JP5641306B2 - Method for producing decorative molded body - Google Patents

Description

  The present invention relates to a method for producing a decorative molded body by a vacuum molding simultaneous decorating method, and more specifically, a decorative molded body formed by integrally bonding a thermoformable resin sheet to an adherend by a vacuum molding method. It relates to the manufacturing method.

As a method of decorating a resin molded body such as an injection molded body, conventionally, a coloring agent such as a pigment is kneaded into the resin and the resin itself is colored and injection molded, or the surface layer of the molded body after injection molding A method of spray-coating clear paint or colored paint is used. However, in recent years, there is a tendency to be avoided from the viewpoint of protection of the working environment against the discharge of chemical substances and the protection of the external environment, and a means to replace the coating method is required.
On the other hand, an adhesive layer is provided on the opposite surface of the sheet in which a surface protective layer made of a cross-linking curable acrylic resin is formed on the surface of a base sheet mainly composed of acrylic resin, polystyrene resin, ABS resin, or the like. There has been proposed a method of providing and forming in a three-dimensional shape by thermoforming and simultaneously attaching to a resin molded body, that is, a vacuum molding simultaneous decorating method (see, for example, Patent Document 1). With this method, it is possible to decorate a printed design on a resin molded body such as an injection molded body without using a solvent.

  On the other hand, in the method described above, many proposals have been made for a design that gives a special aesthetic appearance and touch feeling by giving the surface of the decorative layer unevenness. For example, a heated engraving roll such as a shaping sheet, embossing or shriner processing is used. After the surface of the sheet is physically roughened by contact pressure, it is molded into a three-dimensional shape by thermoforming, and at the same time it is affixed to a resin molding and integrated, or by using ionizing radiation curable resin. A method of thermoforming after applying a concavo-convex pattern layer to a sheet by a method or the like is known. However, both of these are methods for pre-developing the sheet prior to thermoforming, and have a deep-drawn shape that reduces concavities and convexities due to softening by heating during thermoforming and requires a high spread ratio. When using a resin molded product that is a body, the desired unevenness may not be obtained on the decorative surface. Moreover, since an embossing device and a special printing process are required in the sheet manufacturing process, there is a problem that the cost is increased.

  On the other hand, a method of obtaining desired irregularities after heating without giving irregularities to the sheet by a physical method such as embossing has been studied in the past. For example, a method in which a heat-sensitive pattern portion is recessed or roughened by irradiating infrared rays to a composite provided with an arbitrary heat-sensitive pattern on a polymer compound that can be melted at a low temperature provided on a substrate (for example, Patent Document 2), manufacturing a laminate in which a heat-shrinkable resin sheet, a base material, and an image layer containing at least a heat-absorbing colorant are superposed, and then placing another substrate on the base material side of the laminate After forming a composite by superimposing, a heat ray is irradiated from the laminate side to form a recess or an opening in the heat-shrinkable resin sheet in an area corresponding to the heat-absorbing image area. Manufacturing methods are known (see, for example, Patent Documents 3 and 4). A heat generating material such as an infrared absorber absorbs near infrared light or infrared light to generate heat. Patent Documents 2 to 4 make use of this phenomenon to plasticize a polymer compound that is in contact with the heat generating substance to provide a recess or an opening.

  However, the method described in the above document has poor reproducibility, and it has been difficult in recent years to obtain unevenness enough to withstand a desired design. In addition, when the decorative material described in the above-mentioned document is applied to a thermoformed sheet, that is, an adhesive layer is provided on the back surface of the decorative material, and is molded into a three-dimensional shape by thermoforming, and at the same time is attached to a resin molded body to be integrated. In this case, it was not possible to obtain unevenness.

JP 2000-1553587 A JP-A-49-31757 Japanese Patent Laid-Open No. 50-59448 Japanese Patent Laid-Open No. 50-61455

  The problem to be solved by the present invention is to obtain a decorative molded body having irregularities on the decorated surface after decoration without requiring a physical method such as embossing in the simultaneous vacuum molding decoration method. It is to provide a method. It is another object of the present invention to provide a method for producing a decorative molded body that can control the development of unevenness and the molding time and can be satisfactorily decorated even when an adherend that is weak against heat is used.

The present inventors held a resin sheet having heat shrinkability having a portion A provided with an ink containing a metal oxide,
The part A of the resin sheet and the part B adjacent to the part A in the same plane of the resin sheet have different surface temperatures of the part A and the part B, and at least the surface of the part A The resin sheet is irradiated with infrared rays so that the temperature becomes a surface temperature equal to or higher than the orientation return strength inflection point temperature T of the resin sheet, and the film thickness difference is generated between the part A and the part B. The present inventors have found a method for producing a decorative molded body that is attached to an adherend by vacuum forming and integrated.

The heat-shrinkable resin sheet shrinks by heating to restore the sheet to the state before stretching. The force indicated at this time is the orientation return strength, and the strength varies depending on the heating temperature.
The present inventors provide an ink containing a metal oxide on the resin sheet having heat shrinkability, in a state in which the ink is held, and a plurality of parts in the same plane of the resin sheet have different surface temperatures. And when heating is performed so that at least one surface temperature of the plurality of portions is equal to or higher than the orientation return strength inflection point temperature T of the resin sheet, the sheet behavior of the plurality of portions is different as a result. The difference in film thickness is caused in the part, and the film thickness difference and the molding time can be controlled more by providing the ink containing the metal oxide, and even when the adherend that is weak against heat is used. It discovered that it could decorate well. The present invention has succeeded in intentionally producing a film thickness difference, that is, unevenness by utilizing the temperature difference of the sheet and controlling the heating time of the sheet surface and the amount of heat to the adherend.

  The sheet having the film thickness difference has unevenness evenly on both sides of the sheet. Therefore, by sticking to an adherend by a vacuum forming method, sharp irregularities can be obtained with good reproducibility even if the adherend has a deep drawing shape that requires a high spreading magnification.

That is, the present invention, in a state of holding a heat-shrinkable resin sheet having a portion A provided with an ink containing a metal oxide,
The part A of the resin sheet and the part B adjacent to the part A in the same plane of the resin sheet have different surface temperatures of the part A and the part B, and at least the surface of the part A The step (1) of causing the film thickness difference between the part A and the part B by irradiating with infrared rays so that the temperature becomes a surface temperature equal to or higher than the orientation return strength inflection point temperature T of the resin sheet and the resin sheet The manufacturing method of the decorative molded body which has an unevenness | corrugation on the decorative surface which has the process (2) which affixes to a to-be-adhered body by a vacuum forming method, and integrates.

  According to the present invention, in a vacuum forming simultaneous decorating method, a decorative molded body having irregularities on the decorated surface after decorating can be obtained with good reproducibility without requiring a physical method such as embossing. In particular, it is possible to obtain a decorative molded body that can control unevenness expression and molding time and can be well decorated even when an adherend that is weak against heat is used.

(Definition of irregularities)
In the present invention, as described above, the formation of the unevenness is that the adjacent portion A and the portion B in the same plane of the resin sheet have different surface temperatures while holding the resin sheet having heat shrinkability. Arise. In the present invention, a part having a relatively high surface temperature is defined as part A, and a part having a relatively low surface temperature is defined as part B. At this time, the part A becomes a relatively concave part and the part B becomes a relatively convex part.

