a partially matte transfer molded article obtained by adhering the transfer layer side of the transfer sheet to the adherend surface, applying heat and pressure from the base sheet side of the transfer sheet to adhere the transfer layer to the adherend surface, and then peeling the base sheet, the release layer, and the mask layer.

Disclosure of Invention

Technical problem to be solved by the invention

However, the transfer layer of the partially matte transfer molded article described in patent document 1 after transfer has uneven brightness and poor appearance. Further, the partially matte transfer molded article described in patent document 1 sometimes appears whitish in surface appearance.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a decorative molded article in which the brightness of the uneven surface is made uniform and whitening is suppressed, a method for producing the decorative molded article, a transfer sheet used for the decorative molded article, and a display device using the decorative molded article.

Technical solution for solving technical problem

In order to solve the above-mentioned problems, the present invention provides the following [1] to [4 ].

[1] A decorative molded article comprising a protective layer having an uneven surface on an adherend, wherein the decorative molded article satisfies the following condition 1-1.

< Condition 1-1 >

Sample a was prepared by attaching a black plate to the surface of the adherend side with a transparent adhesive layer interposed therebetween. Visible light inclined by 10 degrees from the normal direction of the sample a was incident on the uneven surface, and the perceived reflectance (luminance reflectance) was measured at 0.2 degrees intervals within a range of ± 5.0 degrees around the reference angle with the normal reflection direction of the incident light as the reference angle. Y represents a reflectance of-5.0 degrees with respect to the reference angle_－5.0Y represents a visual reflectance of-4.8 degrees_－4.8Then, will be given with [ (Y)_－4.8－Y_－5.0)/((Y_－4.8+Y_－5.0)/2)]The value represented by the expression X100 was defined as the rate of change of the apparent reflectance at-5.0 degrees. When the change rate of the apparent reflectance at each measurement angle of-5.0 degrees to +4.8 degrees is calculated from the above equation, and an approximate line is created by a least square method with the measurement angle being an x-axis and the change rate being a y-axis, the slope of the approximate line is from "" 2.00 to "" 0.90.

[2] A transfer sheet having a protective layer on a release sheet, wherein at least a part of a surface of the release sheet on a side contacting the protective layer has a concave-convex surface, and the transfer sheet satisfies the following condition 2-1.

< Condition 2-1 >

The transfer sheet was bonded to a black plate via a transparent pressure-sensitive adhesive layer on the surface of the transfer sheet on the protective layer side, and the release sheet was peeled off to produce sample B having the black plate, the transparent pressure-sensitive adhesive layer, and the protective layer having a surface shape complementary to the surface shape of the transfer sheet in this order. Visible light inclined by 10 degrees from the normal direction of the sample B was incident on the uneven surface of the protective layer, and the perceived reflectance was measured at 0.2 degrees intervals within a range of ± 5.0 degrees around the reference angle with the regular reflection direction of the incident light as the reference angle. Y represents a reflectance of-5.0 degrees with respect to the reference angle_－5.0Y represents a visual reflectance of-4.8 degrees_－4.8Then, will be given with [ (Y)_－4.8－Y_－5.0)/((Y_－4.8+Y_－5.0)/2)]The value represented by X100 was defined as the rate of change of the perceived reflectance at-5.0 degrees. The change rate of the apparent reflectance at each measurement angle of-5.0 degrees to +4.8 degrees is calculated from the above formula, and when an approximate line is created by the least square method with the measurement angle as the x-axis and the change rate as the y-axis, the slope of the approximate line is from-2.00 to-0.90.

[3] A method for manufacturing a decorated molded article, wherein,

the following steps (1) and (2) are sequentially performed:

(1) a step of obtaining a laminate by bringing an adherend into close contact with the surface of the transfer sheet according to [2] on the side of the protective layer with respect to the release sheet;

(2) and separating the release sheet of the transfer sheet from the laminate.

[4] A display device comprising the decorative molded article according to [1] above on a front surface of a display element.

ADVANTAGEOUS EFFECTS OF INVENTION

The decorative molded article and the display device using the same can make brightness uniform and inhibit whitening. In addition, the transfer sheet and the method for producing a decorative molded article according to the present invention can easily produce a decorative molded article exhibiting the above-described effects.

Drawings

FIG. 1 is a sectional view showing one embodiment of a decorative molded article of the present invention.

Fig. 2 is a graph showing the distribution of the apparent reflectance in the range of ± 5.0 degrees in the decorative molded articles of example 7 and comparative example 2.

FIG. 3 is a graph showing the distribution of the change rate of the reflectance of visual perception at each measurement angle of-5.0 degrees to +4.8 degrees in the decorative molded article of example 7.

FIG. 4 is a graph showing the distribution of the change rate of the reflectance of visual perception at each measurement angle of-5.0 degrees to +4.8 degrees in the decorative molded article of comparative example 2.

Fig. 5 is a view for explaining a method of measuring the apparent reflectance of the decorative molded article.

Fig. 6 is a sectional view showing one embodiment of the transfer sheet of the present invention.

FIG. 7 is a sectional view showing one embodiment of the process for producing a decorative molded article of the present invention.

Detailed Description

[ decorative moldings ]

The decorative molded article of the present invention includes a protective layer having an uneven surface on an adherend, and satisfies the following condition 1-1.

< Condition 1-1 >

Sample a was prepared by attaching a black plate to the surface of the adherend side with a transparent adhesive layer interposed therebetween. Visible light beams inclined by 10 degrees from the normal direction of the sample a were incident on the uneven surface, and the perceived reflectance was measured at 0.2 degrees intervals within a range of ± 5.0 degrees around the reference angle with the normal reflection direction of the incident light as the reference angle. Y represents a reflectance of-5.0 degrees with respect to the reference angle_－5.0Y represents a visual reflectance of-4.8 degrees_－4.8Then, will be given with [ (Y)_－4.8－Y_－5.0)/((Y_－4.8+Y_－5.0)/2)]The value represented by the expression X100 was defined as the rate of change of the apparent reflectance at-5.0 degrees. The change rate of the apparent reflectance at each measurement angle of-5.0 degrees to +4.8 degrees is calculated from the above formula, and when an approximate line is created by the least square method with the measurement angle as the x-axis and the change rate as the y-axis, the slope of the approximate line is from-2.00 to-0.90.

FIG. 1 is a sectional view showing one embodiment of a decorative molded article of the present invention. The decorative molded article 100 of fig. 1 includes a protective layer 21 having an uneven surface on the attached body 10.

In fig. 1, an adhesive layer 22 is provided between the adherend 10 and the protective layer 21, and the surface of the protective layer includes a region P having an uneven surface and a region Q adjacent to the region P.

< Condition 1-1 >, a process for producing a polycarbonate resin composition, and a process for producing a polycarbonate resin composition

In condition 1-1, the slope of the approximate straight line calculated as described above is required to be-2.00 or more and-0.90 or less. First, the technical significance of condition 1-1 will be explained.

Fig. 2 is a graph showing the distribution of the apparent reflectance in the range of ± 5.0 degrees in the decorative molded articles of example 7 and comparative example 2. The solid line shows the distribution of the apparent reflectance in example 7, and the broken line shows the distribution of the apparent reflectance in comparative example 2. From the comparison between example 7 (solid line) and comparative example 2 (broken line), it was confirmed that the change in the reflectance of the molded article for decoration of example 7 was slower than that of the molded article for decoration of comparative example 2.

