JP7024454B2 - Laminates and articles - Google Patents

Description

The present disclosure relates to a laminated body which is used in an overlay method and can suppress unevenness defects when placed on an adherend.

A decoration method called an overlay method is used as a technique for imparting designs such as colors and patterns to the surfaces of various articles such as vehicle interior / exterior parts, building material interior materials, and home appliance housings (for example, patent documents). 1-2). The overlay method usually has a desired design property, and is performed by a heat treatment step of heat-treating a laminate provided with an adhesive layer and pressing the adhesive layer of the heat-treated laminate against an adherend. It has a laminating step of laminating the laminated body so as to follow the shape of the adherend.

Japanese Unexamined Patent Publication No. 2012-96403 Japanese Unexamined Patent Publication No. 2012-101549

The article decorated by the overlay method has a problem that the surface of the laminated body bonded to the adherend has a yuzu-skin-like or crater-like unevenness defect, and the design is deteriorated.
The present disclosure is an invention made in view of the above circumstances, and an object of the present invention is to provide a laminated body which is used in an overlay method and can suppress the occurrence of unevenness defects, and an article using the same.

In order to solve the above problems, the present disclosure is a laminate used in the overlay method, in which a resin base material layer and an adhesive layer arranged on one surface side of the resin base material layer and containing an adhesive are provided. In the graph obtained by measuring the logarithmic decay rate of the adhesive by the rigid pendulum method and plotting the logarithmic decay rate with respect to the measured temperature, when the peak at the glass transition point temperature of the adhesive is P1, the above P1 Provided is a laminate characterized in that the temperature at the turning point on the increasing side of the above is 120 ° C. or lower.

According to the present disclosure, by having an adhesive layer whose logarithmic decrement rate in the rigid pendulum method exhibits a specific behavior, it is possible to obtain a laminated body capable of suppressing unevenness defects.

The present disclosure has a resin base material layer and an adhesive layer arranged on one surface side of the resin base material layer and containing an adhesive, and the logarithmic decrement of the adhesive is measured by a rigid pendulum method. In the graph plotting the logarithmic decrement with respect to the measured temperature, when the peak at the glass transition temperature of the adhesive is P1, the temperature at the turning point on the increasing side of P1 is 160 ° C. or higher. To provide a laminated body.

According to the present disclosure, by having an adhesive layer whose logarithmic decrement rate in the rigid pendulum method exhibits a specific behavior, it is possible to obtain a laminated body capable of suppressing unevenness defects.

In the above disclosure, the adhesive strength of the adhesive layer may be 10 N / inch or more. This is because the laminated body can be satisfactorily bonded to various adherends.

The present disclosure provides an article comprising the above-mentioned laminated body and an adherend, wherein the adherend and the above-mentioned adhesive layer of the above-mentioned laminate are arranged so as to face each other.

According to the present disclosure, by having the above-mentioned laminated body, it is possible to obtain an article having good design.

The laminated body of the present disclosure is used in an overlay method and has an effect of being able to suppress unevenness defects.

It is a schematic sectional drawing which shows an example of the laminated body of this disclosure. This is an example of a graph in which the logarithmic decrement of the adhesive is measured by the rigid pendulum method and the logarithmic decrement with respect to the measured temperature is plotted. It is a process drawing explaining the outline of the overlay method. It is explanatory drawing explaining the heat treatment method in an overlay method. It is the evaluation result by the rigid pendulum method of the adhesive in Examples 1 to 3 and Comparative Examples 1 and 2.

In the following description, embodiments of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different embodiments and is not construed as being limited to the description of the embodiments exemplified below. Further, in order to clarify the explanation, the drawings may schematically show the width, thickness, shape, etc. of each part as compared with the actual form, but this is just an example and the interpretation of the present disclosure is limited. It's not something to do. Further, in the present specification and each figure, the same elements as those described above with respect to the above-mentioned figures may be designated by the same reference numerals, and detailed description thereof may be omitted as appropriate.
Hereinafter, the details of the laminate and the article of the present disclosure will be described.
In addition, in this specification, "sheet" and "film" are synonymous, and the wording of both "sheet" and "film" may be used for explanation.