In the region A, it is considered that when the resin sheet having heat shrinkability is irradiated with infrared rays, the resin is plasticized and the orientation return of the resin sheet starts to be reduced, so that the thinning of the central portion occurs due to the self-shrinkage behavior.
The thickness change due to this self-shrinking behavior has no starting point and tends to shrink overall and thicken overall when no resin sheet is held. In the state where only the outer periphery or the entire outer periphery is held (hereinafter sometimes simply referred to as “held state”), there is a tendency for shrinkage to occur starting from a clamp portion having a low temperature, and as a result, thinning of the portion A occurs. Conceivable. Therefore, the part A often becomes thinner than the film thickness of the resin sheet before infrared irradiation, that is, before shrinkage.

  On the other hand, the part B is a part adjacent to the part A and has a surface temperature different from the part A and a surface temperature relatively lower than that of the part A. However, the part B is thinned at the center of the part A. Therefore, it is considered that the resin component present in the part A is moved and contracted due to self-shrinkage, and the film thickness is relatively thicker than the part A. In most cases, the part B is often thicker than the film thickness of the resin sheet before infrared irradiation, that is, before shrinkage. In addition, it is observed that the boundary between the part A and the part B becomes thicker (see FIG. 3). Thereby, a stronger sense of unevenness can be obtained.

  In the present invention, the part A is formed with an ink containing a metal oxide. Specifically, a portion A provided with a pattern along a desired concavo-convex portion is formed on a resin sheet having heat shrinkability described later with an ink containing a metal oxide by a method such as printing. The sheet is irradiated with infrared rays so that the surface temperature of the part A is equal to or higher than the orientation return strength inflection point temperature T of the resin sheet, and a difference in film thickness occurs between the part A and the part B. By doing so, irregularities are formed along the portion A where the ink containing the metal oxide is provided.

  Or you may form the said site | part A with mixed ink with infrared rays absorption ink, infrared rays reflection ink, or infrared rays transmission ink.

  Alternatively, the part A may be formed by overprinting with an ink containing a metal oxide and at least one ink selected from the group consisting of an infrared absorbing ink, an infrared reflecting ink, and an infrared transmitting ink.

  As a method of irradiating infrared rays so that a plurality of portions in the same plane of the resin sheet have different surface temperatures and imparting irregularities, the applicant first uses a method of using infrared absorbing ink or infrared reflecting ink (described later). (1) to (3)) have been invented (Japanese Patent Application No. 2010-523225).

Infrared absorbing ink or infrared reflecting ink is ink that absorbs or reflects infrared rays.
Infrared absorbing ink is an ink containing an infrared absorbing agent and the like, and absorbs infrared rays and generates heat. That is, when the resin sheet printed with the infrared absorbing ink is irradiated with infrared rays, only the amount of heat applied by the infrared irradiation is applied only to the portion printed with the infrared absorbing ink.
On the other hand, the infrared reflecting ink is an ink containing an infrared reflecting material and reflects the irradiated infrared rays. When the resin sheet printed with infrared reflecting ink is irradiated with infrared rays from the resin sheet side (that is, the surface opposite to the printing surface of the resin sheet), the infrared rays that have passed through the resin sheet are reflected by the infrared reflecting ink. By this, only the printing part where the infrared transmission part and the reflection part overlap is applied with a heat amount equal to or more than the amount of heat applied by infrared irradiation (specifically, the part A is compared with the part B where no pattern is provided) It is estimated that heat can be supplied to the sheet more efficiently).
That is, since only the amount of heat applied by infrared irradiation is applied only to the portion printed with the infrared absorbing ink or the infrared reflecting ink, the surface temperature of the portion can be increased, and as a result, the infrared absorption of the resin sheet is increased. A temperature difference can be generated between a portion printed with ink and a portion not printed.

  Specifically, (1) The resin sheet having heat shrinkability is provided with a pattern with infrared absorbing ink or infrared reflecting ink, and the portion A and the pattern provided with the pattern with the infrared absorbing ink or infrared reflecting ink are provided. Irradiation with infrared rays is performed so that the surface temperature is different from that of the non-part B. Since only the part A has a heat amount equal to or greater than the amount of heat applied by infrared irradiation, the surface temperature of the part A becomes higher than the part B that is not printed.

Alternatively, (2) the resin sheet having heat shrinkability is provided with a pattern so as to have the portion A having a high ink concentration and the portion B having a low ink concentration with infrared absorbing ink or infrared reflecting ink, Irradiation with infrared rays is performed so that the portion A having a high ink density and the portion B having a low ink density have different surface temperatures.
In this case, both the part A and the part B are subjected to heat more than the amount of heat applied by infrared irradiation, but the part A is heated more as a result of the higher ink density than the part B. Therefore, the surface temperature of the part A is relatively higher than that of the part B.

Alternatively, (3) a resin sheet having heat shrinkability is provided with a pattern with a plurality of infrared absorbing inks or infrared reflecting inks having different infrared absorptivity or reflectance,
The portion A where the pattern is provided with the ink having high infrared absorption or reflectance and the portion B where the pattern is provided with the ink having low infrared absorption or reflectance are set to have different surface temperatures.
In this case, both the part A and the part B are subjected to heat more than the amount of heat imparted by infrared irradiation, but the part A is heated more as a result of providing ink having higher infrared absorption or reflectance than the part B. Therefore, the surface temperature of the part A is relatively higher than that of the part B.

  The sheet having the film thickness difference has unevenness evenly on both sides of the sheet. Therefore, by sticking to an adherend by a vacuum forming method, sharp irregularities can be obtained with good reproducibility even if the adherend has a deep drawing shape that requires a high spreading magnification.

  The ink containing the metal oxide is mixed with the infrared absorbing ink or the infrared reflecting ink, or overprinted to control the expression of the film thickness difference as in the above (1) to (3). And the molding time can be controlled.

  Specifically, in the method (1), when the difference in surface temperature between the part A where the pattern is provided with the infrared absorbing ink or the infrared reflecting ink and the part B where the pattern is not provided is too large, the infrared absorbing ink or Control can be performed by appropriately adding a metal oxide to the infrared reflective ink.

  In addition, in the method (3), as the infrared absorbing ink or infrared reflecting ink having different infrared absorptance or reflectance, is a mixed ink of an ink containing a metal oxide and the infrared absorbing ink or infrared reflecting ink used? Alternatively, the same effect can be obtained by overprinting ink containing a metal oxide.

On the other hand, the infrared transmitting ink is an ink that transmits irradiated infrared rays. Since the portion where the ink is provided does not develop unevenness, it is used as the ink for the portion B according to the desired design. However, in this case, the transmitted infrared rays reach the surface of the adherend, that is, the amount of infrared irradiation is different between the adherent portion of the portion A and the adherent portion of the portion B, thereby causing partial deformation or adhesion of the adherend. May affect sex.
The ink containing the metal oxide is used by mixing with the infrared transmitting ink, and in the step of causing the film thickness difference by infrared irradiation, to the adherend installed on the side opposite to the infrared irradiation portion of the sheet. It also has the effect of preventing damage from infrared rays. Therefore, it is possible to prevent damage to the adherend of infrared rays by mixing with infrared transmitting ink or by overprinting with infrared transmitting ink.