Next, fig. 3 is a graph showing the distribution of the change rate of the apparent reflectance at each measurement angle of-5.0 degrees to +4.8 degrees in the decorative molded article of example 7. The slope of the approximate straight line prepared by the least square method from the distribution of fig. 3 was "-1.81".

On the other hand, FIG. 4 is a graph showing the distribution of the change rate of the reflectance of visual perception at each measurement angle of-5.0 degrees to +4.8 degrees in the decorative molded article of comparative example 2. The slope of the approximate straight line prepared by the least square method from the distribution of fig. 4 was "-2.82".

The slope of the approximate straight line calculated from the distributions of fig. 3 and 4 is associated with the above-described examination of fig. 2. That is, since the approximate straight line in fig. 3 (example 7) is inclined to a smaller extent than the approximate straight line in fig. 4 (comparative example 2), it is understood that the degree of the slope of the approximate straight line shows the degree of change in the apparent reflectance within the range of ± 5.0 degrees.

Therefore, the slope of the approximate straight line is-2.00 or more, which means that the change in the apparent reflectance within the range of ± 5.0 degrees is small. Further, since "transmittance ≈ 100 — perceived reflectance", a change in perceived reflectance of the decorative molded article is small, meaning that a change in transmittance of the decorative molded article is small. Therefore, by setting the slope of the approximate straight line to-2.00 or more, the change of the reflected light and the transmitted light of the decorative molded article can be reduced, and the brightness at the center of the visual field of the decorative molded article can be made uniform.

As described above, by setting the slope of the approximate straight line to-2.00 or more, the brightness at the center of the visual field of the decorative molded article can be made uniform.

On the other hand, the slope of the approximate straight line is close to 0, meaning that the distribution of the apparent reflectance in the range of ± 5.0 degrees in fig. 2 is close to a semicircular shape (the surface reflection of the approximately-decorated molded article is uniformly diffused in all directions). In other words, the slope of the approximate straight line is close to 0, which means that the surface diffusion of the decorative molded article is strong.

Therefore, by setting the slope of the approximate straight line to-0.90 or less, the surface diffusion of the decorative molded article can be suppressed, and whitening can be suppressed.

The slope of the approximate line is preferably-1.80 to-1.00, more preferably-1.50 to-1.10.

In the present specification, "AA to BB" means "from AA to BB.

Fig. 5 is a diagram illustrating a method of measuring the apparent reflectance of the decorative molded article 100.

In order to measure the apparent reflectance of the decorative molded article 100, first, a sample a was prepared by bonding a black plate 400 to the adherend-side surface of the decorative molded article 100 via a transparent adhesive layer 300 (500). Next, visible light inclined by 10 degrees from the normal direction of sample a (500) was incident on the uneven surface. The direction of the chain line in fig. 5 indicates the normal direction, and the solid line in fig. 5 indicates the incident light. Then, the reflectance was measured every 0.2 degrees within a range of ± 5.0 degrees around the reference angle with the regular reflection direction of the incident light as the reference angle. The broken line of fig. 5 corresponds to the regular reflection direction (reference angle) of the incident light.

As the refractive index of the transparent pressure-sensitive adhesive layer 300 used in sample a and sample B described later, a material having a refractive index difference of 0.05 or less from the refractive index of the adherend 10 and the black plate 300 can be used, and the refractive index difference is preferably 0.00. In the present specification, the refractive index refers to a refractive index at a wavelength of 589 nm.

In the present specification, the term "apparent reflectance" refers to a Y value in the XYZ chromaticity system of CIE 1931.

In the present specification, the slope of the approximate straight line in condition 1-1 is defined as the average of the measured values at 10 points. The same applies to the conditions 1-2, 1-3, 1-4, 1-5 and 1-6 and the conditions 2-1 to 2-6 described later.

< other Condition >)

The decorative molded article (sample A formed from the decorative molded article) preferably satisfies one or more of the following conditions 1-2 to 1-6.

< Condition 1-2 >

Within a range of ± 5.0 degrees from the reference angle, an absolute value of a difference between a value of the apparent reflectance calculated from the approximate straight line and an actually measured value of the apparent reflectance at each measurement angle is calculated for each measurement angle. The standard deviation of the absolute value of the difference calculated within a range of + -5.0 degrees is 0.50 to 1.60%.

The standard deviation of the absolute value of the difference of the conditions 1-2 indicates that the angular distribution of the concave-convex surface has a certain randomness. When a defect such as a flaw is generated on the uneven surface by setting the standard deviation of the absolute value of the difference to 0.50% or more, the defect can be made inconspicuous. Further, by setting the standard deviation of the absolute value of the difference to 1.60% or less, a harsh feeling can be made less likely to occur. The "dazzling feeling" is a phenomenon in which fine unevenness in brightness is visible to image light due to the uneven structure.

In the condition 1-2, the standard deviation of the absolute value of the difference is more preferably 0.60 to 1.40%, and still more preferably 0.70 to 1.20%.

< Condition 1-3 >

When the angle of the apparent reflectance of 1/2, which indicates the apparent reflectance at the reference angle, is α, the average of the absolute values of α is 2.5 to 5.0 degrees.

The calculation method of α is described by taking fig. 2 as an example.

The solid line in FIG. 2 is a graph showing the distribution of the reflectance of the decorative molded article of example 7, the reflectance of the decorative molded article at the reference angle (0 degrees) in FIG. 2 is 1.48%, and the value of 1/2 is 0.74%, then the angle at which the reflectance of the decorative molded article is 0.74% is calculated in the positive direction and the negative direction (α), and the average of the absolute values of α under condition 1-2 can be calculated by taking the average of the absolute values of α in the positive direction and α in the negative direction, wherein α in the positive direction is +3.6 degrees, α in the negative direction is-3.6 degrees, and the average of the absolute values is 3.6 degrees in the negative direction in the case of the solid line in FIG. 2.

α denotes a range in which light that has entered and reflected on the uneven surface of the decorative molded article propagates after being diffusely reflected by the low-frequency unevenness, and more specifically α denotes a range in which reflected light propagates by small diffusion.

Therefore, satisfying the conditions 1 to 3 means that a certain amount of small diffusion caused by the irregularities of low frequency is contained, and means that the small diffusion is not too small or excessive.

From the viewpoint of suppressing the phenomenon that the contrast is decreased due to the excessive presence of irregularities of the low frequency component, the upper limit of α is more preferably 4.8 degrees or less, and still more preferably 4.6 degrees or less, and from the viewpoint of imparting antiglare properties by the low frequency irregularities, the lower limit of α is more preferably 3.0 degrees or more, and still more preferably 3.5 degrees or more.

The decorative molded article further preferably satisfies the following conditions 1 to 4.

< Condition 1-4 >

The apparent reflectance Y at the reference angle₀Is 2.0% or less.

By making the perceived reflectance Y₀When the content is 2.0% or less, the antiglare property can be improved. Perceived reflectance Y₀More preferably 1.7% or less, still more preferably 1.5% or less, and still more preferably 1.3% or less. Perceived reflectance Y₀The lower limit of (B) is not particularly limited, but the reflectance Y is perceived by the viewer₀If the content is too low, the decorative molded article tends to be whitened, and therefore, the content is preferably 0.5% or more, more preferably 0.7% or more.