A. Laminated body The laminated body of the present disclosure is a laminated body used in the overlay method, and has a resin base material layer and an adhesive layer arranged on one surface side of the resin base material layer and containing an adhesive. , The logarithmic decay rate of the adhesive is measured by the rigid pendulum method, and in the graph plotting the logarithmic decay rate with respect to the measured temperature, when the peak at the glass transition point temperature of the adhesive is P1, the increase of P1. It is characterized in that the temperature at the turning point on the side is above a specific value or below a specific value.
In the following description, the "peak at the glass transition temperature of the adhesive" will be referred to as "Tg peak", and the "increasing inflection point of Tg peak P1" will be referred to as "increasing inflection point". May be explained.

The layer structure of the laminated body of the present disclosure will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the laminated body of the present disclosure. As shown in FIG. 1, the laminate 10 of the present disclosure is arranged on one surface side of the resin base material layer 1 and the resin base material layer 1, and has at least an adhesive layer 2 containing an adhesive.

The characteristics of the adhesive layer in the laminate of the present disclosure will be described. FIG. 2 is an example of a graph in which the logarithmic decrement of an adhesive is measured by the rigid pendulum method and the logarithmic decrement with respect to the measured temperature is plotted. For example, as shown in Graph 1 in FIG. 2, the adhesive used in the present disclosure has a temperature of 120 ° C. or lower at the inflection point P11 on the increasing side of P1 when the Tg of the adhesive is P1. Or, for example, as shown in Graph 2 in FIG. 2, the temperature at the inflection point P11 on the increasing side of P1 is 160 ° C. or higher.

The laminate of the present disclosure is used in the overlay method. The overlay method to which the laminate of the present disclosure is applied will be described with reference to the drawings. 3 (a) to 3 (c) are process diagrams illustrating an outline of the overlay method. The overlay method usually has at least a heat treatment step and a laminating step. In the heat treatment step, for example, as shown in FIGS. 3A and 3B, heat H is applied to the laminate 10 having the resin base material layer 1 and the adhesive layer 2 containing an adhesive to perform heat treatment. FIG. 3A shows the laminated body 10A before the heat treatment, and FIG. 3B shows the laminated body 10B after the heat treatment. The heat treatment step is a step of softening the laminated body 10B to the extent that it can follow the shape of the adherend. When the adhesive layer 2 is a layer that develops adhesiveness by heating, it is preferable to develop the adhesiveness of the adhesive layer 2 in the heat treatment step.
In the bonding step, as shown in FIG. 3C, the adhesive layer 2 of the heat-treated laminate 10B is pressed against the adherend 20 to press the laminate 10B into the shape of the adherend 20. Follow and stick together. By the above steps, the article 30 in which the laminated body 10 and the adherend 20 are bonded can be obtained.

As described above, in the article manufactured by using the overlay method, the surface of the laminated body bonded to the adherend may have a yuzu-skin-like or crater-like uneven defect, and the design may be deteriorated.
The reason is presumed as follows.
Generally, the heat treatment step of the overlay method is performed by controlling the heat treatment temperature to about 80 ° C. or higher and 200 ° C. or lower. The heat treatment temperature in the overlay method is preferably 100 ° C. or higher and 190 ° C. or lower, and particularly preferably 120 ° C. or higher and 180 ° C. or lower. This is because it is necessary to give the laminate a formability to the extent that it can follow the shape of the adherend by appropriately softening the laminate, while suppressing excessive softening of the laminate. This is because it is necessary to suppress drawdown in which bending occurs due to the weight of the laminated body itself.
The "heat treatment temperature" refers to the temperature of the heat source when the laminate is heat-treated in close proximity to the heat source, and refers to the temperature of the heat treatment atmosphere when the laminate is heat-treated without being in contact with the heat source.
However, in the heat treatment step of the overlay method, it is usually difficult to measure and control the temperature of the actual laminated body, so that the temperature varies in the plane of the laminated body, particularly in the plane of the adhesive layer. It tends to be easy. Further, in the plane of the adhesive layer, the state of the adhesive tends to vary depending on the temperature variation. That is, when the temperature tends to vary in the plane of the adhesive layer, the hardness of the adhesive layer tends to vary. Specifically, a soft portion and a hard portion tend to occur in the surface of the adhesive layer.
Further, in the bonding step, the temperature of the adherend is usually lower than the temperature of the heat-treated laminate. Therefore, when the heat-treated laminate is brought into contact with the adherend, the temperature of the laminate drops sharply.
If the temperature varies within the plane of the adhesive layer of the heat-treated laminate, the temperature of the laminate drops sharply, for example, the time until the adhesive contained in the adhesive layer cures, and the fluidity. It is presumed that irregularities will occur due to variations in the like and the like.