An example in which the unevenness is formed is shown in FIGS. FIG. 1 shows a heat-shrinkable resin sheet printed with a pattern using three types of infrared absorbing ink, mixed ink of metal oxide ink and infrared absorbing ink, and color ink (which does not absorb infrared rays). It is a figure which shows the specific one aspect | mode which showed the state which irradiates infrared rays using an infrared heater, FIG. 2 is the state of the said resin sheet after irradiating infrared rays in the state which hold | maintained the said resin sheet in FIG. FIG.
By irradiating the resin sheet with infrared rays as shown in FIG. 1, as shown in FIG. 2, the printed portion 4 of the infrared absorbing ink, that is, the portion A is most thinned or becomes a concave portion, and the metal oxide ink and the infrared absorbing ink The mixed ink 5 becomes a thicker film than the printing part 4, and becomes a thin film rather than the color ink printing part 6, and becomes a convex part when viewed from the printing part 4. Furthermore, since the color ink printing part 6 becomes the thickest film, it becomes the highest convex part.
In the case of a resin sheet having a non-printing part without using the color ink printing part 6, the high-concentration infrared absorbing ink printing part becomes a concave part, and the mixed ink printing part of the metal oxide ink and the infrared absorbing ink is low. A convex part and a non-printing part become the highest convex part. (Not shown)
As described above, since the film is relatively thin and thick, unevenness is generated.

  The formation of the unevenness occurs evenly on both surfaces of the resin sheet as shown in FIG. Accordingly, the surface of the resin sheet in contact with the adherend is also uneven. However, when it is attached to an adherend by vacuum forming in this state, a decorative molded body having unevenness that is neatly adhered can be obtained without causing a float on the decorative surface of the adherend (FIG. 3). reference). Further, it has been confirmed that the difference in height of the sheet surface between the part A and the part B is more generated than in the state shown in FIG. This is probably because in the vacuum molding method, the resin sheet is molded in a plasticized state (that is, in a heated state), so that the A portion having a small film thickness is also plasticized and brought into contact with the adherend while being plasticized. Therefore, it is presumed that the part A is also in close contact with the adherend surface, and the height of the sheet surface with the relatively thick B part is reproduced more greatly.

  The level difference of the unevenness can be measured with a surface roughness meter or a film thickness meter. If the difference between the highest and lowest surface unevenness after decoration (hereinafter referred to as film thickness difference) is about 10 μm, Can be recognized. In order to express clear irregularities, the film thickness difference is preferably about 15 μm, and more preferably 20 μm or more. On the other hand, since the difference in film thickness becomes smaller in proportion to the expansion ratio, the deeper molded product tends to decrease in uneven film thickness. Moreover, the width of each unevenness tends to increase as the development magnification increases.

In the present invention, the pattern expressed by the unevenness is not particularly limited, and there is no particular limitation on the thickness, size, shape, etc. of the drawing that expresses the pattern shape such as a pattern or a character. That is, in the present invention, any unevenness is possible as long as the means (1) to (3) are used, such as printing and handwriting, as long as the pattern or characters can be printed or printed.
Examples of patterns include drawing expressed with pointillism and line drawing (specifically, outlines of paintings and characters, wood grain, stripes, hairline patterns, etc.), dots, geometric patterns, characters and marks themselves When it is desired, an object having a small pattern area is more preferable. Of course, the present invention is not limited to this, and it is possible to express all patterns of patterns such as patterns and characters.
FIGS. 4 to 7 show examples of pattern patterns expressed by unevenness in the present invention. A black part is the site | part A which provided the ink containing a metal oxide. 4 represents a stripe, FIG. 5 represents a dot, FIG. 6 represents a geometric pattern, and FIG. 7 represents a grain.

(Surface temperature)
In the present invention, “surface temperature of the part A and the part B” is defined as an index of the temperature. As described above, the thermal behavior of the part A and the part B of the resin sheet is the part A. It is presumed that it occurs in a state where the temperature is uniformly applied not only to the surface of the part B but also to the inside. However, since there is no means for measuring the internal temperature, the surface temperature was defined.
In this invention, the surface temperature of the said site | part A and the said site | part B used the radiation thermometer installed in the vacuum forming machine. On the other hand, the adherend surface temperature was measured using a Wahl balance plate (101-4V-037, 043, 065, 082). The temp plate was affixed to the adherend before thermoforming, and the temperature reached by the adherend during thermoforming was determined by the change in the indicator after completion of thermoforming.

(Resin sheet with heat shrinkability)
The heat-shrinkable resin sheet used in the present invention (hereinafter abbreviated as “resin sheet S”) is a resin that exhibits spreadability by heating and can be formed into a film, and further has an orientation return strength inflection point. Furthermore, a thermoplastic resin sheet is preferable from the viewpoint of easy spreadability during vacuum forming.
The orientation return strength inflection point temperature in the present invention is the film temperature when heat is applied to the film from the outside, and when the film itself reaches this temperature, the stretched molecules start to contract, In the present invention, the orientation return strength inflection point temperature T is defined by the following method.

That is, the orientation return strength used in the present invention is measured according to ASTM D-1504. The orientation return strength is the force that the sheet shows when it is heated to restore its state before stretching, and the maximum stress at each measured temperature is divided by the cross-sectional area of the sheet. It becomes a parameter | index calculated | required as a value and shows the degree of molecular orientation of the stretched sheet.
In the present invention, the temperature T of the inflection point that becomes the convex of the right-upward graph showing the relationship between the orientation return strength and the heating temperature was obtained using the heat shrinkage stress measurement method. When there are a plurality of inflection points that are convex, the temperature of the inflection point in the highest temperature range is defined as the orientation return strength inflection point temperature T.
Specifically, D.N. Using an N-type stress tester, the voltage adjustment memory is set to 6, the heater temperature is raised in increments of 5 ° C., the orientation return stress at each measurement temperature is measured, and after the shrinkage stress is expressed, the orientation return strength and the heating temperature The inflection point temperature T of the graph showing the relationship with An example is shown in FIG. FIG. 16 is a graph when measuring a biaxially stretched PET sheet “Soft Shine X1130 (film thickness 125 μm)” (sheet S1 in Examples) manufactured by Toyobo Co., Ltd. The inflection point temperature T188 ° C. which is convex in the highest temperature range of the graph was defined as the orientation return strength inflection point temperature T of the sheet S1.

The resin is not particularly limited as long as it is a stretchable resin. For example, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, acrylic resins and polystyrene resins, nylon and vinylon Etc. can be used. Among them, a soft type in which a soft component such as a copolyester composed of an aromatic dicarboxylic acid component and a glycol component containing ethylene glycol and branched aliphatic glycol and / or alicyclic glycol is used as a part of the raw material component The polyester resin is preferable from the viewpoint of moldability.
As described above, the resin sheet having the orientation return strength inflection point is generally subjected to stretching treatment. As the stretching treatment method, the resin is melt-extruded into a sheet shape by an extrusion film forming method or the like, and then simultaneously biaxial. It is common to perform stretching or sequential biaxial stretching. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.