The decorative molded article preferably includes the region P having the uneven surface and the region Q adjacent to the region P on the surface of the protective layer. By providing the surface of the protective layer with different regions, the decorative molded article can be made to have good design properties.

The arrangement of the region P and the region Q is arbitrary. Examples thereof include: a structure in which a region P is disposed in the central portion and a region Q is disposed in the peripheral portion of the surface of the protective layer; a structure in which a region Q is disposed in the central portion and a region P is disposed in the peripheral portion of the surface of the protective layer; a structure in which a region P and a region Q are arranged in parallel; a configuration in which a plurality of independent regions P are arranged near the center of the surface of the protective layer and a region Q is arranged around the plurality of regions P; and a configuration in which a plurality of independent regions Q are arranged near the center of the surface of the protective layer, and a region P is arranged around the plurality of regions Q.

In addition, the surface of the protective layer may have other regions.

In the decorative molded article, the region P and the region Q preferably satisfy the following conditions 1 to 5.

< Condition 1-5 >

Visible light beams inclined by 10 degrees from the normal direction of the sample a are incident on the surfaces of the region P and the region Q of the sample a, and the perceived reflectance is measured at 0.2 degrees intervals within a range of ± 5.0 degrees around the reference angle with the regular reflection direction of the incident light as the reference angle. The apparent reflectance at the reference angle of the region P is Y_0PAnd Y represents the apparent reflectance at the reference angle in the region Q_0QWhen, Y_0Q－Y_0PIs more than 1.5 percent.

By satisfying the conditions 1 to 5, the region P and the region Q can be easily distinguished, and the decorative molded article can be made to have good design properties.

Y_0Q－Y_0PMore preferably 2.0% or more, and still more preferably 2.5% or more. Furthermore, Y_0Q－Y_0PThe upper limit of (b) is not particularly limited, but is preferably 4.5% or less, more preferably 3.5% or less.

The decorative molded article preferably satisfies the following conditions 1 to 6 in the region P and the region Q.

< Condition 1-6 >

The method comprises the steps of allowing visible light beams inclined by 10 degrees from the normal direction of the sample A to enter the surfaces of the region P and the region Q of the sample A, measuring the apparent reflectance at intervals of 0.2 degrees within a range of + -5.0 degrees around the reference angle with the regular reflection direction of the incident light as the reference angle, and setting the angle of the apparent reflectance of 1/2 representing the apparent reflectance at the reference angle of the region P to α_PAnd α represents the angular degree of the perceived reflectance of 1/2 that represents the perceived reflectance at the reference angle in the region Q_QWhen in time, [ α_PAverage of absolute values of]－[α_QAverage of absolute values of]Is more than 2.5 degrees.

By satisfying the conditions 1 to 6, the region P and the region Q can be easily distinguished, and the decorative molded article can be made to have good design properties.

[α_PAverage of absolute values of]－[α_QAverage of absolute values of]More preferably 3.0 degrees or more, still more preferably 3.5 degrees or more, [ α ]_PAverage of absolute values of]－[α_QAverage of absolute values of]The upper limit of (d) is preferably less than 5.0 degrees, more preferably less than 4.8 degrees, and further preferably less than 4.6 degrees.

Further, in order to make it easy to satisfy the conditions 1 to 5 and the conditions 1 to 6, the region Q is preferably substantially smooth. Specifically, JIS B0601 of region Q: the arithmetic average roughness Ra of 1994 is preferably less than 0.10. mu.m, more preferably 0.05 μm or less. On the other hand, Ra of the region P is preferably more than 0.10 μm and 0.30 μm, more preferably 0.15 to 0.25 μm.

Area S of region P₁And area S of region Q₂Ratio of (S)₂/S₁]Since the difference varies depending on the relationship with the given design, it is not particularly limited, and it is preferable to satisfy 0.1. ltoreq. S from the viewpoint of making the contrast between the region P and the region Q clear₂/S₁The relationship (2) of (c). In addition, from the viewpoint of improving the antiglare property of the decorative molded article, it is preferable to satisfy S₂/S₁The relation of less than or equal to 7.0.

< other optical characteristics >)

The portion having an uneven surface (region P) of the decorative molded article is measured according to JIS K7361-1: 1997 has a total light transmittance of preferably 80% or more, more preferably 90% or more.

When the decorative molded article includes a region P having an uneven surface and a region Q adjacent to the region P, the total light transmittance of the region Q is not particularly limited. That is, the region Q may have a substantially concealing property or a light transmitting property.

The portion (region P) having the uneven surface of the decorative molded article was obtained according to JISK 7136: the haze value of 2000 is preferably 5 to 40%, more preferably 10 to 35%, and further preferably 20 to 30%.

When the decorative molded article includes a region P having an uneven surface and a region Q adjacent to the region P, the haze of the region Q is not particularly limited. That is, the region Q may have a substantially concealing property and may not have a measurable haze, or may have a predetermined haze.

Preferably, the decorative molded article has a surface of the protective layer including a first region having the uneven surface, a second region adjacent to the first region, and a third region adjacent to the second region, wherein the first region is a region of a surface having a thickness according to JISZ 8741: 1997 measured 60 degree specular gloss GS₁(60 °) is smaller than the third region in the range of the particle diameter distribution according to JIS Z8741: 1997 measured 60 degree specular gloss GS₃(60 °), the second region is measured according to JIS Z8741: 1997 measured 60 degree specular gloss GS₂(60 °) in GS as it goes from the first region side to the third region side₁GS at 60 ℃ or higher₃(60 ℃) or less.

The 60 degree specular gloss of the decorative molded article is preferably measured by preparing the above sample A.

In the second region, the glossiness changes as described above, so that the first region 1 having the matte feeling and the third region having the glossy feeling are in a seamless state, and the decorative molded article can be designed well.

In the decorative molded article, coloring or patterning may be applied to an arbitrary portion (for example, a surface of the adherend opposite to the protective layer). In such a decorative molded article, when the decorative molded article is viewed from the front and when the decorative molded article is viewed from an oblique direction, the coloring or the pattern may give a different impression to the edge portion of the first region. However, by changing the glossiness of the second region as described above, the difference in the impression as described above of the edge portion of the first region can be alleviated. The above-described effects are easily exhibited remarkably only when coloring or patterning is applied to a portion of the decorative molded article corresponding to the third region.

GS₁(60 ℃) to GS₃(60 ℃) ratio [ GS₁(60°)/GS₃(60°)]Preferably 0.6 or less, more preferably 0.55 or less, and further preferably 0.45 or less.

GS for obtaining sufficient matte feeling₁The (60 °) is preferably 100% or less. In addition, the secondary suppressor GS₁From the viewpoint of whitening impression due to too small a temperature of (60 °), GS is preferable₁(60 ℃) 30% or more, preferably 40 to 90%, and more preferably 50 to 80%.

The increasing degree of the 60-degree specular gloss may be proportional to the distance from the first region, or the increasing rate with respect to the distance may be changed halfway. From the viewpoint of suppressing the second region from being visually recognized as a clear line, it is more preferable that the increase rate is gradually increased so as to be small in the vicinity of the first region and the vicinity of the third region and to have an inflection point in the vicinity of the middle between the two regions.

The difference in the 60-degree specular gloss of each region can be adjusted by, for example, the difference in the surface roughness of each region.