On the other hand, in the present disclosure, by having an adhesive layer in which the logarithmic decrement rate in the rigid pendulum method exhibits a specific behavior, it is possible to suppress variations in the in-plane state of the adhesive layer in the heat treatment temperature range of the overlay method. Therefore, it is possible to obtain a laminated body capable of suppressing unevenness defects.
Specifically, the adhesive layer contains an adhesive having a temperature of the increasing turning point of the Tg peak of 120 ° C. or lower, so that the adhesive contained in the adhesive layer is sufficiently softened in the heat treatment temperature range of the overlay method. Therefore, the entire in-plane of the adhesive layer can be softened. Therefore, since it is possible to suppress the variation in the in-plane state of the adhesive layer, it is possible to obtain a laminated body capable of suppressing unevenness defects.
On the other hand, since the adhesive layer contains an adhesive having a temperature of the increasing turning point of the Tg peak of 160 ° C. or higher, the hardness of the adhesive contained in the adhesive layer is sufficiently increased in the heat treatment temperature range of the overlay method. Since it can be maintained, the entire in-plane of the adhesive layer can be sufficiently hardened. Therefore, since it is possible to suppress the variation in the in-plane state of the adhesive layer, it is possible to obtain a laminated body capable of suppressing unevenness defects.

Here, the laminate of the present disclosure has an adhesive layer containing an adhesive. In the present disclosure, the adhesive layer is usually composed of an adhesive. Specifically, the adhesive formed in a layer is used as the adhesive layer.

In the present disclosure, it is specified whether or not the variation point of the logarithmic decrement peak indicating the glass transition point of the adhesive layer, which is measured by the rigid pendulum method, is less than or equal to a specific value. It is characterized in that it is equal to or more than the value of.
In the present specification, the logarithmic decrement measured by the rigid pendulum method means the logarithmic decrement measured in accordance with ISO122013-2 “Method for measuring thermal properties (Tg, hardness) of coating film”. The logarithmic decrement rate by the rigid pendulum method is, for example, a value calculated from a damping curve measured by the following measuring method.
As a measuring device, a rigid pendulum physical property tester RPT-3000W manufactured by A & D Co., Ltd. is used. A 5 cm × 1.5 cm laminate is prepared as a sample. The sample is placed on a sample table (CHB100) with the adhesive layer side facing upward. Next, a pendulum frame (FRB-400) having a round bar shape type (RBP-020; 2 mmφ) edge was placed on the adhesive layer of the sample, the pendulum measurement interval was 3.0 seconds, and the pendulum adsorption time was 2. The measurement is performed at 0 ° C. from 0 ° C. to a temperature exceeding 180 ° C. while raising the temperature at 3 ° C./min.

The "peak at the glass transition temperature of the adhesive" means the maximum value in the graph obtained by measuring the logarithmic decrement of the adhesive by the rigid pendulum method and plotting the logarithmic decrement with respect to the measured temperature. When there are a plurality of maximum values, the "peak of the logarithmic decrement indicating the glass transition point of the adhesive" means the maximum value on the highest temperature side.

The laminate of the present disclosure is roughly classified into two embodiments according to the nature of the adhesive layer. Hereinafter, each embodiment will be described.

I. First Embodiment The laminated body of the first embodiment is a laminated body used in the overlay method, and is arranged on one surface side of the resin base material layer and the resin base material layer, and is an adhesive layer containing an adhesive. When the logarithmic decrement of the adhesive is measured by the rigid pendulum method and the peak at the glass transition temperature of the adhesive is P1 in the graph plotting the logarithmic decrement with respect to the measured temperature. The temperature at the turning point on the increasing side of P1 is 120 ° C. or lower.

According to this embodiment, by having an adhesive layer including an adhesive layer in which the temperature of the increasing inflection point of the Tg peak is 120 ° C. or lower, the entire adhesive layer can be sufficiently softened in the heat treatment step of the overlay method. Since it is possible to suppress variations in the state of the adhesive layer in the plane, it is possible to obtain a laminated body capable of suppressing unevenness defects.
Hereinafter, the laminate of the first aspect will be described in detail.