  The tenter method is advantageous in that a wide range of products can be obtained and productivity is high. There are no particular restrictions on the stretching conditions, etc., depending on the resin plasticity and the desired physical properties and moldability, but the surface magnification is usually 1.2 to 18 times, more preferably 2.0 to 15 times. . In the case of sequential stretching, the draw ratio in the flow direction is 1.2 to 5 times, preferably 1.5 to 4.0 times, and the draw ratio in the cross direction with respect to the flow direction is preferably 1.1 to 5 times. Is 1.5 to 4.5 times. The draw ratio in each direction of simultaneous biaxial stretching is 1.1 to 3.5 times, preferably 1.2 to 4.2 times.

  Specifically, although a stretched sheet such as a uniaxially stretched sheet or a biaxially stretched sheet can be used, a biaxially stretched sheet is preferable because it can maximize the effects of the present invention. In addition, if it is a simultaneous biaxially stretched sheet, the in-plane shrinkage rate is uniform, so an uneven design without distortion can be obtained. On the other hand, when strain is calculated in advance and uniaxially stretched or two-stage sequential biaxially stretched sheet is used There is also.

The stretched sheet is preferably heat-set so that the molecular orientation state by stretching can be maintained. The heat setting is usually carried out in an oven such as a tenter and is not particularly limited, but in the case of a polyester resin, it is preferably carried out under conditions of 150 to 240 ° C. for about 5 to 60 seconds. In particular, the polyester resin containing a glycol component, which is a soft component preferably used in the present invention, starts to relax the orientation of the sheet and generate drawdown before the temperature at which the unevenness appears unless heat setting is performed, and is sufficient in the molding region. There is a possibility that a decorative molded body having irregularities cannot be obtained.
In addition, since the resin sheet which maintained the molecular orientation by sufficient heat setting can express a larger unevenness | corrugation, it is still preferable. This is because the phenomenon of relaxation of oriented molecules proceeds rapidly (when the temperature of the resin sheet becomes equal to or higher than the heat setting temperature during vacuum forming), and therefore, in the sheet subjected to stretching and heat setting, part A and part B It is assumed that the difference in strength occurring at the orientation return strength inflection point temperature T becomes clearer. That is, it is presumed that the energy due to irradiation with electromagnetic waves, particularly infrared rays, can be effectively used for the expression of unevenness.

  The film thickness of the resin sheet S may be a film thickness usually used for a decorative sheet, but since the balance between infrared heating and heat dissipation is good, the film thickness of a thermoforming sheet normally used for vacuum forming is 0.04 mm. The above is preferable. Including the viewpoint of printability, 0.04 mm to 1.0 mm is preferable, and it is possible to obtain a roll shape capable of gravure printing. Therefore, 0.04 mm to 0.5 mm is more preferable, and 0.1 mm to 0.00 mm is more preferable. 3 mm.

(Ink containing metal oxide)
In the ink containing the metal oxide used in the present invention, specific examples of the metal oxide include zinc oxide, titanium oxide, and barium titanate. As zinc oxide or titanium oxide having crystal polymorphism, wurtzite zinc oxide and rutile titanium oxide are particularly desirable. What is necessary is just to use what is marketed as industrial products use, such as for coating materials and resin, or cosmetics, etc. as these metal oxides. In addition, if it is a metal oxide having a white particle size and a nano-size particle diameter, particularly when used in combination with infrared absorbing ink, infrared reflecting ink, or infrared transmitting ink, there is little loss of color. , Color development can be maintained.
The particle size of the metal oxide is preferably 5 to 500 nm, particularly preferably 10 to 200 nm. In addition, the mixing ratio of the metal oxide is not particularly limited, but if the amount is too small, it is difficult to obtain the effect derived from the metal oxide, while if the amount is too large, the infrared absorption ability or reflectivity of the metal oxide itself is higher. In particular, in order to control the difference in film thickness, the desired effect may be difficult to obtain, so 0.5 to 10% by mass is preferable with respect to the ink solid content, and 0.5 to 5% is preferable. Particularly preferred.

(When mixed and used)
When the ink containing the metal oxide is used as a mixed ink with an infrared absorbing ink, an infrared reflecting ink, or an infrared transmitting ink, the ink containing the adjusted metal oxide, the infrared absorbing ink, and the infrared reflecting ink, respectively. Or a mixed ink with an infrared transmitting ink may be mixed and used, or a metal oxide may be added to the infrared absorbing ink, the infrared reflecting ink, or the infrared transmitting ink. When mixing inks, dispersion stability may be impaired due to the influence of the solvent and additives used, so add a metal oxide to the infrared absorbing ink, infrared reflecting ink, or infrared transmitting ink. The method is preferred. By mixing and using, it is possible to improve infrared transmission and control the amount of infrared absorption or reflection without impairing the color of the infrared absorber or infrared reflecting material, so that the unevenness and sheet heating time can be controlled. Alternatively, infrared damage to the adherend can be reduced.

(When overprinting)
Moreover, you may perform overprinting with the ink containing these metal oxides and at least 1 ink chosen from the group which consists of infrared rays absorption ink, infrared rays reflection ink, and infrared rays transmission ink. In this case, overprinting may be performed along a pattern drawn with infrared absorbing ink, infrared reflecting ink, or infrared transmitting ink, or solid printing may be performed. In the case of overprinting along the pattern, it is possible to control the development of unevenness. On the other hand, in the case of solid printing, it is possible to control the sheet heating time or the infrared damage to the adherend in addition to the control of the unevenness.
When overprinting with infrared absorbing ink, it is preferable to perform overprinting so that the infrared absorbing ink layer is on the side irradiated with infrared rays, while when overprinting with infrared transmitting ink, the side irradiated with infrared rays is preferred. It is preferable to perform overprinting so that the ink containing the metal oxide comes to the surface.

(Infrared absorbing ink, infrared reflecting ink)
The infrared absorbing ink used in the present invention is an ink containing an infrared absorbing agent, and the infrared reflecting ink is an ink containing an infrared reflecting substance, both of which are used as security inks.
As described above, the infrared absorbing ink absorbs the irradiated infrared rays and generates heat. That is, when the resin sheet printed with the infrared absorbing ink is irradiated with infrared rays, only the amount of heat applied by the infrared irradiation is applied only to the portion printed with the infrared absorbing ink. On the other hand, the infrared reflecting ink is an ink containing an infrared reflecting material and reflects the irradiated infrared rays. When the resin sheet printed with infrared reflecting ink is irradiated with infrared rays from the resin sheet side (that is, the surface opposite to the printing surface of the resin sheet), the infrared rays that have passed through the resin sheet are reflected by the infrared reflecting ink. Thus, only the amount of heat applied by infrared irradiation is applied only to the print region where the infrared transmission region and the reflection region overlap. That is, since only the amount of heat applied by infrared irradiation is applied only to the portion printed with the infrared absorbing ink or the infrared reflecting ink, the surface temperature of the portion can be increased, and as a result, the infrared absorption of the resin sheet is increased. A temperature difference can be generated between a portion printed with ink and a portion not printed.