Width d of the second region₂The difference in gloss impression between the first region and the third region is preferably such that the difference is not clearly seen in the second region. From such a viewpoint, d₂Preferably, the maximum diameter L of the decorative film is 0.1 to 2.0%, more preferably 0.1 to 1.5%, and still more preferably 0.1 to 1.0%.

< protective layer >

The protective layer preferably contains a cured product of the curable resin composition as a main component. The main component is 50 mass% or more of the total solid content constituting the protective layer, and the proportion is preferably 70 mass% or more, more preferably 80 mass% or more, and still more preferably 90 mass% or more.

The cured product of the curable resin composition includes a cured product of a thermosetting resin composition and a cured product of an ionizing radiation curable resin composition, and among these, a cured product of an ionizing radiation curable resin composition is preferable.

The protective layer may contain a thermoplastic resin, but the amount thereof is preferably a small amount from the viewpoint of improving scratch resistance. Specifically, the content of the thermoplastic resin in the protective layer is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably less than 0.1% by mass, and still more preferably 0% by mass.

Hereinafter, the cured product of the curable resin composition and the thermoplastic resin are sometimes referred to as "resin components".

The thermosetting resin composition is a composition containing at least a thermosetting resin and is cured by heating. Examples of the thermosetting resin include acrylic resins, polyurethane resins, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. In the thermosetting resin composition, a curing agent is added to these curable resins as needed.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as "ionizing radiation curable compound"). Examples of the ionizing radiation curable functional group include an ethylenically unsaturated bond group such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group and an oxetanyl group.

The ionizing radiation curable resin is preferably a compound having an ethylenically unsaturated bond group. From the viewpoint of suppressing scratching of the resin layer during the production of the transfer sheet, the ionizing radiation curable resin is more preferably a compound having 2 or more ethylenically unsaturated bond groups, and particularly preferably a polyfunctional (meth) acrylate compound having 2 or more ethylenically unsaturated bond groups. As the polyfunctional (meth) acrylate compound, both a monomer and an oligomer can be used.

The ionizing radiation is a radiation having an energy quantum capable of polymerizing or crosslinking molecules among electromagnetic waves or charged particle rays, and ultraviolet rays (UV) or Electron Beams (EB) are generally used, and electromagnetic waves such as X-rays and γ -rays, α rays, charged particle rays such as ion rays, and the like can also be used.

In the polyfunctional (meth) acrylate compound, examples of the 2-functional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, bisphenol a tetraethoxydiacrylate, bisphenol a tetrapropoxy diacrylate, 1, 6-hexanediol diacrylate, and the like.

Examples of the 3-or more-functional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and isocyanuric acid-modified tri (meth) acrylate.

The (meth) acrylate monomer may be a monomer in which a part of the molecular skeleton is modified, or a monomer modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, an alkyl group, a cyclic alkyl group, an aromatic group, or a bisphenol.

Examples of the polyfunctional (meth) acrylate oligomer include acrylate polymers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.

The urethane (meth) acrylate can be obtained, for example, by reacting a polyol and an organic diisocyanate with a hydroxy (meth) acrylate.

Preferred epoxy (meth) acrylates are (meth) acrylates obtained by reacting a 3-or more-functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with (meth) acrylic acid; a (meth) acrylate obtained by reacting a 2-or more-functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or the like with a polybasic acid and (meth) acrylic acid; and (meth) acrylic esters obtained by reacting phenols and (meth) acrylic acid with 2-or more-functional aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and the like.

The ionizing radiation curable resin may be used alone in 1 kind, or in combination with 2 or more kinds.

When the ionizing radiation curable resin is an ultraviolet curable resin, the resin layer forming coating liquid preferably contains an additive such as a photopolymerization initiator or a photopolymerization accelerator.

Examples of the photopolymerization initiator include 1 or more selected from acetophenone, benzophenone, α -hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α -acyloxime ester, thioxanthone and the like.

The photopolymerization accelerator is a substance capable of reducing polymerization inhibition by air during curing and accelerating the curing speed, and examples thereof include 1 or more selected from isoamyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, and the like.

The curable resin composition may be in a semi-cured state at the time of forming the protective layer, and after being transferred to an adherend, the curable resin composition may be cured completely by heating, irradiation with ionizing radiation, or the like. By doing so, the protective layer has good followability to the adherend, and hence moldability can be improved.

The protective layer may contain particles such as organic particles and inorganic particles. By including the particles in the protective layer, the glare and the defects can be made less noticeable by the development of the internal haze caused by the difference in refractive index from the resin component. These particles may be contained in a functional layer such as an adhesive layer and an anchor layer described later for the same purpose. In addition, from the viewpoint of suppressing cracks at the time of molding, it is preferable to contain particles in the functional layer rather than particles in the protective layer.

Examples of the organic particles include particles made of polymethyl methacrylate, polyacrylic acid-styrene copolymer, melamine resin, polycarbonate, polystyrene, polyvinyl chloride, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine-based resin, polyester-based resin, and the like.

Examples of the inorganic particles include particles made of silica, alumina, antimony, zirconia, titania, and the like.

The average particle diameter of the particles is preferably 0.05 to 5.0 μm, more preferably 0.5 to 3.0. mu.m.

In the present specification, the average particle diameter is a 50% particle diameter (d 50: median diameter) when the particles in a solution are measured by a dynamic light scattering method and the particle diameter distribution is expressed as a volume cumulative distribution. The 50% particle diameter can be measured, for example, by a Microtrac particle size analyzer (manufactured by Nikkiso K.K.).

The content of the particles is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the resin component of the protective layer.

By setting the content of the particles to 0.1 part by mass or more, defects can be made less noticeable and a sense of glare can be easily suppressed. In addition, when the surface of the protective layer has a plurality of regions by setting the content of the particles to 20 parts by mass or less, it is possible to suppress a decrease in design property due to difficulty in distinguishing the regions.

The thickness of the protective layer is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, and still more preferably 3 to 10 μm from the viewpoint of the balance between the surface hardness and the moldability.

< adherend > < body to be adhered >

Examples of the adherend include a resin molded body made of a thermoplastic resin or a thermosetting resin that can be injection molded.

In the case of producing the decorative molded article of the present invention by in-mold molding, a thermoplastic resin is preferably used. Examples of such thermoplastic resins include polystyrene resins, polyolefin resins, ABS resins (including heat-resistant ABS resins), AS resins, AN resins, polyphenylene ether resins, polycarbonate resins, polyacetal resins, acrylic resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polysulfone resins, and polyphenylene sulfide resins.

< other layers >

The decorative molded article of the present invention may have a functional layer such as an anchor layer, a print layer, and an adhesive layer between the adherend and the protective layer.

< adhesive layer > <

The adhesive layer has a function of improving adhesion between an adherend such as a resin molded article and a transfer layer such as a protective layer, and improving transfer work.

When the protective layer has good adhesion to the adherend, the adhesive layer may not be provided.

The adhesive layer is preferably made of a heat-sensitive or pressure-sensitive resin suitable for the material of the adherend. For example, when the material of the adherend is an acrylic resin, the acrylic resin is preferably used. When the material of the adherend is a polyphenylene ether-polystyrene resin, a polycarbonate resin, or a styrene resin, it is preferable to use an acrylic resin, a polystyrene resin, a polyamide resin, or the like having affinity with these resins. When the material of the adherend is a polypropylene resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer resin, a cyclized rubber, or a coumarone-indene resin is preferably used.