1. 1. Adhesive layer The adhesive layer in the first aspect contains an adhesive. Further, for the adhesive contained in the adhesive layer, the logarithmic decay rate of the adhesive is measured by the rigid pendulum method, and the peak at the glass transition temperature of the adhesive is shown in the graph plotting the logarithmic decay rate with respect to the measured temperature. When P1 is set, the temperature at the turning point on the increasing side of P1 is 120 ° C. or lower. In the first embodiment, in the heat treatment temperature range of the overlay method, for example, by putting all the adhesives contained in the adhesive layer in a molten state, the in-plane of the adhesive layer can be made uniform, and unevenness can be obtained. The occurrence of defects can be suppressed.

The temperature of the increasing inflection point of the Tg peak in the adhesive may be 120 ° C. or lower, for example, 100 ° C. or lower, or 80 ° C. or lower. Further, the lower limit of the temperature of the increasing inflection point of the Tg peak in the adhesive is not particularly limited, but may be, for example, 40 ° C. or higher, or 50 ° C. or higher. This is because the adhesive layer can be prevented from exhibiting adhesiveness and tackiness in the laminated body before the heat treatment, and the laminated body can be easily handled.

The glass transition point (Tg) temperature of the adhesive is usually higher than the inflection point described above. The glass transition temperature of the adhesive may be, for example, 120 ° C. or higher and 160 ° C. or lower, or 120 ° C. or higher and 140 ° C. or lower.

In this embodiment, the adhesive may or may not have a peak other than the Tg peak.
Let P2 be a peak other than the Tg peak. P2 usually exists in a temperature range lower than P1 which is a Tg peak. The temperature difference between P1 and P2 may be, for example, 50 ° C. or lower, 70 ° C. or lower, or 90 ° C. or lower.

The adhesive strength of the adhesive layer is not particularly limited as long as the laminate of the first aspect can be bonded and fixed to the surface of the adherend, and is preferably 10 N / inch or more, preferably 20 N / inch or more. It is preferable to have. Further, the upper limit of the adhesive strength can be appropriately selected depending on the use of the laminated body and the like, and is not particularly limited. The adhesive strength may be, for example, 300 N / inch or less.
The adhesive strength of the adhesive layer is a value measured by the following measuring method.
First, the adhesive sheet provided with the separator on one surface of the adhesive layer is cut into a size of 25.4 mm in length and 150 mm in width. Next, an acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin") film is prepared. Next, the ABS resin film is attached to the surface opposite to the side where the separator is provided, that is, the surface where the adhesive layer is exposed, using a manual roller. From the above, a measurement sample is obtained.
Next, the measurement sample is bonded to the ABS resin plate. A simple molding device is used as the device. The molding device has a heat heater at the top and a flat pedestal at the bottom. An ABS resin plate (2 mm) cut into a size of 25.4 mm in length and 150 mm in width is placed in the center of the pedestal. Next, prepare a metal frame. The prepared measurement sample is sandwiched between metal frames, the separator attached to the adhesive layer is peeled off, and the sample is placed near the upper heat heater. A thermo label (registered trademark) is attached to the ABS resin film of the measurement sample, and with the thermo label (registered trademark) showing 120 ° C., the metal frame is lowered and brought into contact with the ABS resin plate (2 mm). The ABS resin film is attached to the ABS resin plate via the adhesive layer.
After that, the adhesive layer with the ABS resin film is peeled off by hand from the ABS resin plate by about 30 mm, and it conforms to JIS Z0237 using a tensile tester (manufactured by A & D Co., Ltd., model number: RTF-1150H). The adhesive strength (N / inch) to the ABS resin plate surface can be measured under the above conditions (tensile speed: 300 mm / min, peeling distance: 150 mm, peeling angle: 180 °). In addition, 1 inch is 25.4 mm.

The adhesive is not particularly limited as long as it has the above-mentioned increased inflection points and adhesiveness. Examples of the adhesive include a mixed material of styrene rubber and tack fire, a polyurethane-based elastomer, a polyamide-based elastomer, a polyester-based elastomer, and a polystyrene-based elastomer.

The form of the adhesive may be, for example, a film or a gel, or may be a liquid, but a film is preferable. Examples of the adhesive include ZA-810 manufactured by Hitachi Kasei Co., Ltd., DUS-641 manufactured by Seadam Co., Ltd., and X2200 manufactured by Shiki Spinning Co., Ltd. as commercially available products.

The thickness of the adhesive layer is not particularly limited as long as the laminated body can be adhered to the adherend, and can be appropriately selected depending on the type of the adherend and the like. The thickness of the adhesive layer may be, for example, 1 μm or more and 400 μm or less, or 20 μm or more and 150 μm or less.