Specifically, the temperature of the resin sheet S itself is raised by infrared irradiation to obtain an elastic region suitable for thermoforming. At this time, if there is a portion provided with infrared absorbing ink or infrared reflecting ink on the resin sheet S, unevenness is generated due to the addition of heat, but the portion A at this time (a portion having a relatively high surface temperature) However, what is necessary is just to become the surface temperature more than the orientation return strength inflection point temperature T of the resin sheet S. Furthermore, the temperature difference between the part A and the part B is preferably 7 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 15 ° C. or higher because deeper irregularities can be imparted.
Infrared irradiation may be performed so that only part A has a surface temperature equal to or higher than the orientation return strength inflection point temperature T, and both part A and part B have surface temperatures equal to or higher than the orientation return strength inflection point temperature T. You may irradiate with infrared rays. In this case, deeper irregularities can be obtained in the latter case.

  Infrared absorbing ink is a material that is generally commercially available as an infrared absorbing agent, or various known infrared absorbing pigments that have a function of generating heat by absorbing wavelengths in the wavelength range of red, near infrared, and infrared laser light. Ink containing dyes and dyes is preferred. Specific examples of the infrared absorber include insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments. , Isoindolinone pigment, quinophthalone pigment, dyed lake pigment, azine pigment, nitroso pigment, nitro pigment, natural pigment, fluorescent pigment, inorganic pigment, carbon black, azo dye, metal complex azo dye, pyrazolone azo dye, anthraquinone Dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, carbon black, titanium black, phthalocyanine, naphthalocyanine, cyanine and other pigments and dyes, polymethine pigments and dyes, squarylium Red absorbers such as iodine, near infrared absorbents, infrared absorbents and the like.

  The infrared reflective material contained in the infrared reflective ink is a metal such as aluminum, gold, silver, copper, brass, titanium, chromium, nickel, nickel chrome, stainless steel, or antimony dichromate, and is in the form of powder or strips. Those are preferably used.

The particle size of the infrared absorber or infrared reflecting material is not particularly limited, and can be used without any particular problem as long as it is a range used as a normal ink.
On the other hand, as the ink density increases, the amount of heat applied to the portion A increases. Therefore, it is preferable to change the content appropriately depending on the desired degree of unevenness. On the other hand, if the concentration is too low, the amount of heat generated by infrared irradiation and the amount of infrared reflection are too small to form a recess, and if the concentration is too high, the amount of heat generated and the amount of infrared reflection are too large, causing tears and holes. Therefore, it is necessary to adjust appropriately so that the elastic modulus at the time of molding does not become 0.5 MPa or less as described later.

  The ink varnish is not particularly limited, and a known varnish resin or the like can be used. Examples of the varnish resin include acrylic resin, polyurethane resin, polyester resin, vinyl resin (vinyl chloride, vinyl acetate, vinyl chloride-vinyl acetate copolymer resin), chlorinated olefin resin, ethylene-acrylic resin, petroleum Well-known inks such as a resin-based resin and a cellulose derivative resin can be used.

  Moreover, according to the desired designability, a general-purpose color material may be contained in the infrared absorbing ink or the infrared reflecting ink. At this time, if a highly transparent material is used as the infrared absorber or infrared reflecting material, a general-purpose color material can be utilized, which is preferable. In addition, a pattern layer may be separately provided with ink containing a general-purpose color material by changing the plate. The color material used in this case is not particularly limited, but it is preferable to change the blending ratio as appropriate according to the purpose because the heat-absorbing color material can cause unevenness in the printed portion.

(Infrared transmitting ink)
Infrared transmissive ink is ink that transmits infrared rays and is used as security ink. In addition to the commercially available product, the infrared transmitting ink is 99.9% in the present invention, as measured by the ATR method of a Fourier transform infrared spectrophotometer (JASCO FTIR4200) at a heating infrared wave number of 3845 cm-1. Ink that transmits infrared rays at a transmittance (% T) or more is referred to as infrared transmitting ink.

As a method of providing a pattern on the resin sheet S with infrared absorbing ink or infrared reflecting ink, handwriting, coating, printing, and the like can be mentioned, but printing is preferable industrially. The method is not particularly limited, and examples thereof include gravure printing, offset printing, screen printing, ink jet printing, brush coating, roll coating, comma coating, rod gravure coating, and micro gravure coating. Of these, the gravure printing method is preferred.
The pattern is usually protected by the resin sheet S when it is provided between the resin sheet S and the adherend when the resin sheet S is attached to the adherend. This is preferable because it gives a beautiful appearance. Usually, as shown in FIG. 1, irradiation is performed so that infrared rays pass through the resin sheet and reach the infrared absorbing ink or infrared reflecting ink layer. In particular, when infrared reflection ink is used, unless such irradiation method is used, the infrared reflection ink reflects the infrared rays before passing through the resin sheet, that is, the infrared rays reach the printing portion of the resin sheet. Without being plasticized. Therefore, for example, when the infrared irradiation device of the vacuum forming apparatus to be used is installed between the holding (clamp) portion of the forming sheet and the adherend, that is, when the forming sheet is heated, When using a vacuum forming device designed to heat from the close contact surface with the body, the decorative part of the resulting decorative molded body is an ink layer containing a substance that reflects heat obtained from infrared rays It is preferable to mold in the order of / resin sheet S / adhered body.

(Other optional layers Adhesive layer)
In addition to the resin sheet S, the resin sheet S may have other layers as long as the effects of the present invention are not impaired. In particular, the adhesive layer and the pressure-sensitive adhesive layer are preferably provided from the viewpoint of construction or the like. The adhesive layer may be provided on the resin sheet S before the unevenness is generated, and may be irradiated with infrared rays to generate the unevenness, or may be provided later on the resin sheet S where the unevenness is generated.

  For example, as an adhesive, for example, acrylic resin, urethane resin, urethane-modified polyester resin, polyester resin, epoxy resin, ethylene-vinyl acetate copolymer resin (EVA), vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, natural Examples thereof include synthetic rubbers such as rubber, SBR, NBR, and silicone rubber. Solvent type or solventless type can be used.

  The pressure-sensitive adhesive is not particularly limited as long as it has tackiness at the temperature at which it is thermoformed. For example, solvents such as acrylic resin, isobutylene rubber resin, styrene-butadiene rubber resin, isoprene rubber resin, natural rubber resin, silicone resin, etc. Type adhesive, acrylic emulsion resin, styrene butadiene latex resin, natural rubber latex resin, styrene-isoprene copolymer resin, styrene-butadiene copolymer resin, styrene-ethylene-butylene copolymer resin, ethylene-vinyl acetate resin Solvent-free pressure-sensitive adhesives such as polyvinyl alcohol, polyacrylamide, and polyvinyl methyl ether.

  Particularly preferable examples of the adhesive include an acrylic resin and a polyurethane resin (for example, DIC Corporation: Thai hose, Krispon, Nippon Polyurethane Co., Ltd .: Nipponporan). Examples of the pressure-sensitive adhesive include solvent-based acrylic resin pressure-sensitive adhesives (for example, DIC Corporation: Quickmaster, Finetack, Soken Chemicals: SK Dyne) in terms of transparency and weather resistance. You may use these in mixture of 2 or more types.