Additives such as ultraviolet absorbers and infrared absorbers may be added to the adhesive layer.

The thickness of the adhesive layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

< anchoring layer >)

The anchor layer is a layer provided as needed for improving heat resistance when placed in a high-temperature environment such as in-mold molding. The anchor layer is preferably formed between the protective layer and the adhesive layer.

The anchor layer preferably contains a cured product of a curable resin composition.

Examples of the curable resin composition include a thermosetting resin composition and an ionizing radiation curable resin composition.

The embodiments of the thermosetting resin composition and the ionizing radiation curable resin composition of the anchor layer are the same as those of the thermosetting resin composition and the ionizing radiation curable resin composition of the protective layer.

The thickness of the anchor layer is preferably 0.1 to 6 μm, more preferably 0.5 to 5 μm.

< printing layer >)

The printed layer is a layer for imparting a desired design property to the decorative molded article, and is provided as desired.

The pattern of the print layer is arbitrary, and examples thereof include wood grain, stone grain, cloth grain, sand grain, circle, quadrangle, polygon, geometric pattern, character, full-coat printing, and the like.

The printing layer preferably contains a binder resin such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, or a cellulose resin, and a pigment and/or a dye.

From the viewpoint of design, the thickness of the printed layer is preferably 0.5 to 40 μm, and more preferably 1 to 30 μm.

The functional layer disposed between the adherend and the protective layer preferably contains a binder resin and particles, and the refractive index n of the binder resin₁Refractive index n of the particles₂Different.

By including the particles in the functional layer on the adherend side of the protective layer, defects such as cracks can be suppressed during molding or the like. In the case where the functional layer has a plurality of layers, the functional layer closest to the adherend side preferably contains particles.

In addition, when the transfer layer is transferred to the adherend, the functional layer is located lower than the protective layer. Therefore, in the configuration in which the functional layer contains the particles, the internally diffused light can be easily propagated in a wider angle range before reaching the surface of the protective layer, defects generated on the surface of the protective layer can be made less noticeable, and the glare can be easily suppressed, as compared with the configuration in which the protective layer contains the particles. The structure in which the functional layer contains particles is preferable in that the above-described effects (invisibility of defects, suppression of a harsh feeling) can be easily obtained even if the content of particles is small, as compared with the structure in which the protective layer contains particles.

Refractive index n of binder resin₁And refractive index n of the particles₂Preferably n is₂/n₁Is 0.98 or less, or 1.02 or more.

In addition, from the viewpoint of enhancing internal haze (internal diffusion) and making defects and a sense of harshness more less noticeable, n₂/n₁More preferably 0.98 or less. In addition, let n₂/n₁When the amount is 0.98 or less, it is preferable in that the amount of particles necessary for obtaining the same degree of internal haze (internal diffusion) can be easily reduced.

Furthermore, by n₂/n₁It is also preferably 0.98 or less, or 1.02 or more, from the viewpoint of being able to easily suppress interference fringes.

The embodiments of the kind, average particle diameter, and addition amount of the particles added to the functional layer are the same as those of the kind, average particle diameter, and addition amount of the particles added to the protective layer.

Preferably, the decorative molded article has particles in at least a part of an interface between the functional layer closest to the adherend (functional layer in contact with the adherend) and the adherend, and the refractive index of the binder resin in the functional layer in contact with the adherend is n₁Let the refractive index of the particles be n₂N represents a refractive index of the resin of the adherend₃When the condition (i) or (ii) is satisfied.

n₁＜n₂＜n₃(i)

n₃＜n₂＜n₁(ii)

The conditions (i) and (ii) mean the refractive index n of the binder resin (resin 1) of the functional layer in contact with the adherend₁Refractive index n of resin (resin 3) adhered to object₃Different. When the refractive indices of the resin 1 and the resin 3 are different from each other in this way, interference fringes are generally generated in the decorative molded article.

However, when the condition (i) or (ii) is satisfied, the particle located at the interface between the functional layer in contact with the adherend and the adherend (hereinafter, sometimes referred to as "interfacial particle") and the refractive index difference between the resin 1 and the resin 3 cause the generation of the internal haze, and the interference fringes can be suppressed. Further, by generating the internal haze, defects of the decorative molded article can be made less noticeable, and the yield can be improved.

Further, the decorative molded article satisfying the condition (i) or (ii) has a refractive index n of the particles at the interface₂Over n₁And is lower than n₃Or more than n₃And is lower than n₁Therefore, reflection due to the difference in refractive index between the resin 1 and the resin 3 can be suppressed, and whitening due to reflection can be suppressed.

When the condition (i) is satisfied, n is preferably₂/n₁More than 1.00 and 1.03 or less, and n₂/n₃Is 0.97 or more and less than 1.00, more preferably n₂/n₁Is 1.01 or more and 1.03 or less, and n₂/n₃Is 0.97 to 0.99 inclusive.

When the condition (ii) is satisfied, n is preferably n₂/n₁Is 0.97 or more and less than 1.00, and n₂/n₃More than 1.00 and not more than 1.03, more preferably n₂/n₁Is 0.97 or more and 0.99 or less, and n₂/n₃Is 1.01 to 03 inclusive.

With respect to the condition (i) or the condition (ii), by satisfying the above preferable conditions, the balance between suppression of interference fringes and whitening can be further improved.

For example, the particles may be present in at least a part of the interface between the functional layer in contact with the adherend and the adherend by (a) previously incorporating the particles in the adherend, and/or (b) previously incorporating the particles in the functional layer in contact with the adherend. Among the above-described embodiments, the embodiment (b) is preferable in which the particles are easily present at least in part of the interface between the adherend and the functional layer and the amount of the particles used is easily suppressed.

In the case of the above-described aspect (a) and/or (b), the content of the particles is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, and further preferably 1 to 10 mass% of the total solid content of the particle-containing layer.

The embodiment of the kind and average particle diameter of the particles at the interface is the same as the embodiment of the kind and average particle diameter of the particles added to the protective layer.

However, in the case of the embodiment (b), the thickness T of the functional layer in contact with the adherend and the average particle diameter D of the interface particles preferably satisfy the relationship of 1.0 < D/T. D/T is more preferably 1.1 to 2.0, and still more preferably 1.3 to 1.7.

The respective layers of the protective layer, the adhesive layer, the anchor layer, the printing layer, and the like constituting the transfer layer can be formed, for example, by: each layer such as a protective layer, an adhesive layer, an anchor layer, and a print layer constituting a transfer layer can be formed by adjusting a coating liquid containing a constituent component of each layer, applying the coating liquid to a release sheet by a coating method such as a gravure coating method or a roll coating method, a printing method such as a gravure printing method or a screen printing method, drying the coating liquid, and irradiating ionizing rays as necessary to cure the coating liquid.

The decorative molded article of the present invention can be suitably used as a member constituting, for example, communication equipment such as a mobile phone, information equipment in an automobile, home electric appliances, various display devices, and the like.

[ transfer sheet ]

The transfer sheet of the present invention has a protective layer on a release sheet, and at least a part of a surface of the release sheet on a side contacting the protective layer has a concave-convex surface, and satisfies the following condition 2-1.