The adhesive layer is arranged on one surface side of the resin base material layer described later. In the present embodiment, when another layer is laminated and arranged on the resin base material layer, the adhesive layer may be arranged on the surface side of the resin base material layer, and may be arranged on the surface side of the other layer. It may have been done.
The adhesive layer is a layer that is most arranged on the adherend side when the laminate of the present embodiment is arranged on the adherend.

2. 2. Resin base material layer The resin base material layer is a layer that supports the adhesive layer.
As the resin constituting the resin base material layer, for example, a thermoplastic resin is preferable.
Further, as the thermoplastic resin, a resin that softens to the extent that it exhibits moldability is usually used in the heat treatment step of the overlay method. The glass transition point of the thermoplastic resin is preferably, for example, 120 ° C. or higher and 200 ° C. or lower. The glass transition point of the thermoplastic resin is a value obtained by differential scanning calorimetry (DSC) based on JIS K7121-1987.
Examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene-acrylic acid ester resin, and acrylic resin. Examples of the thermoplastic resin include polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, vinyl chloride resins, polyethylene terephthalate (PET) resins and the like. As the resin constituting the resin base material layer, only one type of the above-mentioned thermoplastic resin may be used, or two or more types may be mixed and used. In this embodiment, the resin constituting the resin base material layer is preferably ABS resin. This is because it is possible to impart good three-dimensional moldability to the laminated body of the present embodiment.

The thickness of the resin base material layer can be appropriately selected depending on the use of the laminated body, the shape of the adherend, and the like, and is not particularly limited. The thickness of the resin base material layer is preferably, for example, 50 μm or more and 800 μm or less, 100 μm or more and 600 μm or less, or 150 μm or more and 400 μm or less.

The resin base material layer may or may not have transparency. When the laminate of this embodiment has a decorative layer described later and the resin base material layer is arranged on the user side of the decorative layer, it is preferable that the resin base material layer has transparency. .. The transparency of the resin substrate refers to the transparency of the decorative layer to the extent that the design can be observed, including colorless transparency and colored transparency to the extent that it does not interfere with visibility, and is not defined by a strict transmittance. ..

The resin base material layer may or may not have the design property of the resin base material layer itself. When the resin base material layer has a design property, for example, the resin base material layer may be colored. Further, for example, the resin base material layer may have an uneven pattern on its surface. The uneven pattern can be imparted, for example, by embossing the resin base material layer.

3. 3. Decorative layer The laminated body of this embodiment may further have a decorative layer. The decorative layer is a layer having a function of imparting design to the laminated body. The decorative layer may be, for example, a colored resin layer in which a pigment, a dye, or the like is dispersed, or a resin layer in which metal particles are dispersed. Further, the decorative layer may be, for example, a metal thin film layer.
Since the details of the decorative layer can be the same as those used in the general overlay method, the description thereof is omitted here.

4. Other Structures The laminate of the present embodiment is not particularly limited as long as it has the above-mentioned adhesive layer and resin base material layer, and may further have other layers if necessary. As the other layer, the same layer as that used for a decorative film for a general overlay method can be used, and examples thereof include a primer layer, a protective layer, an adhesive layer, and a color clear layer. Since the other resin layers can be the same as the layers used in general decorative sheets, the description thereof is omitted here.

II. Second Embodiment The laminate of the second embodiment has a resin base material layer and an adhesive layer arranged on one surface side of the resin base material layer and containing an adhesive, and is bonded by the rigid pendulum method. In the graph obtained by measuring the logarithmic decay rate of the agent and plotting the logarithmic decay rate with respect to the measured temperature, when the peak at the glass transition point temperature of the adhesive is P1, the temperature at the turning point on the increasing side of P1. Is characterized by a temperature of 160 ° C. or higher.

According to this embodiment, by having an adhesive layer containing an adhesive in which the temperature of the increasing inflection point of the Tg peak is 160 ° C. or higher, the entire adhesive layer can be sufficiently hardened in the heat treatment step of the overlay method. Since it is possible to suppress variations in the state of the adhesive layer in the plane, it is possible to obtain a laminated body capable of suppressing unevenness defects.

Regarding the laminate of the second embodiment, the points other than the adhesive layer can be the same as those described in the above-mentioned "I. First embodiment" section. Hereinafter, the adhesive layer in the second embodiment will be described.