Moreover, in the said adhesive, you may add a tackifier (tackifier) in order to adjust adhesive strength. The tackifier is not particularly limited. For example, rosin resin, rosin ester resin, terpene resin, terpene phenol resin, phenol resin, xylene resin, coumarone resin, coumarone indene resin, styrene resin, aliphatic petroleum resin, aromatic series Examples thereof include petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic hydrocarbon resins, and modified products, derivatives and hydrogenated products thereof.
The compounding quantity of a tackifier is not specifically limited, It is 100 mass parts or less with respect to 100 mass parts of total resin solid content, Preferably it is 50 mass parts or less.

  Further, even a cross-linked resin layer exhibiting plasticity at a temperature higher than that of the resin sheet S can be added as long as it has flexibility to follow the film thickness difference between the part A and the part B to some extent. is there. From this point of view, for the purpose of imparting characteristics such as friction resistance, scratch resistance, weather resistance, stain resistance, water resistance, chemical resistance, heat resistance, etc., it is partially crosslinked to such an extent that it does not interfere with spreadability. The surface protective layer may be provided. There are no particular limitations on the form of cross-linking, thermosetting reaction between isocyanate and hydroxyl group, thermosetting reaction between epoxy group and hydroxyl group, UV or thermosetting reaction using radical polymerization reaction of (meth) acryloyl group, silanol group or hydrolysis An existing reaction such as a hydrolytic condensation reaction of a functional silyl group may be used, but a thermosetting reaction between an isocyanate and a hydroxyl group is preferable because the crosslinking reaction can be promoted by using heat applied during thermoforming.

  The thickness of the adhesive layer or the pressure-sensitive adhesive layer is not particularly limited, but 2 to 100 μm is preferable from the viewpoint of coating workability, and 10 to 50 μm is particularly preferable from the viewpoint of adhesive strength and cost.

  The resin sheet S used in the present invention is not particularly limited as long as the film thickness as a whole including the ink layer or other layers is a film thickness usually used for a thermoforming sheet used for vacuum forming. Absent.

(Manufacturing method)
Specifically, the method for producing a decorative molded body having irregularities on the decorative surface of the present invention,
In a state of holding a resin sheet having heat shrinkage having a portion A provided with an ink containing a metal oxide,
The part A of the resin sheet and the part B adjacent to the part A in the same plane of the resin sheet have different surface temperatures of the part A and the part B, and at least the surface of the part A The step (1) of causing the film thickness difference between the part A and the part B by irradiating with infrared rays so that the temperature becomes a surface temperature equal to or higher than the orientation return strength inflection point temperature T of the resin sheet and the resin sheet A step (2) of adhering to the adherend by vacuum forming and integrating them.

  Specifically, an existing thermoforming machine used for a vacuum forming method, a compressed air vacuum forming method, or the like is used. In this invention, since the said process (1) and the said process (2) are performed continuously, the thermoforming machine which has an infrared irradiation means is preferable.

(Step 1 retention)
In the step 1, the held state is a state in which only a part of the outer periphery of the resin sheet S or the entire outer periphery is fixed as described above, that is, the surface of the sheet S to be attached to the adherend is a substrate or the like. Refers to an unsupported state. Specifically, there are a method of fixing a part of the resin sheet S by clamping or the like, and a method of clamping and fixing the entire periphery of the resin sheet S by a frame-shaped clamp. A method in which the entire periphery of the sheet is clamped and fixed by a frame-like clamp is preferable.
In addition, fixation here is possible also by preventing plasticization and shrinkage | contraction of the resin sheet S other than the method of clamping using jigs, such as a frame-shaped clamp. Specifically, by keeping the sheet temperature of the resin sheet S other than the surface to be adhered to the adherend, preferably the sheet outer peripheral portion below the glass transition temperature (hereinafter sometimes referred to as Tg), plasticization is prevented. Can also be fixed.

(Process 1 Infrared)
In the state where the resin sheet S is held, infrared irradiation is performed so that at least the surface temperature of the portion A is equal to or higher than the orientation return strength inflection point temperature T of the resin sheet. Is heated to a different surface temperature, and as a result, a difference in film thickness occurs between the part A and the part B.
The infrared rays irradiated at this time are not particularly limited as long as they are in the wavelength range from red to near infrared and infrared laser light. The upper limit of the amount of infrared irradiation is not particularly limited. However, if a very high amount of heat is applied, the resin sheet S may be deteriorated in rigidity, which may cause plasticization and breakage. The temperature of the highest part is preferably 0.5 MPa or more, more preferably 1 MPa or more as the value of the storage elastic modulus (E ′) of the dynamic viscoelasticity measurement determined by the JIS K7244-1 method. It is preferable to set the dose so that
In many cases, an existing thermoforming machine used for a vacuum forming method, a compressed air vacuum forming method or the like can be installed or externally provided with an infrared irradiation device as a heating means. Infrared irradiators need to irradiate wavelengths that can only be absorbed by heat-generating substances, so halogen heaters with short wavelength peaks in the mid-infrared to near-infrared region, short-wave heaters, carbon heaters, mid-infrared heaters, etc. Is preferably used. It is preferable that the peak of the main wavelength of these infrared irradiation devices is within 1.0 to 3.5 μm, an efficient film thickness can be generated, and the temperature difference between the endothermic material and other parts is not excessive. The range of 1.5 to 3.0 μm is more preferable because efficient production is possible.

In many cases, an infrared irradiation device installed as a heating means is temperature controlled. Therefore, in this invention, the infrared irradiation amount was evaluated from the surface temperature of the site | part A and the site | part B of the resin sheet S as a result of irradiating infrared rays instead of irradiation amount itself.
The minimum amount of infrared irradiation is set so that at least the surface temperature of the part A of the resin sheet S is equal to or higher than the orientation return strength inflection point temperature T of the resin sheet. On the other hand, if the temperature of the part A is too high, plasticization of the part A may progress and defects such as perforation may occur, so E ′ measured by the dynamic viscoelasticity measurement of the part A is 0. It is preferable to set the maximum amount of infrared irradiation so as to be 5 MPa or more, and more preferably 1.0 MPa or less.

  The infrared irradiation is preferably performed under vacuum. In normal vacuum forming, heating is performed by infrared irradiation under atmospheric pressure, but in the present invention, it has been found that a larger film thickness difference can be effectively expressed even at the same temperature by performing infrared irradiation in a vacuum state. . This is presumed to be because the wavelength of infrared rays efficiently reaches the resin sheet S and ink without being affected by heat conduction in the atmosphere. In other words, it is estimated that excess heat is hardly transmitted to the part A and the part B because there is almost no ambient heated air.

  Thereafter, unnecessary portions may be trimmed as necessary. The trimming method is not particularly limited, and the trimming method can be processed by a method of cutting with scissors or a cutter, a die cutting method, a laser cutting method, a water jet method, or a punching blade press method.

(Adherent)
The adherend used in the present invention is not particularly limited and may be anything as long as it is transparent or opaque and requires surface design. Specifically, various shapes such as resin, metal, glass, wood, and paper can be used, and the shapes may be decorated by a regular decoration method such as painting, plating, and scratching.
In the present invention, even when an adherend that is weak against infrared rays, that is, heat, is used, a good decorative molded body can be obtained.