< Condition 2-1 >

The transfer sheet was bonded to a black plate via a transparent pressure-sensitive adhesive layer on the surface of the transfer sheet on the protective layer side, and the release sheet was peeled off to produce sample B having the black plate, the transparent pressure-sensitive adhesive layer, and the protective layer having a surface shape complementary to the surface shape of the transfer sheet in this order. Visible light inclined by 10 degrees from the normal direction of the sample B was incident on the uneven surface of the protective layer, and the perceived reflectance was measured at 0.2 degrees intervals within a range of ± 5.0 degrees around the reference angle with the regular reflection direction of the incident light as the reference angle. Y represents a reflectance of-5.0 degrees with respect to the reference angle_－5.0Y represents a visual reflectance of-4.8 degrees_－4.8Then, will be given with [ (Y)_－4.8－Y_－5.0)/((Y_－4.8+Y_－5.0)/2)]The value represented by X100 was defined as the rate of change of the perceived reflectance at-5.0 degrees. The change rate of the apparent reflectance at all measurement angles is calculated, and when an approximate line is created by the least square method with the measurement angle as the x-axis and the change rate as the y-axis, the slope of the approximate line is from-2.00 to 0.90.

Fig. 6 is a sectional view showing one embodiment of the transfer sheet 200 of the present invention. The transfer sheet 200 of fig. 6 has a protective layer 21 on the release sheet 30. The transfer sheet 200 of fig. 6 includes a region P ' having a concave-convex surface and a region Q ' adjacent to the region P ' on the surface of the release sheet 30 on the side contacting the protective layer 21.

The surface of the release sheet 30 of the transfer sheet 200, which is in contact with the protective layer 21, has a shape complementary to the surface shape of the decorative molded article. That is, the shape of the region P' of fig. 6 is complementary to the shape of the region P of fig. 1. In addition, the shape of the region Q' of fig. 6 is complementary to the shape of the region Q of fig. 1.

The technical meaning of the slope of the approximate line in condition 2-1 is the same as in condition 1-1. That is, by setting the slope of the approximate straight line of the condition 2-1 to-2.00 or more, the brightness at the center of the field of view of the decorative molded article produced using the transfer sheet of the present invention can be made uniform. Further, by setting the slope of the approximate line under condition 2-1 to-0.90 or less, the surface diffusion of the decorative molded article produced using the transfer sheet of the present invention can be suppressed, and the whitening can be suppressed.

The slope of the approximate line of condition 2-1 is preferably-1.80 to-1.00, more preferably-1.50 to-1.10.

< other Condition >)

The sample B formed from the transfer sheet preferably satisfies one or more of the following conditions 2-2 to 2-6.

The technical significance of the conditions 2-2 to 2-6 is the same as that of the conditions 1-2 to 1-6. The preferable embodiments of conditions 2-2 to 2-6 are the same as conditions 1-2 to 1-6.

< Condition 2-2 >

Within a range of ± 5.0 degrees from the reference angle, an absolute value of a difference between a value of the apparent reflectance calculated from the approximate straight line and an actually measured value of the apparent reflectance at each measurement angle is calculated for each measurement angle. The standard deviation of the absolute value of the difference calculated within a range of + -5.0 degrees is 0.50 to 1.60%.

< Condition 2-3 >

When the angle of the apparent reflectance of 1/2, which represents the apparent reflectance at the reference angle, is α, the average of the absolute values of α is 2.5 to 5.0 degrees.

< Condition 2-4 >

The apparent reflectance Y at the reference angle₀Is 2.0% or less.

The transfer sheet 200 preferably includes a region P ' having a concave-convex surface and a region Q ' adjacent to the region P ' on the surface of the release sheet 30 on the side contacting the protective layer 21 (fig. 6). By providing the release sheet with a different region on the surface on the side in contact with the protective layer, the decorative molded article produced using the transfer sheet can be made excellent in design.

In the transfer sheet, the region P 'and the region Q' preferably satisfy the following conditions 2 to 5.

< Condition 2-5 >

Visible light beams inclined by 10 degrees from the normal direction of the sample B were incident on the surfaces of the region P 'and the region Q' of the sample B, and the perceived reflectance was measured at 0.2 degrees intervals within a range of ± 5.0 degrees around the reference angle with the regular reflection direction of the incident light as the reference angle. The apparent reflectance at the reference angle of the region P' is Y_0PAnd Y represents the apparent reflectance at the reference angle in the region Q_0QWhen, Y_0Q－Y_0PIs more than 1.5 percent.

In the transfer sheet, the region P 'and the region Q' preferably satisfy the following conditions 2 to 6.

< Condition 2-6 >

Visible light beams inclined by 10 degrees from the normal direction of the sample B were made incident on the region P 'of the sample B'And the surface of the region Q 'is measured in a range of + -5.0 degrees around the reference angle with the regular reflection direction of the incident light as the reference angle, and the apparent reflectance is measured every 0.2 degrees, wherein the angle of the apparent reflectance of 1/2 showing the apparent reflectance at the reference angle of the region P' is α degrees_PAnd α represents the angular degree of the perceived reflectance of 1/2 that represents the perceived reflectance at the reference angle in the region Q_QWhen in time, [ α_PAverage of absolute values of]－[α_QAverage of absolute values of]Is more than 2.5 degrees.

As described above, the surface of the release sheet on the side contacting the protective layer preferably includes the region P ' having the uneven surface and the region Q ' adjacent to the region P '.

In addition, in the release sheet, the ratio of the amount of the release agent is set in accordance with JIS B0601: 1994 measured arithmetic average roughness Ra of 0.8mm of cut-off value of the region P₁And according to JIS B0601: 1994, and the arithmetic average roughness Ra of the cut-off value of 0.8mm in the region Q₂Preferably satisfies Ra₁＞Ra₂The relationship (2) of (c).

The shape of the surface of the transfer layer after the transfer layer is transferred to the adherend has a shape complementary to the surface shape of the release sheet. That is, the surface shapes of the region P 'and the region Q' of the release sheet correspond to the surface shape formed on the surface of the adherend.

Thus, Ra is satisfied₁＞Ra₂The relationship (2) means that 2 kinds of regions having different surface shapes can be formed on the adherend. And, by satisfying Ra₁＞Ra₂The relation (2) and the 2 kinds of regions having different surface shapes for the adherend can improve the design of the adherend.

Ra₁－Ra₂Preferably 0.05 to 1.00. mu.m, more preferably 0.07 to 0.80. mu.m, and still more preferably 0.12 to 0.30. mu.m.

Ra₁Preferably 0.06 to 1.20 μm, more preferably 0.10 to 1.00. mu.m, still more preferably 0.13 to 0.50. mu.m, and still more preferably 0.15 to 0.35. mu.m.

Ra₂Preferably below 010 μm, more preferably 0.07 μm or less, and still more preferably 0.05 μm or less.

In addition, in the release sheet, the ratio of the amount of the release agent is set in accordance with JIS B0601: 1994 measured average roughness Rz of ten points at 0.8mm cutoff value of the above region P₁And the above Ra₁Preferably satisfies 2.0. ltoreq. Rz₁/Ra₁The relation of less than or equal to 15.0.

By making Rz₁/Ra₁When the ratio is 15.0 or less, a phenomenon that a difference between the peel strength of the region P 'and the peel strength of the region Q' is large can be suppressed, and a phenomenon that a striped pattern is generated when the release sheet is peeled can be suppressed.

In addition, by making Rz₁/Ra₁At 2.0 or more, a certain randomness can be imparted to the irregularities of the region P', and defects in the region P after transfer can be made less noticeable. In addition, since defects are less noticeable, a reduction in design and yield of the decorative molded article can be suppressed.