The adhesive layer in the second embodiment contains an adhesive. Further, the adhesive contained in the adhesive layer is characterized in that the increasing inflection point of the Tg peak is 160 ° C. or higher. In the second embodiment, in the heat treatment temperature range of the overlay method, for example, by keeping the entire adhesive contained in the adhesive layer in a solid state, the in-plane of the adhesive layer can be made uniform, and unevenness defects can be obtained. Can be suppressed.
The temperature of the increasing inflection point of the Tg peak of the adhesive may be 160 ° C. or higher. Further, the inflection point of the Tg peak of the adhesive is preferably 220 ° C. or lower, for example.

The temperature of the glass transition point of the adhesive is usually higher than the increasing inflection point of the Tg peak. The temperature of the glass transition point of the adhesive is preferably, for example, 165 ° C. or higher and 250 ° C. or lower.
In the adhesive layer of the second embodiment, the reason why the adhesive develops adhesiveness at a temperature lower than the glass transition point is not clear, but it is presumed as follows. It is presumed that only the adhesive on the polar surface of the adhesive layer melts, the components of the melted adhesive soak into the adherend, and when the temperature returns to room temperature, the adhesive hardens again and adheres to the adherend. That is, in the second embodiment, the adhesive on the surface of the adhesive layer is melted by heat, but the adhesive layer as a whole is hardly melted, so that it is presumed that the effect of the rigid pendulum method on the logarithmic decrement is extremely small. ..

In the graph obtained by measuring the logarithmic decrement of the adhesive by the rigid body pendulum method and plotting the logarithmic decrement with respect to the measured temperature, for example, an increasing variation point of the Tg peak is observed up to a temperature range of 160 ° C. or higher. By not doing so, it can be confirmed that the temperature of the increasing turning point is 160 ° C. or higher. It can be confirmed that the glass transition point also exists on the higher temperature side than the measured temperature by not observing the Tg peak in the above graph.

The adhesive in the second embodiment preferably has a small change in logarithmic decrement in a range higher than 120 ° C and lower than 160 ° C. For example, the adhesive may have a difference between the maximum value and the minimum value of the logarithmic decrement in a range higher than 120 ° C. and lower than 160 ° C. of 0.2 or less, and may be 0.1 or less.
Further, the adhesive in the second embodiment may have a peak in a range higher than 120 ° C. and lower than 160 ° C., and may not have a peak, but the latter is more preferable.
This is because the variation in the state of the adhesive layer within the range of the heat treatment temperature in the overlay method can be further reduced, so that unevenness defects can be suitably suppressed.

The adhesive in the second embodiment may or may not have a peak in a temperature range lower than 120 ° C., for example.

The adhesive strength of the adhesive layer is not particularly limited as long as the laminate of the second embodiment can be bonded and fixed to the surface of the adherend, and is preferably 10 N / inch or more, preferably 20 N / inch or more, for example. Is more preferable, and 30 N / inch or more is further preferable. Further, the adhesive strength of the adhesive layer may be, for example, 300 N / inch or less.
Since the method for measuring the adhesive strength of the adhesive layer can be the same as that described in the above-mentioned "I. First Embodiment 1. Adhesive layer", the description thereof is omitted here.

The adhesive is not particularly limited as long as it has the above-mentioned increased inflection points and adhesiveness. Examples of the adhesive include a material containing a polyurethane resin.
The form of the adhesive may be, for example, a film or a liquid, but is preferably a film. As the adhesive, as a commercially available product, for example, DUS614 manufactured by Seadam Co., Ltd. can be mentioned.

Since the thickness of the adhesive layer can be the same as that described in the above-mentioned "I. First aspect 1. Adhesive layer", the description thereof is omitted here.

III. Laminated body The laminated body of the present disclosure can be used as a decorative sheet or a decorative film, for example, when the resin base material layer itself has a design property or when it further has a decorative layer. On the other hand, when the laminate of the present disclosure does not have a design property, it can be used as a member constituting a decorative sheet or a decorative film.