  When the adherend is a resin molded body that is transparent or translucent, it can be seen through the resin sheet S, and a depth can be imparted to the color tone. A translucent or opaque resin molded body is usually obtained by molding a molding resin containing a colorant. The colorant is not particularly limited, and customary inorganic pigments, organic pigments, dyes, and the like used for coloring general thermoplastic resins can be used according to the intended design. For example, titanium oxide, titanium yellow, iron oxide, complex oxide pigment, ultramarine, cobalt blue, chromium oxide, bismuth vanadate, carbon black, ivory black, peach black, lamp black, bitumen, graphite, iron black, titanium black Inorganic pigments such as zinc oxide, calcium carbonate, barium sulfate, silica, talc; azo pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, anthraquinone pigments, isoindolinone pigments, isoindoline pigments, Organic pigments such as perylene pigments, perinone pigments, quinophthalone pigments, thioindigo pigments and diketopyrrolopyrrole pigments; metal complex pigments and the like. In addition, it is preferable to use one or two dyes mainly selected from the group of oil-soluble dyes.

  Also, the resin to be used is not particularly limited. For example, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate and polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene. Resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile-ethylene rubber-styrene resin, (meth) acrylic acid ester-styrene resin, styrene resin such as styrene-butadiene-styrene resin, ionomer resin, polyacrylonitrile, polyamide such as nylon Resin, ethylene-vinyl acetate resin, ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene-vinyl alcohol Resin, chlorine resin such as polyvinyl chloride and polyvinylidene chloride, fluorine resin such as polyvinyl fluoride and polyvinylidene fluoride, polycarbonate resin, modified polyphenylene ether resin, methylpentene resin, cellulose resin, etc., and olefin elastomer, chloride Thermoplastic elastomers such as vinyl elastomers, styrene elastomers, urethane elastomers, polyester elastomers and polyamide elastomers can be used. Further, two or more kinds of the exemplified resins may be mixed or multilayered. Furthermore, reinforcing additives such as inorganic fillers, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, lubricants, and other conventional additives may be added, and these additives are used alone. Or you may use 2 or more types together.

  Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “part” and “%” are based on mass.

(Resin sheet S)
As the resin sheet S, the following six sheets were used.
Sheet S1: Biaxially stretched PET sheet “Soft Shine X1130” manufactured by Toyobo Co., Ltd. (film thickness 125 μm)

(Orientation return strength inflection point temperature T measurement method)
The orientation return strength inflection point temperature T of the resin sheet S was performed as follows.
D. manufactured by NRI Corporation. An N-type stress tester was used, the voltage adjustment memory was set to 6, the heater temperature was increased in increments of 5 ° C., the orientation return stress at each measurement temperature was measured, and the orientation return strength inflection point temperature T was read. (See Figure 8)
result,
Sheet S1 orientation return strength inflection point temperature T: 188 ° C.

(Infrared absorbing ink, infrared reflecting ink, infrared transmitting ink)
The following inks were used for each of the infrared absorbing ink, the infrared reflecting ink, and the infrared transmitting ink.
Ink G1: Gravure printing ink “NH-NT” black (Z) manufactured by DIC Graphics, Inc. 40% by mass of carbon black based on the total solid content and used as an infrared absorbing ink.
Ink G2: Gravure printing ink “NH-LT” manufactured by DIC Graphics, Inc. SPHG Silver (D) An aluminum paste containing 13% by mass with respect to the total solid content and used as an infrared reflecting ink.
Ink G3: Ink for gravure printing “NH-NT” manufactured by DIC Graphics, Inc. Blue (A) Used as an infrared transmitting ink.
Ink G4: Ink for gravure printing “NH-NT” manufactured by DIC Graphics, Inc., white (A) Contains 50% by mass of titanium oxide based on the total solid content, and is used as an infrared absorbing ink.
Ink G5: Gravure printing ink “NH-NT” manufactured by DIC Graphics, Inc. (D) Contains no pigment. Used as medium ink.

(Ink containing metal oxide)
The following inks were used as inks containing metal oxides.
Ink MO1: Add 0.5 to 10% by mass of zinc oxide to ink G1.
Ink MO2: 0.5 to 10% by mass of titanium oxide is added to ink G3.
Ink MO3: 0.5 to 10% by mass of barium titanate is added to ink G3.
Ink MO4: 0.5 to 10% by mass of zinc oxide is added to ink G5.
Ink MO5: 0.5 to 10% by mass of titanium oxide added to ink G5.
Ink MO6: 0.5 to 10% by mass of barium titanate is added to ink G5.

(Picture printing method 1st edition)
A line having a width of about 2 cm was drawn on the resin sheet S by hand using the ink. (See Figure 9)

(Pattern printing method Overprint 2nd to 4th)
A pattern having a thickness of 5 to 7 μm was printed on the resin sheet using a gravure four-color printer using the ink. The same version was used.

(Method for confirming surface temperature of resin sheet, surface temperature arrival time, adherend temperature, and film thickness difference in step (1))
Using the resin sheet S1, a straight line having a width of about 2 cm was drawn using the ink in the flow direction (MD) and the cross direction (CD). Using the “NGF-0709 molding machine” manufactured by Fuse Vacuum Co., Ltd., which will be described later, the resin sheet S1 is straightened using a mid-infrared heater manufactured by Helius in a state where the periphery of the sheet is completely clamped under vacuum. Indirect heating was performed from the side opposite to the surface on which the film was drawn. The surface temperatures of the part A and the part B were measured using a radiation thermometer installed in a vacuum forming machine.
Further, the time required for the surface temperature of the resin sheet S1 to be used to rise to the heater set temperature (this temperature is usually a temperature for determining that thermoforming is possible) was measured.
The adherend surface temperature was measured using a Wahl balance plate (101-4V-037, 043, 065, 082). The temp plate was affixed to the adherend before thermoforming, and the temperature reached by the adherend during thermoforming was determined by the change in the indicator after completion of molding.
The film thickness of the resin sheet S1 before and after thermoforming was measured using a Mitutoyo Coolant Proof Micrometer MDC-25MJ.

(Vacuum forming simultaneous pasting method)
Thermoforming was performed using “NGF-0709 molding machine” manufactured by Fuse Vacuum Co., Ltd.
After completely fixing the periphery of the resin sheet S provided with the pattern by the above method with a clamp, the upper and lower boxes of the molding machine are closed, the inside of the box is almost completely vacuumed, and then a mid-infrared heater manufactured by Helius is used as the heater. Then, the resin sheet S is indirectly heated from the upper surface, and after the surface temperature of the resin sheet S rises to a set temperature, the table on which the adherend is placed is raised, and 0.2 MPa of compressed air is blown into the upper box, The resin sheet S was attached to an adherend and integrally formed. The distance between the heater and the resin sheet S at this time was 250 mm, and the adherend was a white ABS flat plate having a length of 295 mm, a width of 210 mm, and a thickness of 3 mm.
The heater is a system for starting the temperature rise before molding, but the final temperature of the heater was about 900 to 930 ° C.
Moreover, the measurement of whether the surface temperature of the resin sheet S reached preset temperature was performed with the FT-H30 radiation thermometer by Keyence Corporation.