Rz₁/Ra₁Preferably 3.0 to 10.0, more preferably 3.5 to 8.0, and further preferably 4.0 to 7.0.

Rz₁Preferably 0.25 to 5.00. mu.m, more preferably 0.50 to 2.50. mu.m, and still more preferably 1.00 to 2.00. mu.m.

In the present specification, regarding Ra and Rz, samples cut out from portions where there is no abnormal point such as stain or flaw when visually observed are prepared, and the average value of measured values at 20 arbitrary positions where there is no defect or abnormal point in the portions corresponding to the region P 'and the region Q'.

< Release sheet >

The release sheet 30 can be composed of a support 31 and a resin layer 32, as shown in fig. 6, for example. Of course, the release sheet may be a single layer of the support or the resin layer, or may have a configuration of 3 or more layers including layers other than the support and the resin layer.

Although not shown, the release sheet preferably has a release layer on the outermost surface on the side in contact with the protective layer.

< support >

Examples of the support include plastic films containing resins such as polyolefin resins such as polyethylene and polypropylene, vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymers and ethylene-vinyl alcohol copolymers, polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, acrylic resins such as polymethyl (meth) acrylate and polyethylene (meth) acrylate, styrene resins such as polystyrene, and polyamide resins represented by nylon 6 and nylon 66.

Among these plastic films, a biaxially stretched polyester film excellent in heat resistance and dimensional stability and excellent in alignment suitability at the time of transfer is preferable.

The thickness of the support is preferably 12 to 150 μm, more preferably 25 to 100 μm, from the viewpoint of moldability, shape-following property, and handling property.

In addition, the surface of the support may be subjected to physical treatment such as corona discharge treatment or oxidation treatment, or may be coated with a coating material such as an anchor agent or primer agent in advance in order to improve adhesion to a resin layer or the like.

When the release sheet is formed of a single layer of the support, the surface of the support may be shaped by a plate (plate) having a surface shape of the protective layer.

< resin layer > <

The resin layer preferably contains a resin component such as a thermoplastic resin, a cured product of a thermosetting resin composition, or a cured product of an ionizing radiation-curable resin composition as a main component. The main component is 50 mass% or more of the total solid content constituting the resin layer, and the proportion is preferably 70 mass% or more, and more preferably 90 mass% or more.

Among the above resin components, a cured product of an ionizing radiation curable resin composition which is excellent in strength and can be instantaneously cured to give an accurate and precise shape is preferable. In addition, from the viewpoint of easily obtaining the effects of the ionizing radiation curable resin composition, the cured product of the ionizing radiation curable resin composition is preferably contained in an amount of 70 mass% or more, more preferably 90 mass% or more, further preferably 95 mass% or more, and still further preferably 100 mass% of the total resin components constituting the resin layer.

The resin layer can be formed by applying a coating liquid containing particles and a binder resin, but is preferably formed by printing using a plate having a shape complementary to the surface shape of the resin layer, from the viewpoint of forming an accurate and precise shape. The details of the method for forming the resin layer using the plate will be described later.

In addition, when the resin layer is formed by coating, particles contained in the coating liquid are aggregated in a large amount, and various measures are required to satisfy the condition 1-1, and the process becomes complicated, which is not preferable.

The embodiments of the thermosetting resin composition and the ionizing radiation curable resin composition of the resin layer are the same as those of the thermosetting resin composition and the ionizing radiation curable resin composition of the protective layer described above.

The thickness of the resin layer is not particularly limited, but is preferably 1 to 15 μm, and more preferably 2 to 12 μm.

From the viewpoint of improving releasability between the release sheet and the transfer layer, it is preferable that the resin layer contains substantially no particles. Specifically, the content of the particles in the resin layer is preferably less than 1% by mass, more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and still more preferably 0% by mass.

The interface between the release sheet and the transfer layer is formed to be capable of being peeled off when it is closely adhered to the object to be transferred.

In order to improve the releasability, the release sheet preferably has a release layer on at least a part of a surface on the side in contact with the transfer layer. In addition, from the viewpoint of uniformizing the releasability in the surface of the transfer sheet, the release sheet preferably has a release layer over the entire surface of the surface on the side in contact with the transfer sheet.

Further, by forming the release layer on the uneven surface of the release sheet, an uneven shape with few high-frequency components can be transferred to the surface of the adherend, and whitening and a harsh feeling of the decorative molded article can be easily suppressed.

Preferably, the release layer is composed mainly of a resin.

The resin of the release layer is not particularly limited as long as it has a predetermined film strength and has a low adhesive force with the transfer layer, and examples thereof include general-purpose thermoplastic resins, cured products of thermosetting resin compositions, and cured products of ionizing radiation-curable resin compositions. Specific examples thereof include fluorine-based resins, silicone-based resins, acrylic resins, polyester-based resins, polyolefin-based resins, polystyrene-based resins, polyurethane-based resins, cellulose-based resins, vinyl chloride-vinyl acetate copolymer resins, and nitrocellulose.

Among these, a cured product of a thermosetting resin composition is preferable, and a cured product of a thermosetting resin composition containing an acrylic polyol and an isocyanate is more preferable.

The releasing layer may further contain a releasing agent in order to improve releasability. Examples of the release agent include waxes such as synthetic wax and natural wax. The synthetic wax is preferably a polyolefin wax such as polyethylene wax or polypropylene wax.

The thickness of the release layer is preferably 0.1 to 5.0 μm, more preferably 0.2 to 1.5 μm, and still more preferably 0.3 to 1.0. mu.m.

The thickness of the release layer can be calculated, for example, by taking a photograph of a cross section of a release sheet cut at a center portion thereof in the vertical direction, measuring the thickness of the release layer at least at 20 places at intervals of 500 μm from the photograph of the cross section, and calculating the thickness of the release layer as an average value of the measured thicknesses.

The release sheet may have other layers.

As the other layer, an antistatic layer can be cited. By having the antistatic layer, peeling electrification at the time of peeling the release sheet can be suppressed, and the workability of transfer can be improved.

The antistatic layer preferably contains an antistatic agent such as an electron-conductive antistatic agent or an ion-conductive antistatic agent, and a binder resin.

Preferably, an antistatic layer is formed on the surface of the release sheet opposite to the surface thereof in contact with the transfer layer.

The antistatic layer is preferably adjusted to have a surface resistivity of 1.0X 10^-9Ω/□～1.0×10^-12Range of omega/□.

In addition, the antistatic agent may be contained in another layer such as a resin layer to exhibit antistatic properties.

< method for producing Release sheet >

The release sheet can be produced, for example, by the following steps (a1) to (a 2).

(A1) And a step of applying a coating liquid for forming a resin layer containing an ionizing radiation curable resin composition on a support to form a layer containing an ionizing radiation curable resin composition.

(A2) And a step of forming the uncured resin layer using a plate having a shape complementary to the surface shape of the resin layer and curing the formed resin layer by irradiating the uncured resin layer with an ionizing radiation.

When the ionizing radiation curable resin composition contains a solvent, the solvent is preferably dried in the step (a 1).

When the release sheet has a release layer, the step (A3) of forming the release layer on the resin layer may be performed after the step (a 2).