IV. Overlay method The laminate of the present disclosure is used in the overlay method. The overlay method applied to the laminate of the present disclosure is usually a heat treatment step of heat-treating the laminate and pressing the adhesive layer of the heat-treated laminate against the adherend to press the laminate. It has a bonding step of following the shape of the adherend and bonding.
The heat treatment method of the laminated body in the heat treatment step can be the same as the heat treatment method used in the general overlay method. As a method for heat-treating the laminate, for example, as shown in FIG. 4A, the laminate 10 may be brought into contact with the heat source s to perform the heat treatment, and as shown in FIG. 4B, the heat source s may be heat-treated. The heat treatment may be performed without contacting the laminate 10. In the present disclosure, the latter is more preferred. Compared to the case where the heat source and the laminate are brought into contact with each other for heat treatment, when the heat treatment is performed without contacting the heat source and the laminate, the amount of heat transferred from the heat source to the laminate is likely to vary, and the surface of the laminate is likely to vary. The temperature inside tends to vary. Therefore, it is possible to exert a high effect of suppressing unevenness defects by applying the laminated body of the present disclosure.

The heat treatment temperature in the heat treatment step is 80 ° C. or higher and 200 ° C. or lower, preferably 100 ° C. or higher and 190 ° C. or lower, and particularly preferably 120 ° C. or higher and 180 ° C. or lower.
The heat source can be the same as the heat source used in a general overlay method, and examples thereof include a heater and a hot plate.

The pressing method of the laminated body in the bonding step can be the same as the pressing method used in a general overlay method. The pressing method may be a method of pressing by placing the adherend and the laminated body under reduced pressure, and by reducing the pressure in the gap between the adherend and the laminated body, the laminated body becomes the adherend. It may be a method of being pressed by, or a method of pressing by using compressed air.

In the present disclosure, a second heat treatment step may be provided in which the laminated body and the adherend are bonded to each other to prepare an article, and then the article is heat-treated, if necessary. By performing the second heat treatment step, the adhesiveness between the laminated body and the adherend can be further improved. The heat treatment method in the second heat treatment step can be the same as the method used in the general overlay method. As an example, heat treatment using steam can be mentioned.

The overlay method may be, for example, the TOM (Three dimension Overly Method) method of Fuse Vacuum Co., Ltd., or the method using the air transfer device NATS (Navitas Air-heat Transfer System) of Navitas Co., Ltd. A method using a hot plate vacuum coating molding machine TFH of Asano Laboratories Co., Ltd. may be used.

B. Article The article of the present disclosure has the laminate described in "A. Laminate" described above and an adherend, and the adherend and the adhesive layer of the laminate are arranged so as to face each other. It is characterized by that.

According to the present disclosure, by having the above-mentioned laminated body, it is possible to make an article having a good design.

Since the laminated body used in the article of the present disclosure is described in the above-mentioned section "A. Laminated body", the description thereof is omitted here. In the articles of the present disclosure, the laminate is usually molded to follow the shape of the adherend.

The adherend in the present disclosure is not particularly limited as long as the above-mentioned laminated body can be bonded by the overlay method. The material of the adherend may be, for example, resin, ceramics, wood, or metal.
When the material of the adherend is a resin, the type of the resin is not particularly limited and can be appropriately selected depending on the shape of the adherend and the like. In the present disclosure, the resin used for the adherend may contain ABS resin.

The shape of the adherend is not particularly limited and can be appropriately selected depending on the type of the article. The shape of the adherend preferably has a three-dimensional shape.

An overlay method is usually used as a method for manufacturing an article. Since the overlay method can be the same as that described in "A. Laminated body III. Others" described above, the description thereof is omitted here.

The present disclosure is not limited to the above embodiment. The above embodiment is an example, and any object having substantially the same structure as the technical idea described in the claims of the present disclosure and having the same effect and effect is the present invention. Included in the technical scope of the disclosure.

Examples are shown below, and the present disclosure will be described in more detail.

[Example 1]
An acrylic resin film having a thickness of 125 μm was prepared as the resin base material layer. As an adhesive, ZA-810 manufactured by Hitachi Kasei Co., Ltd. was applied to a release film at 100 μm to prepare. The adhesive layer was attached to an acrylic resin film with a laminating roller, and the release film was peeled off to form an adhesive layer having a thickness of 100 μm on one surface side of the resin base material layer. By the above procedure, a laminated body was obtained.

[Example 2]
Using a laminating roller heated to about 80 ° C., a sheet (thickness 100 μm) of DUS614 manufactured by Seadam Co., Ltd. was directly bonded to an acrylic resin film having a thickness of 125 μm to obtain a laminated body.

[Example 3]
A laminated body was obtained in the same manner as in Example 2 except that an X2200 sheet (thickness 30 μm) manufactured by Shiki Spinning Co., Ltd. was used.