Examples of using ink mixed with Examples 1-6 metal oxide
Using the ink for the resin sheet S1, according to the “pattern printing method 1st edition”, a 1-sheet sheet with a pattern layer was prepared. The ink types are shown in Tables 1 and 2. The sheet was thermoformed according to the vacuum forming simultaneous pasting method to obtain a decorative molded body. The set temperature of the heater was 193 ° C.
Table 1 shows the case where zinc oxide (ZnO in the table) is used as the metal oxide, Table 2 shows the case where titanium oxide (TiO2 in the table) is used, and Table shows the case where barium titanate (BaTiO3 in the table) is used. It is shown in 2. The reference example is a case where no metal oxide is used.

(Reference Examples 1-2)
Except having changed the kind of ink as described in Table 1 and Table 2, it carried out similarly to Examples 1-6, and obtained the decorative molded object. The results are shown in Tables 1 and 2.
From the results in Table 1, it was confirmed that the zinc oxide alone can exhibit unevenness (Example 1) and can be controlled to slightly relax the molding temperature arrival time and the film thickness difference of the infrared absorbing ink.
In addition, from the results in Table 2, titanium oxide and barium titanate exhibit unevenness even when used alone (Examples 3 and 5). In particular, when used by mixing with an infrared transmitting ink, It was confirmed that the surface temperature of the adherend could be controlled to be relaxed (120 ° C. → 110 ° C.). (Examples 4 and 6)

(Examples 7-9 Example of overprinting of metal oxide ink and at least one ink selected from the group consisting of infrared absorbing ink, infrared reflecting ink, and infrared transmitting ink)
Using the ink for the resin sheet S1, a two-sheet sheet with a pattern layer was prepared according to the “pattern printing method 2nd edition”. The ink types are shown in Tables 3 and 4. The sheet was thermoformed according to the vacuum forming simultaneous pasting method to obtain a decorative molded body. The set temperature of the heater was 193 ° C. Reference Examples 3 to 4 are cases where no metal oxide is used. The results are shown in Tables 3 and 4.

(Reference Examples 3-4)
Except having changed the kind of ink as described in Table 1 and 2, it carried out similarly to Examples 7-9, and obtained the decorative molded object. The results are shown in Table 4. Thereby, it was confirmed that zinc oxide can be controlled so as to slightly relax the molding temperature arrival time and the film thickness difference of the infrared absorbing ink and to increase the surface temperature of the adherend. Further, it was confirmed that titanium oxide and barium titanate can be controlled to relax the surface temperature of the adherend (121 ° C. → 110 ° C. in Example 8 and 110 ° C. in Example 9).

(Examples 10 to 18 metal oxide amount of ink containing metal oxide)
Resin sheet S1 uses ink G1 and ink MO4 (however, the amount of zinc oxide is set to 0.5, 5, and 10% by mass), and has two image layers according to the above “image printing method 2 plate” Created a sheet. The sheet was thermoformed according to the vacuum forming simultaneous pasting method to obtain a decorative molded body. The set temperature of the heater was 193 ° C.
The molding conditions are
-Adhering body temperature shall be 65-117 degreeC or less, More desirably, it shall be 70-110 degreeC or less.
-Concavities and convexities (film thickness difference) are in the range of 40 to 105 μm.
The molding temperature (193 ° C.) arrival time is in the range of 50 to 130 seconds, and more preferably in the range of 60 to 120 seconds.
It was a goal.

  As a result, the zinc oxide was able to be 67 seconds within the desired time for reaching the molding temperature by using the ink added with 5% by mass. (See Table 5, Example 11) In addition, the temperature of the adherend rose to 71 ° C., which was within the target range, and a sufficient effect was obtained by adding 5% by mass of zinc oxide.

  Table 6 shows an example in which 0.5 to 10% by mass of titanium oxide was added. When titanium oxide is added in an amount of 0.5 to 10% by mass, the surface temperature of the adherend becomes 110 ° C., regardless of the amount added, the surface temperature of the adherend is lowered, and deformation due to overheating of the adherend is alleviated. The effect to do was obtained. (See Table 6 Examples 13-15)

  Table 7 shows an example in which 0.5 to 10% by mass of barium titanate is added. Barium titanate, like titanium oxide, could reduce the surface temperature of the adherend and alleviate deformation due to overheating of the adherend regardless of the amount added. (See Table 7 Examples 16-18)

: It is a figure which shows the specific 1 aspect which showed the state which irradiates infrared rays using the infrared heater to the resin sheet which has the heat shrinkability printed by the infrared absorption ink. : It is the figure which showed the state of the resin sheet after irradiating infrared rays in the state holding the said resin sheet. : It is the figure which showed the state which affixed and integrated the resin sheet of FIG. 2 on the to-be-adhered body by the vacuum forming method. : An example of the pattern print layer used in the present invention. The black part is the printed layer. (stripe) : An example of the pattern print layer used in the present invention. The black part is the printed layer. (Dot) : An example of the pattern print layer used in the present invention. The black part is the printed layer. (Geometric pattern) : An example of the pattern print layer used in the present invention. The black part is the printed layer. (grain) : Toyobo Co., Ltd. biaxially stretched PET sheet “Soft Shine X1130 (film thickness 125 μm)” (Sheet S1 in Examples) is a graph of orientation return strength and temperature measured in accordance with ASTM D-1504. . It is a schematic diagram of the pattern printing 1 plate used in the Example. A part is an ink hand-drawn part.

1: Infrared heater 2: Infrared 3: Resin sheet having heat shrinkability
4: Infrared absorbing ink printing part 5: Mixed ink printing part of metal oxide ink and infrared absorbing ink 6: Color ink printing part 7 (does not absorb infrared rays) 7: Substrate

Claims (4)

In a state of holding a resin sheet having heat shrinkage having a portion A provided with an ink containing a metal oxide,
The part A of the resin sheet and the part B adjacent to the part A in the same plane of the resin sheet have different surface temperatures of the part A and the part B, and at least the surface of the part A A step (1) of causing a film thickness difference between the part A and the part B by irradiating with infrared rays so that the temperature becomes a surface temperature equal to or higher than the orientation return strength inflection point temperature T of the resin sheet;
And a step (2) of attaching and integrating the resin sheet to an adherend by a vacuum forming method, and a method for producing a decorative molded body having irregularities on a decorative surface. The method for producing a decorative molded body having irregularities on the decorative surface according to claim 1, wherein the ink containing the metal oxide is a mixed ink with an infrared absorbing ink, an infrared reflecting ink, or an infrared transmitting ink. The said site | part A provides overprinting of the ink containing a metal oxide, and at least 1 ink chosen from the group which consists of infrared rays absorption ink, infrared rays reflection ink, and infrared rays transmission ink. A method for producing a decorative molded body having irregularities on its decorative surface. The manufacturing method of the decorative molded object in any one of Claims 1-3 whose resin sheet which has the said heat-shrinkability is biaxially-stretchable polyethylene terephthalate.

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