When the surface of the resin layer has 2 or more kinds of regions (for example, the region P 'and the region Q'), a plate having a shape complementary to the shape of the surface of the resin layer including 2 or more kinds of regions may be used as the plate in the step (a 2).

The plate used in the step (a2) can be obtained by engraving the surface of the cylinder into a desired shape by etching, sandblasting, cutting, laser processing, or a combination thereof, for example. Alternatively, a plate used in the step (a2) is obtained by preparing a plate of a male mold (a plate having the same shape as the resin layer) by laser engraving, photo-shaping, or the like, turning the plate over, and winding the turned plate around the surface of the cylinder.

(A2) The surface of the plate used in the step is preferably plated with nickel, chromium or the like, and more preferably with hard chromium plating.

Among the above-mentioned plate production methods, sandblasting is preferable from the viewpoint of easy control of the conditions 1-1 and the like.

In the blasting, the uneven shape can be adjusted by controlling, for example, the material of the surface of the barrel, the particle diameter of the abrasive, the shape of the abrasive, the material of the abrasive, the number of times the abrasive collides with the barrel, the distance between the nozzle and the barrel, the diameter of the nozzle, the angle of the nozzle with respect to the workpiece, the ejection pressure, the ejection frequency, and the like.

Among the above-described control methods, the "number of collisions of the abrasive with the cartridge" is the simplest and most effective for the control under condition 1-1. That is, when the number of times of collision of the polishing material with the surface of the cylinder is small, the slope of the approximate line is far from 0, and as the number of times of collision of the polishing material with the surface of the cylinder is large, the slope of the approximate line tends to be close to 0. This is considered to be because the irregularities are gradually averaged by increasing the number of times of collision of the polishing material. However, although the slope of the approximate straight line is close to 0 by increasing the number of collisions, there is a limit to this, and the slope gradually saturates. The number of times for averaging the unevenness is different depending on the blasting conditions, and it is preferable to perform blasting on the same surface of the cylinder about 3 to 8 times depending on the blasting conditions of the embodiment.

Further, when a polishing material having an amorphous shape is used, the dispersion to a large angle is likely to occur, and the distribution of the apparent reflectance is close to a semicircular shape, so that the slope of the approximate straight line tends to be close to 0.

Further, when the material of the surface of the cylinder is hardened, the cylinder is not easily ground deeply by the abrasive, and therefore, the slope of the approximate curve tends to be close to 0.

When the particle diameter of the abrasive is large, the unevenness is averaged, and the slope of the approximate curve tends to be close to 0.

Even if the distance between the nozzle and the cylinder and the injection pressure are changed, the averaging of the unevenness is less affected. Therefore, the distance from the nozzle to the barrel and the ejection pressure are not considered to have a large influence on the condition 1-1.

The degree of averaging of the unevenness is also related to the condition 1-2. That is, when the degree of averaging of the unevenness is high, the standard deviation of the condition 1-2 becomes small, and when the degree of averaging of the unevenness is low, the standard deviation of the condition 1-2 becomes large.

The average of the absolute values of α in conditions 1 to 3 can be adjusted according to the inclination angle of the uneven surface, for example, α tends to be smaller when the particle size of the abrasive is larger and α tends to be larger when the particle size of the abrasive is smaller, and α tends to be larger when the shape of the abrasive is amorphous.

Further, the perceived reflectance Y of the conditions 1 to 4₀Can be adjusted according to the proportion of the substantially smooth region existing in the concave-convex surface. For example, the presence of a reduced proportion of smooth regions can reduce the perceived reflectance Y₀The tendency of (c).

In addition, when another layer such as a release layer is formed on the resin layer, the surface irregularities of the release sheet are reduced as compared with the surface irregularities of the resin layer. Therefore, when another layer is formed on the resin layer, the plate used in the step (a2) may be a plate having a shape in which the unevenness is reduced.

The release sheet can be produced, for example, by the following steps (B1) to (B2).

(B1) And filling the plate having a shape complementary to the surface shape of the protective layer with the resin layer-forming coating liquid.

(B2) And a step of transferring the coating liquid for forming a resin layer filled in the plate onto a support, and drying and curing the coating liquid as required to form a resin layer.

The above-mentioned steps (a1) to (a2) are preferable from the viewpoint of forming an accurate and precise shape.

A transfer layer is formed on the release sheet.

The transfer layer 20 is a layer to be transferred to an adherend, and is formed to cover the entire surface of the release sheet 30, for example, as shown in fig. 6. As shown in fig. 6, for example, the transfer layer 20 includes a protective layer 21 and an adhesive layer 22 in this order from the side close to the release sheet 30.

The embodiments of the protective layer and the adhesive layer of the transfer sheet are the same as those of the protective layer and the adhesive layer of the decorative molded article.

The transfer sheet may have functional layers such as an anchor layer, a print layer, and an adhesive layer. The embodiments of these functional layers are the same as those of the functional layers of the decorative molded article described above.

[ method for producing decorative moldings ]

The method for producing a decorative molded article of the present invention is a method in which the following steps (1) and (2) are sequentially performed.

(1) And a step of obtaining a laminate by bringing the adherend 10 into close contact with the surface of the transfer sheet 200 of the present invention on the side of the protective layer 21 with the release sheet 30 as a reference.

(2) And a step of separating the release sheet 30 of the transfer sheet 200 from the laminate.

Fig. 7 is a sectional view showing an embodiment of the steps (1) and (2).

As a specific method for producing the decorative molded article, a known transfer method can be used.

For example, there are (i) a method of producing a laminate by bringing the protective layer side surface of a transfer sheet into close contact with a transfer target formed in advance, and then separating (peeling) a release sheet of the transfer sheet from the laminate; (ii) a method of producing a laminate by bringing the surface of the transfer sheet on the protective layer side into close contact with a flat-plate-shaped object to be transferred, and separating (peeling) the transfer sheet from the laminate; (iii) a method of producing a laminate in which a transfer target is integrated (adhered) with the protective layer side surface of a transfer sheet at the time of injection molding, and separating (peeling) a release sheet of the transfer sheet from the laminate [ in-mold molding (injection molding simultaneous transfer decoration method) ], and the like. Of these, in the case of in-mold molding (injection molding and simultaneous transfer decoration method), a resin molded article having a complicated surface shape such as a three-dimensional curved surface can be decorated and molded, and this is preferable.

One embodiment of a method for producing a decorative molded article using a transfer sheet of the present invention by in-mold molding includes a method including the steps of:

(a) disposing the surface of the transfer sheet on the side of the protective layer with respect to the release sheet so as to face the inside of the mold for in-mold molding;

(b) injecting and injecting resin into the mold for in-mold molding;

(c) a step of obtaining a laminate in which the surface of the transfer sheet on the protective layer side is integrated (bonded) with the resin; and

(d) and a step of separating (peeling) the transfer sheet from the laminate after the laminate is taken out from the mold.

By manufacturing the decorative molded article by such a manufacturing process, a complicated design can be realized on the surface of the attached body.

When the protective layer is in a semi-cured state, it is preferable that the protective layer is completely cured by irradiation with ultraviolet light after the end of the step (d).

[ display device ]

The display device of the present invention is formed by providing the decorative molded article of the present invention on the front surface of the display element.

Examples of the display element include a liquid crystal display element, an EL display element, a plasma display element, and an electronic paper element.

The display device of the present invention can make brightness uniform and inhibit whitening, so that the visibility is very good.