[Comparative Example 1]
A laminated body was obtained in the same manner as in Example 2 except that a sheet (thickness 90 μm) of SHM103 manufactured by Seadam Co., Ltd. was used.

[Comparative Example 2]
A laminated body was obtained in the same manner as in Example 2 except that a G-5 sheet (thickness 100 μm) manufactured by Kurabo Industries Ltd. was used.

[evaluation]
(Evaluation by rigid pendulum method)
The logarithmic reduction rate of the adhesives used in Examples 1 to 3 and Comparative Examples 1 and 2 was measured by the rigid pendulum method under the conditions described in the above-mentioned item "A. Laminated body". A graph was created by plotting the logarithmic reduction rate with respect to the measured temperature, and the Tg peak P1 and the increasing inflection point were obtained. The results are shown in Table 1 and FIG. As shown in FIG. 5, in Example 1, a peak was confirmed at a position of about 30 ° C. in addition to the Tg peak. Further, in Example 2, since no peak was confirmed, it was confirmed that the glass transition point of the adhesive was present at a position exceeding 180 ° C. In Table 1, the temperature exceeding 180 ° C. is indicated by “> 180 ° C.”.

(Evaluation of surface unevenness defects)
By the overlay method, the laminated bodies of Examples 1 to 3 and Comparative Examples 1 and 2 were bonded to an ABS resin plate as an adherend. The condition of the overlay method was a method in which the laminated body was pressed against the adherend by reducing the pressure in the gap between the adherend and the laminate at an atmospheric temperature of 120 ° C. The presence or absence of surface unevenness defects in the laminated body after bonding was evaluated. The results are shown in Table 1. In addition, in Table 1, "◯" indicates that the ratio of the area where unevenness was confirmed to the area of the whole laminated body after bonding was 10% or less. Further, "Δ" indicates that the ratio of the area where the unevenness was confirmed to the area of the entire laminated body after bonding was 50% or less. Further, "x" indicates that the ratio of the area where the unevenness was confirmed to the area of the entire laminated body after bonding exceeded 50%. The ratio of the area where unevenness is confirmed to the total area of the laminated body after bonding is specifically the surface area of the portion of the laminated body that has been bonded to the adherend (of the adherend). It refers to the ratio of the surface area where unevenness is confirmed to the total surface area of the laminated body bonded on one side surface and side surface.

(Evaluation by adhesive strength test)
Under the conditions described in the item of "A. Laminated body" described above, the adhesive strength of the adhesive layer in the laminated bodies of Examples 1 to 3 and Comparative Examples 1 and 2 was measured. The results are shown in Table 1.

(Evaluation of adhesion start temperature)
The adhesion start temperature of the laminates of Examples 1 to 3 and Comparative Examples 1 and 2 was measured.
The method for measuring the adhesion start temperature is as follows.
The temperature of the flat plate press was set to a specific temperature. The laminated body and the ABS resin plate were prepared, and were laminated and arranged so that the adhesive layer side of the laminated body faced the ABS resin plate. Next, the ABS and the laminate were pressed at a pressure of 0.3 MPa for 1 minute using the flat plate press. The lowest temperature (the set temperature of the flat plate press machine) at which it was confirmed that the acrylic resin film of the laminated body after pressing and the ABS resin plate were bonded to each other when they were manually peeled off was set as the bonding start temperature. And said. The set temperature of the flat plate press was measured by changing the temperature in increments of 80 ° C to 10 ° C.

From the measurement results, it is possible to suppress surface unevenness defects in the laminates of Examples 1 to 4 using the adhesive having the temperature of the increasing inflection point of the Tg peak of 120 ° C. or lower or 160 ° C. or higher. confirmed.

1 ... Resin base material layer 2 ... Adhesive layer 10 ... Laminated body 20 ... Adhesive body 30 ... Article

Claims (2)

A laminate used in the overlay method,
It has a resin base material layer and an adhesive layer arranged on one surface side of the resin base material layer and containing an adhesive.
When the logarithmic decrement of the adhesive is measured by the rigid pendulum method and the peak at the glass transition point temperature of the adhesive is P1 in the graph plotting the logarithmic decrement with respect to the measured temperature, the increasing side of P1. The temperature at the turning point of is 120 ° C or less ,
A laminate in which the resin base material layer is made of acrylonitrile-butadiene-styrene resin . An article having the laminate according to claim 1 and an adherend, in which the adherend and the adhesive layer of the laminate are arranged so as to face each other.

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